CN109476575A

CN109476575A - Compound, resin, composition and corrosion-resisting pattern forming method and circuit pattern forming method

Info

Publication number: CN109476575A
Application number: CN201780045244.3A
Authority: CN
Inventors: 越后雅敏
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2016-07-21
Filing date: 2017-07-21
Publication date: 2019-03-15
Also published as: JP2022033731A; WO2018016640A1; KR20190033537A; JP7110979B2; JPWO2018016640A1; JP7283515B2; TW201815738A

Abstract

Following formula (0) compound represented.(0)(R^Y: the aryl of hydrogen atom, the alkyl of carbon number 1~30 or carbon number 6~30, R^Z: the group or singly-bound, R of the N valence of carbon number 1~60^T: optionally hydrogen atom group replaced the group containing vinyl phenylmethyl (alkyl, aryl, alkenyl, alkoxy optionally include ehter bond, ketonic bond or ester bond) of the alkyl of the carbon number 1~30 with substituent group, the aryl of the optionally carbon number 6~30 with substituent group, the alkenyl of the optionally carbon number 2~30 with substituent group, the alkoxy of the optionally carbon number 1~30 with substituent group, halogen atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl, R^TAt least one be hydroxyl hydrogen atom group replaced the group containing vinyl phenylmethyl.X: oxygen atom, sulphur atom are no bridge joint, the integer (integer that at least one is 1~9) of m:0~9, the integer of N:1~4, the integer of r:0~2).

Description

Compound, resin, composition and corrosion-resisting pattern forming method and circuit pattern are formed Method

Technical field

The present invention relates to specific structure compound, resin and contain their compositions.In addition, being related to using this The pattern forming method (corrosion-resisting pattern forming method and circuit pattern forming method) of composition.

Background technique

In the manufacture of semiconductor devices, the microfabrication based on the photoetching for using photo anti-corrosion agent material is carried out, but close Nian Lai, along with the highly integrated and high speedization of LSI, it is desirable that the further miniaturization based on pattern rule.In addition, resist pattern The light source of the photoetching used when case formation is from krf excimer laser (248nm) short wavelengthization to arf excimer laser (193nm), it is also contemplated that the importing of extreme ultraviolet (EUV, 13.5nm).

However, in photoetching using previous macromolecular anticorrosive additive material, molecular weight greatly to 10,000~100,000 or so, Molecular weight distribution is also wide, therefore, generates roughness in patterned surfaces, the control of pattern dimension becomes difficult, and there are limits for miniaturization.

Therefore, so far, in order to provide resolution ratio higher corrosion-resisting pattern, various low molecular weight resist materials are proposed Material.Low molecular weight anticorrosive additive material since molecular dimension is small, can expect to provide high resolution, roughness small against corrosion Pattern.

Currently, as such low molecule system anticorrosive additive material, it is known to a variety of.For example, proposing using low molecular weight Multicore polyphenolic substance is (literary referring for example to following patents as the minus radiation-sensitive composition of the alkali developable of principal component Offer 1 and patent document 2), the candidate as the low molecular weight anticorrosive additive material with high-fire resistance, it is also proposed that use low molecule Cyclic annular polyphenolic substance is measured as the minus radiation-sensitive composition of the alkali developable of principal component (referring for example to following patents Document 3 and non-patent literature 1).In addition, the basic compound as anticorrosive additive material, it is known that polyphenolic substance is low molecular weight And high-fire resistance can be assigned, resolution ratio, the roughness for improving corrosion-resisting pattern are useful (referring for example to following non-special Sharp document 2).

It is excellent as elching resistant, simultaneously dissolve in solvent and can apply wet process material, the inventors of the present invention proposition The anti-corrosion agent composition of compound containing specific structure and organic solvent (referring for example to following patent documents 4).

In addition, corrosion-resisting pattern falls after leading to the problem of resolution ratio or development if promoting the miniaturization of corrosion-resisting pattern The problems such as collapsing, therefore, it is desirable to the filmings of resist.However, becoming difficult to obtain if only carrying out the filming of resist The film thickness of sufficient corrosion-resisting pattern for substrate processing.Therefore, the technique for not only needing corrosion-resisting pattern, but also be also required to anti- Production resist lower membrane and the resist lower membrane also have between erosion agent and the semiconductor substrate processed adds as substrate The technique of the function of the mask in working hour.

Now, as the resist lower membrane of this technique, it is known to various substances.For example, as realization and in the past The photoetching of the fast selection ratio different and with the dry etching rate close with resist of resist lower membrane of etching speed use The substance of resist lower membrane proposes multilayer resist technique lower layer's film formation material containing resin component and solvent, The resin component at least has and is detached from end group by energy as defined in applying and generates the substituent group of sulfonic acid moieties (referring for example to following patent documents 5).In addition, as the selection ratio realized compared with resist with small dry etching rate The substance of photoetching resist lower membrane proposes the resist lower layer membrane material comprising the polymer with specific repetitive unit Expect (referring for example to following patent documents 6).In turn, it is selected compared with semiconductor substrate with small dry etching rate as realization The substance of the photoetching of ratio resist lower membrane proposes the repetitive unit comprising making acenaphthylene class and has substituted or non-substituted The resist lower layer membrane material of polymer made of the repetitive unit copolymerization of hydroxyl (referring for example to following patent documents 7).

On the other hand, commonly known to pass through original as the material with high elching resistant in this resist lower membrane The amorphous carbon lower membrane that material is formed using the CVD of methane gas, ethane gas, acetylene gas etc..However, from technologic sight Point sets out, it is desirable that the resist lower layer membrane material of resist lower membrane can be formed using wet process such as spin-coating method, silk-screen printings Material.

In addition, and heat resistance excellent as elching resistant is high, the material that dissolves in solvent and can apply wet process, The lower layer film for lithography that inventor etc. proposes the compound containing specific structure and organic solvent formed composition (referring for example to Following patent documents 8).

It should be noted that the formation of the middle layer used in the formation in the resist lower membrane in 3 layer process Method, such as forming method (referring for example to following patent documents 9), the CVD forming method of silicon nitride film of known silicon nitride film (referring for example to following patent documents 10).In addition, the intermediate layer material as 3 layer process, it is known to include silsesquioxane The material of the silicon compound on basis (referring for example to following patent documents 11 and 12).

In turn, composition is formed as optical component, proposes many kinds of substance.For example, acrylic resin can be enumerated (referring for example to following patent documents 13~14).

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2005-326838 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2008-145539 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2009-173623 bulletin

Patent document 4: International Publication No. 2013/024778

Patent document 5: Japanese Unexamined Patent Publication 2004-177668 bulletin

Patent document 6: Japanese Unexamined Patent Publication 2004-271838 bulletin

Patent document 7: Japanese Unexamined Patent Publication 2005-250434 bulletin

Patent document 8: International Publication No. 2013/024779

Patent document 9: Japanese Unexamined Patent Publication 2002-334869 bulletin

Patent document 10: International Publication No. 2004/066377

Patent document 11: Japanese Unexamined Patent Publication 2007-226170 bulletin

Patent document 12: Japanese Unexamined Patent Publication 2007-226204 bulletin

Patent document 13: Japanese Unexamined Patent Publication 2010-138393 bulletin

Patent document 14: Japanese Unexamined Patent Publication 2015-174877 bulletin

Non-patent literature

Non-patent literature 1:T.Nakayama, M.Nomura, K.Haga, M.Ueda:Bull.Chem.Soc.Jpn., 71, 2979(1998)

Non-patent literature 2: ridge rugged inferior 22 people of letter " new development of photo anti-corrosion agent material exploitation " CMC Corporation Publication, in September, 2009, p.211-259

Summary of the invention

Problems to be solved by the invention

Although forming composition and downwards with film as described above, proposing a variety of photoetching towards resist purposes in the past The photoetching of tunic purposes film forms composition, but they all do not have can be suitable for the wet types work such as spin-coating method, silk-screen printing The high solvent dissolubility of skill, nor heat resistance and elching resistant are taken into account with high level, it is desirable that the exploitation of new material.Separately Outside, the exploitation for being suitable for obtaining the new material of the permanent film against corrosion of alkali-developable, luminous sensitivity and excellent in resolution is also required.

In addition, proposed a variety of compositions towards optical component in the past, but heat resistance, transparent can not be taken into account with high level Property and refractive index, it is desirable that the exploitation of new material.

The present invention makes in order to solve the above problems, it is intended that being related to: for the dissolubility of safety solvent High, heat resistance and the good compound of elching resistant and resin and using its composition and use the anti-of aforementioned composition Lose pattern forming method and circuit pattern forming method.

The solution to the problem

The inventors of the present invention further investigate repeatedly in order to solve aforementioned problems, as a result, it has been found that: by using with specific structure Compound or resin, can solve aforementioned problems, so far complete the present invention.

That is, the present invention is as described below.

<1>a kind of following formula (0) compound represented.

(in formula (0), R^YFor the aryl of hydrogen atom, the alkyl of carbon number 1~30 or carbon number 6~30,

R^ZFor the group or singly-bound of the N valence of carbon number 1~60,

R^TBe each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally have the carbon number 6 of substituent group~ 30 aryl, optionally the carbon number 2~30 with substituent group alkenyl, optionally have substituent group carbon number 1~30 alkoxy, halogen Plain atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom replaced the group containing vinyl phenylmethyl Group, aforesaid alkyl, aforesaid aryl, foregoing alkenyl, aforementioned alkoxy optionally include ehter bond, ketonic bond or ester bond, herein, R^T's At least one is hydrogen atom group replaced the group containing vinyl phenylmethyl of hydroxyl,

X expression oxygen atom, sulphur atom is no bridge joint,

M is each independently 0~9 integer, herein, the integer that at least one of m is 1~9,

N be 1~4 integer, N be 2 or more integer when, the structural formula in N number of [] is optionally identical or different,

R is each independently 0~2 integer.)

<2>compound according to aforementioned<1>, wherein previously described formula (0) compound represented is shown in following formula (1) Compound.

(in formula (1), R⁰With aforementioned R^YFor identical meanings,

R¹For the group or singly-bound of the n valence of carbon number 1~60,

R²~R⁵It is each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally with the carbon number of substituent group 6~30 aryl, optionally the carbon number 2~30 with substituent group alkenyl, optionally have substituent group carbon number 1~30 alcoxyl Base, halogen atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom by the group containing vinyl phenylmethyl Replaced group, aforesaid alkyl, aforesaid aryl, foregoing alkenyl, aforementioned alkoxy optionally include ehter bond, ketonic bond or ester bond, this Place, R²~R⁵At least one be hydroxyl hydrogen atom group replaced the group containing vinyl phenylmethyl,

m²And m³It is each independently 0~8 integer,

m⁴And m⁵It is each independently 0~9 integer,

Wherein, m²、m³、m⁴And m⁵It is not simultaneously 0,

N and aforementioned N are identical meanings, and herein, when the integer that n is 2 or more, the structural formula in n [] is optionally identical or not Together,

p²~p⁵It is identical meanings with aforementioned r.)

<3>compound according to aforementioned<1>, wherein previously described formula (0) compound represented is shown in following formula (2) Compound.

(in formula (2), R^0AWith aforementioned R^YFor identical meanings,

R^1AFor the n of carbon number 1~60^AThe group or singly-bound of valence,

R^2ABe each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally have the carbon number 6 of substituent group~ 30 aryl, optionally the carbon number 2~30 with substituent group alkenyl, optionally have substituent group carbon number 1~30 alkoxy, halogen Plain atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom replaced the group containing vinyl phenylmethyl Group, aforesaid alkyl, aforesaid aryl, foregoing alkenyl, aforementioned alkoxy optionally include ehter bond, ketonic bond or ester bond, herein, R^2A's At least one is hydrogen atom group replaced the group containing vinyl phenylmethyl of hydroxyl,

n^AIt is identical meanings, herein, n with aforementioned N^AFor 2 or more integer when, n^AStructural formula in a [] it is optionally identical or Difference,

X^AIt is identical meanings with aforementioned X,

m^2AIt is each independently 0~7 integer, wherein at least one m^2AFor 1~7 integer,

q^AIt is each independently 0 or 1.)

<4>compound according to aforementioned<2>, wherein previously described formula (1) compound represented is following formula (1-1) institute The compound shown.

(in formula (1-1), R⁰、R¹、R⁴、R⁵、n、p²~p⁵、m⁴And m⁵With it is aforementioned be identical meanings,

R⁶~R⁷It is each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally with the carbon number of substituent group Alkenyl, halogen atom, nitro, amino, carboxylic acid group, the sulfydryl of 6~30 aryl, the optionally carbon number 2~30 with substituent group,

R¹⁰~R¹¹It is each independently hydrogen atom or the group containing vinyl phenylmethyl,

Herein, R¹⁰~R¹¹At least one be the group containing vinyl phenylmethyl,

m⁶And m⁷It is each independently 0~7 integer,

Wherein, m⁴、m⁵、m⁶And m⁷It is not simultaneously 0.)

<5>compound according to aforementioned<4>, wherein previously described formula (1-1) compound represented is following formula (1-2) Compound represented.

(in formula (1-2), R⁰、R¹、R⁶、R⁷、R¹⁰、R¹¹、n、p²~p⁵、m⁶And m⁷With it is aforementioned be identical meanings,

R⁸~R⁹With aforementioned R⁶~R⁷For identical meanings,

R¹²~R¹³With aforementioned R¹⁰~R¹¹For identical meanings,

m⁸And m⁹It is each independently 0~8 integer,

Wherein, m⁶、m⁷、m⁸And m⁹It is not simultaneously 0.)

<6>compound according to aforementioned<3>, wherein previously described formula (2) compound represented is following formula (2-1) institute The compound shown.

(in formula (2-1), R^0A、R^1A、n^A、q^AAnd X^AIt is identical meanings with explanation in previously described formula (2).

R^3ABe each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally have the carbon number 6 of substituent group~ Alkenyl, halogen atom, nitro, amino, carboxylic acid group, the sulfydryl of 30 aryl, the optionally carbon number 2~30 with substituent group,

R^4AIt is each independently hydrogen atom or the group containing vinyl phenylmethyl,

Herein, R^4AAt least one be the group containing vinyl phenylmethyl,

m^6AIt is each independently 0~5 integer.)

<7>a kind of resin is using compound described in aforementioned<1>as obtained from monomer.

<8>resin according to aforementioned<7>, with structure shown in following formula (3).

(in formula (3), L be the alkylidene of the optional carbon number 1~30 with substituent group, the carbon number 6 optionally with substituent group~ The alkylene oxide group or singly-bound of 30 arlydene, the optionally carbon number 1~30 with substituent group, it is aforementioned alkylidene, aforementioned arlydene, preceding Stating alkylene oxide group optionally includes ehter bond, ketonic bond or ester bond,

R⁰With aforementioned R^YFor identical meanings,

R¹For the group or singly-bound of the n valence of carbon number 1~60,

R²~R⁵It is each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally with the carbon number of substituent group 6~30 aryl, optionally the carbon number 2~30 with substituent group alkenyl, optionally have substituent group carbon number 1~30 alcoxyl Base, halogen atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom by the group containing vinyl phenylmethyl Replaced group, aforesaid alkyl, aforesaid aryl, foregoing alkenyl, aforementioned alkoxy optionally include ehter bond, ketonic bond or ester bond,

m²And m³It is each independently 0~8 integer,

m⁴And m⁵It is each independently 0~9 integer,

Wherein, m²、m³、m⁴And m⁵It is not simultaneously 0, R²~R⁵At least one be hydroxyl hydrogen atom by contain ethenylphenyl Group replaced the group of methyl.

p²~p⁵It is identical meanings with aforementioned r.)

<9>resin according to aforementioned<7>, with structure shown in following formula (4).

(in formula (4), L be the alkylidene of the optional carbon number 1~30 with substituent group, the carbon number 6 optionally with substituent group~ The alkylene oxide group or singly-bound of 30 arlydene, the optionally carbon number 1~30 with substituent group, it is aforementioned alkylidene, aforementioned arlydene, preceding Stating alkylene oxide group optionally includes ehter bond, ketonic bond or ester bond,

R^0AWith aforementioned R^YFor identical meanings,

R^1AFor the n of carbon number 1~30^AThe group or singly-bound of valence,

X^AIt is identical meanings with aforementioned X,

m^2AIt is each independently 0~7 integer, wherein at least one m^2AFor 1~6 integer,

q^AIt is each independently 0 or 1.)

<10>a kind of composition, contains: selected from the compound as described in any one of aforementioned<1>~<6>and aforementioned<7> One or more of the group of the composition of resin described in any one of~<9>.

<11>composition according to aforementioned<10>, also contains solvent.

<12>composition according to aforementioned<10>or aforementioned<11>, also contains acid agent.

<13>composition according to any one of aforementioned<10>~<12>, also contains crosslinking agent.

<14>composition according to aforementioned<13>, wherein aforementioned crosslinking agent is selected from by phenolic compounds, epoxy compound Object, cyanate esters, amino-compound, benzoxazine compound, melamine compound, guanamines compound, glycoluril chemical combination It is at least one kind of in the group that object, carbamide compound, isocyanate compound and azido compound form.

<15>composition according to aforementioned<13>or<14>, wherein aforementioned crosslinking agent has at least one allyl.

<16>composition according to any one of aforementioned<13>~<15>, wherein relative to containing selected from by it is aforementioned< 1>~any one of<6>described in resin composition described in any one of compound and aforementioned<7>~<9>group in a kind with On composition 100 mass parts of total quality, the content of aforementioned crosslinking agent is 0.1~100 mass parts.

<17>composition according to any one of aforementioned<13>~<16>, also contains crosslinking accelerator.

<18>composition according to aforementioned<17>, wherein aforementioned crosslinking accelerator be selected from by amine, imidazoles, It is at least one kind of in organic phosphine and the group of lewis acid composition.

<19>composition according to aforementioned<17>or<18>, wherein relative to containing selected from by aforementioned<1>~<6> Any one of described in compound and one or more of the group of resin composition described in any one of aforementioned<7>~<9>combination 100 mass parts of total quality of object, the content of aforementioned crosslinking accelerator are 0.1~5 mass parts.

<20>composition according to any one of aforementioned<10>~<19>, also contains radical polymerization initiator.

<21>composition according to any one of aforementioned<10>~<20>, wherein aforementioned radical polymerization initiator For in the group being made of ketone system Photoepolymerizationinitiater initiater, organic peroxide system polymerization initiator and azo system polymerization initiator It is at least one kind of.

<22>composition according to any one of aforementioned<10>~<21>, wherein relative to containing selected from by it is aforementioned< 1>~any one of<6>described in resin composition described in any one of compound and aforementioned<7>~<9>group in a kind with On composition 100 mass parts of total quality, the content of aforementioned radical polymerization initiator is 0.05~25 mass parts.

<23>composition according to any one of aforementioned<10>~<22>, is used for photoetching and is formed with film.

<24>composition according to any one of aforementioned<10>~<22>, is used for permanent film against corrosion and is formed.

<25>composition according to any one of aforementioned<10>~<22>, is used for optical component and is formed.

<26>a kind of corrosion-resisting pattern forming method comprising following process: using composition described in aforementioned<23>in base After forming photoresist layer on plate, predetermined region illumination radiation line to aforementioned photoresist layer and the process developed.

<27>a kind of corrosion-resisting pattern forming method comprising following process: using composition described in aforementioned<23>in base Lower membrane is formed on plate, after forming at least 1 layer of photoresist layer in aforementioned lower membrane, to the regulation of aforementioned photoresist layer Area illumination radiation simultaneously develops.

<28>a kind of circuit pattern forming method comprising following process: using composition described in aforementioned<23>in base Form lower membrane on plate, form interlayer film in aforementioned lower membrane using interlayer film material against corrosion, in the foregoing between tunic It is upper form at least 1 layer of photoresist layer after, predetermined region illumination radiation line to aforementioned photoresist layer simultaneously develops, from And corrosion-resisting pattern is formed, later, aforementioned interlayer film is etched using aforementioned corrosion-resisting pattern as mask, by gained middle layer Film figure is etched aforementioned lower membrane as etching mask, carries out using gained lower layer film figure as etching mask to substrate Thus etching forms pattern in substrate.

<29>a kind of following formula (5) compound represented.

(in formula (5), R^5AFor the N of carbon number 1~60^BThe group or singly-bound of valence,

M¹⁰It is each independently 1~3 integer,

N^BFor 1~4 integer, N^BFor 2 or more integer when, N^BStructural formula in a [] is optionally identical or different.)

The effect of invention

In accordance with the invention it is possible to provide, heat resistance high for the dissolubility of safety solvent and the good chemical combination of elching resistant Object and resin and using its composition and formed using the corrosion-resisting pattern forming method and circuit pattern of aforementioned composition Method.

Specific embodiment

Hereinafter, embodiments of the present invention will be described.It should be noted that the following embodiments and the accompanying drawings is for illustrating Example of the invention, the present invention are not limited only to the embodiment.The compound of present embodiment is to change shown in aftermentioned formula (0) It closes object or the compound will be worked as resin obtained from monomer.The compound and resin of present embodiment can be applicable in wet type Technique, for forming heat resistance, the photoresist and photoresist excellent for the dissolubility and elching resistant of safety solvent Agent with lower membrane be it is useful, can be used for forming useful composition with film to photoetching and be formed using the pattern of the composition Method etc..In addition, sensitivity, excellent in resolution when the compound and resin of present embodiment are for photosensitive material, for Formed maintain high-fire resistance while, it is further compatible with miscellaneous organic solvents, other compounds, resin component and additive The excellent permanent film against corrosion of property is useful.

Combinations of the above object has used the compound or resin that heat resistance is high, solvent solubility is also high, with specific structure, Therefore, the deterioration of film when high-temperature baking is suppressed, and can be formed also excellent to the elching resistant of oxygen plasma etch etc. Resist and lower membrane.In addition, in the case where forming lower membrane, it is also excellent with the adaptation of resist layer, therefore, it can be formed excellent Different corrosion-resisting pattern.

In turn, above-mentioned composition is since refractive index is high and by from low temperature to and the heat treatment of the wide scope of high temperature Color is inhibited, and therefore, it is also useful for forming composition as various optics.

" compound and resin "

The compound of present embodiment is indicated with following formula (0).

R^ZFor the group or singly-bound of the N valence of carbon number 1~60,

X expression oxygen atom, sulphur atom is no bridge joint,

R is each independently 0~2 integer.)

R^YFor the aryl of hydrogen atom, the alkyl of carbon number 1~30 or carbon number 6~30.Straight-chain, branched can be used in alkyl Or cricoid alkyl.R^YFor the virtue of hydrogen atom, the straight-chain of carbon number 1~30, branched or cricoid alkyl or carbon number 6~30 Base, therefore heat resistance is relatively high, improves solvent solubility.

In addition, R^YWhen for the aryl of the straight-chain of carbon number 1~30, branched or cricoid alkyl or carbon number 6~30, in turn It is preferred from the viewpoint of inhibiting the oxygenolysis of this compound, inhibiting coloring, heat resistance height, improve solvent solubility.

R^zFor the group or singly-bound of the N valence of carbon number 1~60, each aromatic rings is by the R^zAnd it is bonded.The integer that N is 1~4, N For 2 or more integer when, the structural formula in N number of [] is optionally identical or different.It should be noted that for the base of aforementioned N valence Group: indicating the alkyl of carbon number 1~60 in N=1, and the alkylidene of carbon number 1~30 is indicated in N=2, indicates carbon number in N=3 2~60 three base of alkane indicates four base of alkane of carbon number 3~60 in N=4.As the group of aforementioned N valence, for example, tool There is the group of straight-chain alkyl, branched alkyl or alicyclic type hydrocarbon.It herein, also include bridge joint about aforementioned alicyclic type hydrocarbon Alicyclic type hydrocarbon.In addition, the alkyl of aforementioned N valence optionally has the fragrance of alicyclic type hydrocarbon, double bond, hetero atom or carbon number 6~60 Race's group.

R^TBe each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally have the carbon number 6 of substituent group~ 30 aryl, optionally the carbon number 2~30 with substituent group alkenyl, optionally have substituent group carbon number 1~30 alkoxy, halogen Plain atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom replaced the group containing vinyl phenylmethyl Group, aforesaid alkyl, aforesaid aryl, foregoing alkenyl, aforementioned alkoxy optionally include ehter bond, ketonic bond or ester bond.In addition, R^T's At least one is hydrogen atom group replaced the group containing vinyl phenylmethyl of hydroxyl.It should be noted that aforementioned alkane Base, alkenyl and alkoxy are optionally straight-chain, branched or cricoid group.

Herein, " group containing vinyl phenylmethyl " is the group with vinyl phenylmethyl, for example, Vinyl phenylmethyl and vinyl phenylmethyl methyl, vinyl phenylmethyl phenyl etc., oxygen atom, alkylidene, sub- benzene The group that base, oxygroup alkylidene etc. are replaced by vinyl phenylmethyl.

X indicates oxygen atom, sulphur atom or is no bridge joint.In the case that X is oxygen atom or sulphur atom, has and show high-fire resistance Tendency, therefore it is preferred that, more preferably oxygen atom.From the viewpoint of dissolubility, X is preferably without bridge joint.In addition, m is respectively independent The integer that ground is 0~9, the integer that at least one of m is 1~9.

In formula (0), position shown in naphthalene structure is as follows: it is single ring architecture in r=0, is bicyclic ring structures in r=1, It is tricyclic structure when r=2.R is each independently 0~2 integer.Above-mentioned m determines its numerical value according to the ring structure determined by r Range.

Previously described formula (0) has high resistance to although compound represented is relatively low molecular weight because of the rigidity of its structure It is hot, therefore, also it can be used under the conditions of high-temperature baking.In addition, having tertiary carbon or quaternary carbon in molecule, crystallinity is suppressed, Can be suitable as can be used in photoetching that photoetching is manufactured with film with film formed composition come using.

In addition, previously described formula (0) compound represented is high for the dissolubility of safety solvent, heat resistance and elching resistant are good Good, the photoetching of present embodiment forms composition with resist and obtains good corrosion-resisting pattern shape.

In turn, previously described formula (0) compound represented is due to for relatively low molecular weight and be low viscosity, even if being Substrate (especially fine space, sectional hole patterns etc.) with difference in height, is also easy to fill uniformly with it to its difference in height Each corner and the flatness for improving film, as a result, forming composition using the lower layer film for lithography of the compound can compare Advantageously improve embedment and planarization characteristics.In addition, due to also can for the compound with relatively high concentration of carbon Assign high elching resistant.

Previously described formula (0) compound represented is since aromatic series density is high, so refractive index is high, in addition, by from low temperature to The heat treatment of the wide scope of high temperature can inhibit to colour, therefore it is also useful for forming composition as various optical components.Before When stating formula (0) compound represented with quaternary carbon, from inhibiting, the oxygenolysis of the compound, inhibition coloring, heat resistance is high, improves It is preferred from the perspective of solvent solubility.Optical component is other than with film-form, sheet use, as plastic lens (prismatic lens, grating lens, lenticule, Fresnel lens, viewing angle control lens, contrast improve lens etc.), phase difference are thin Film, electromagnetic wave shielding film, prism, fiber optics, flexible printed wiring solder resist, resistance plating agent, multilayer board are used Interlayer dielectric, photonasty light-guide wave path are useful.

[formula (1) compound represented]

The compound of present embodiment preferably uses following formula (1) to indicate.Formula (1) compound represented is constituted as described below, Therefore, heat resistance is high, solvent solubility is also high.

(in formula (1), R⁰With aforementioned R^YFor identical meanings,

R¹For the group or singly-bound of the n valence of carbon number 1~60,

R²~R⁵It is each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally with the carbon number of substituent group 6~30 aryl, optionally the carbon number 2~30 with substituent group alkenyl, optionally have substituent group carbon number 1~30 alcoxyl Base, halogen atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom by the group containing vinyl phenylmethyl Replaced group, aforesaid alkyl, aforesaid aryl, foregoing alkenyl, aforementioned alkoxy optionally include ehter bond, ketonic bond or ester bond, this Place, R²~R⁵At least one be hydroxyl hydrogen atom group replaced the group containing vinyl phenylmethyl, m²And m³Respectively From the integer for independently being 0~8,

m⁴And m⁵It is each independently 0~9 integer,

Wherein, m²、m³、m⁴And m⁵It is not simultaneously 0,

p²~p⁵It is identical meanings with aforementioned r.)

R⁰With aforementioned R^YFor identical meanings.

R¹For the group or singly-bound of the n valence of carbon number 1~60, each aromatic rings is by the R¹Bonding.N is identical contain with aforementioned N Justice, when the integer that n is 2 or more, the structural formula in n [] is optionally identical mutually or different.It should be noted that for aforementioned n valence Group: in n=1 indicate carbon number 1~60 alkyl, in n=2 indicate carbon number 1~60 alkylidene, indicated in n=3 Three base of alkane of carbon number 2~60 indicates four base of alkane of carbon number 3~60 in n=4.As the group of aforementioned n valence, such as can lift Provide straight-chain alkyl, branched alkyl or group of alicyclic type hydrocarbon etc..Herein, it for aforementioned alicyclic type hydrocarbon, also wraps Include bridge joint alicyclic type hydrocarbon.In addition, the alkyl of aforementioned n valence can have alicyclic type hydrocarbon, double bond, hetero atom or carbon number 6~60 Aromatic group.

R²~R⁵It is each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally with the carbon number of substituent group 6~30 aryl, optionally the carbon number 2~30 with substituent group alkenyl, optionally have substituent group carbon number 1~30 alcoxyl Base, halogen atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom by the group containing vinyl phenylmethyl Replaced group, aforesaid alkyl, aforesaid aryl, foregoing alkenyl, aforementioned alkoxy optionally include ehter bond, ketonic bond or ester bond.Separately Outside, R²~R⁵At least one be hydroxyl hydrogen atom group replaced the group containing vinyl phenylmethyl.It needs to illustrate , aforesaid alkyl, alkenyl and alkoxy can be straight-chain, branched or cricoid group.

m²And m³It is each independently 0~8 integer, m⁴And m⁵It is each independently 0~9 integer.Wherein, m²、m³、m⁴ And m⁵It is not simultaneously 0.p²~p⁵It is each independently identical meanings with aforementioned r.

Previously described formula (1) although compound represented be relatively low molecular weight, due to its structure rigidity and have height Heat resistance, therefore even if could be used that under the conditions of high-temperature baking.In addition, having tertiary carbon or quaternary carbon in molecule, crystallinity is pressed down System, can be suitable as can be used in photoetching that photoetching manufacture with film with film formation composition come using.

In addition, the dissolubility for safety solvent is high, heat resistance and elching resistant are good, and the photoetching of present embodiment is used anti- It loses dosage form and obtains good corrosion-resisting pattern shape at composition.

In turn, due to for relatively low molecular weight and be low viscosity, even if (especially for the substrate with difference in height It is fine space, sectional hole patterns etc.), it is also easy to fill uniformly with it to each corner of its difference in height, and be easy to improve The flatness of film, as a result, embedment can advantageously be improved by forming composition using the lower layer film for lithography of the compound And planarization characteristics.In addition, due to can also assign high elching resistant for the compound with relatively high concentration of carbon.

Formula (1) compound represented is since aromatic series density is high, so refractive index is high, in addition, by from low temperature to high temperature The heat treatment of wide scope can inhibit to colour, therefore, it is also useful for forming composition as various optical components.With season It is excellent from the viewpoint of inhibiting the oxygenolysis of the compound, inhibiting coloring, heat resistance height, improve solvent solubility when carbon Choosing.Optical component other than with film-form, sheet use, as plastic lens (prismatic lens, grating lens, lenticule, Fresnel lens, viewing angle control lens, contrast improve lens etc.), phase-contrast film, electromagnetic wave shielding film, prism, light Fiber, flexible printed wiring solder resist, resistance plating agent, multilayer board interlayer dielectric, photonasty light-guide wave path are Useful.

Dissolubility from the viewpoint of crosslinking easiness and in organic solvent, previously described formula (1) compound represented is excellent Select following formula (1-1) compound represented.

In formula (1-1), R⁰、R¹、R⁴、R⁵、n、p²~p⁵、m⁴And m⁵With aforementioned for identical meanings, R⁶~R⁷It is each independently Straight-chain, branched or the cricoid alkyl of the optional carbon number 1~30 with substituent group, the optionally carbon number 6 with substituent group~ Alkenyl, halogen atom, nitro, amino, carboxylic acid group, the sulfydryl of 30 aryl, the optionally carbon number 2~30 with substituent group, R¹⁰~ R¹¹It is each independently hydrogen atom or the group containing vinyl phenylmethyl.

Herein, R¹⁰~R¹¹At least one be the group containing vinyl phenylmethyl, m⁶And m⁷It is each independently 0~7 Integer.Wherein, m⁴、m⁵、m⁶And m⁷It is not simultaneously 0.

In addition, changing shown in previously described formula (1-1) from the viewpoint of being easier crosslinking and dissolubility in organic solvent Close the preferred following formula of object (1-2) compound represented.

In formula (1-2), R⁰、R¹、R⁶、R⁷、R¹⁰、R¹¹、n、p²~p⁵、m⁶And m⁷With aforementioned for identical meanings, R⁸~R⁹With it is aforementioned R⁶~R⁷For identical meanings, R¹²~R¹³With aforementioned R¹⁰~R¹¹For identical meanings.m⁸And m⁹It is each independently 0~8 integer.Its In, m⁶、m⁷、m⁸And m⁹It is not simultaneously 0.

In addition, previously described formula (1-2) compound represented is preferably following formula (1a) from the viewpoint of the supply of raw material Compound represented.

In previously described formula (1a), R⁰~R⁵、m²~m⁵And explanation is identical meanings in n and previously described formula (1).

From the viewpoint of dissolubility in organic solvent, previously described formula (1a) compound represented is more preferably following formula (1b) compound represented.

In previously described formula (1b), R⁰、R¹、R⁴、R⁵、R¹⁰、R¹¹、m⁴、m⁵, explanation is identical meanings, R in n and previously described formula (1)⁶、 R⁷、R¹⁰、R¹¹、m⁶、m⁷It is identical meanings with explanation in previously described formula (1-1).

From the viewpoint of reactivity, previously described formula (1a) compound represented is more preferably shown in following formula (1b ') Compound.

From the viewpoint of dissolubility in organic solvent, under previously described formula (1b) compound represented is more preferably State formula (1c) compound represented.

In previously described formula (1c), R⁰、R¹、R⁶~R¹³、m⁶~m⁹, explanation is identical meanings in n and previously described formula (1-2).

From the viewpoint of reactivity, previously described formula (1b ') compound represented is preferably chemical combination shown in following formula (1c ') Object.

In previously described formula (1c '), R⁰、R¹、R⁶~R¹³、m⁶~m⁹, explanation is identical meanings in n and previously described formula (1-2).

The concrete example of following example previously described formula (0) compound represented, but formula (0) compound represented is not limited to herein The concrete example enumerated.

In previously described formula, illustrate to be identical meanings, R in X and previously described formula (0)^T’With the R illustrated in previously described formula (0)^TIt is identical Meaning, m are each independently 1~6 integer.

In previously described formula, illustrate to be identical meanings, R in X and previously described formula (0)^T’With the R illustrated in above-mentioned formula (0)^TIt is identical Meaning, m are each independently 1~6 integer.

And then the concrete example of following example previously described formula (0) compound represented, but not limited thereto example that place enumerates.

In previously described formula, illustrate to be identical meanings, R in X and previously described formula (0)^Y’、R^Z’With the R illustrated in previously described formula (0)^Y、R^Z For identical meanings.In turn, OR^4AAt least one be hydroxyl hydrogen atom base replaced the group containing vinyl phenylmethyl Group.

In previously described formula, illustrate to be identical meanings, R in X and previously described formula (0)^Z’With the R illustrated in previously described formula (0)^ZIt is identical Meaning.In turn, OR^4AAt least one be hydroxyl hydrogen atom group replaced the group containing vinyl phenylmethyl.

In previously described formula, illustrate to be identical meanings in X and previously described formula (0).In addition, R^Z’With the R illustrated in previously described formula (0)^Z For identical meanings.In turn, OR^4AAt least one be hydroxyl hydrogen atom base replaced the group containing vinyl phenylmethyl Group.

In previously described formula, illustrate to be identical meanings in X and previously described formula (0), in addition, R^Z’With the R illustrated in previously described formula (0)^Z For identical meanings.In turn, OR^4AAt least one be hydroxyl hydrogen atom base replaced the group containing vinyl phenylmethyl Group.

The concrete example of following example previously described formula (1) compound represented, but not limited to this example that place enumerates.

In aforesaid compound, R²、R³、R⁴、R⁵It is identical meanings with explanation in previously described formula (1).m²And m³For 0~6 it is whole Number, m⁴And m⁵For 0~7 integer.

Wherein, it is selected from R²、R³、R⁴、R⁵In at least one be hydroxyl hydrogen atom by the group containing vinyl phenylmethyl Replaced group.m²、m³、m⁴、m⁵It is not simultaneously 0.

Wherein, it is selected from R²、R³、R⁴、R⁵In at least one be hydroxyl hydrogen atom by the group containing vinyl phenylmethyl Replaced group, m²、m³、m⁴、m⁵It is not simultaneously 0.

In aforesaid compound, R¹⁰、R¹¹、R¹²、R¹³It is identical meanings with explanation in previously described formula (1-2), herein, R¹⁰~R¹³ At least one be hydroxyl hydrogen atom group replaced the group containing vinyl phenylmethyl.

From the viewpoint of dissolubility further in organic solvent, previously described formula (1) compound represented is particularly preferred For following formula (bif-1)~(bif-10) compound represented (R in concrete example¹⁰~R¹³With above-mentioned for identical meanings).

Hereinafter, the concrete example of further example above-mentioned formula (0) compound represented, but formula (0) compound represented is not It is defined in concrete example listed herewith.

In previously described formula, R⁰、R¹, explanation is identical meanings, R in n and previously described formula (1-1)^10’And R^11’With previously described formula (1-1) The R of middle explanation¹⁰And R¹¹For identical meanings, R^4’And R^5’Be each independently optionally with substituent group carbon number 1~30 alkyl, The aryl of the optional carbon number 6~30 with substituent group, the alkenyl of the optionally carbon number 2~30 with substituent group, optionally with substitution The alkoxy of the carbon number 1~30 of base, halogen atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom contained second Group replaced the group of alkenyl phenyl methyl, aforesaid alkyl, aforesaid aryl, foregoing alkenyl, aforementioned alkoxy optionally include Ehter bond, ketonic bond or ester bond, R^10’And R^11’At least one be hydroxyl hydrogen atom replaced the group containing vinyl phenylmethyl Group, m^4’And m^5’For 0~8 integer, m^10’And m^11’For 1~9 integer, m^4’+m^10’And m^4’+m^11’It is each independently 1~ 9 integer.

R⁰For example, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, 11 Alkyl, dodecyl, melissyl, phenyl, naphthalene, anthryl, pyrenyl, xenyl, heptacene base.

R^4’And R^5’For example, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, melissyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, Cyclodecyl, ring undecyl, cyclo-dodecyl, ring melissyl, norborny, adamantyl, phenyl, naphthalene, anthryl, pyrene Base, xenyl, heptacene base, vinyl, allyl, melene base, methoxyl group, ethyoxyl, melissane oxygroup, fluorine atom, Chlorine atom, bromine atom, iodine atom, sulfydryl.

Aforementioned R⁰、R^4’、R^5’Each example include isomers.For example, including normal-butyl, isobutyl group, sec-butyl, uncle in butyl Butyl.

In previously described formula, R¹⁰~R¹³Illustrate to be identical meanings, R with previously described formula (1-2)¹⁶For carbon number 1~30 straight-chain, Branched or cricoid alkylidene, carbon number 6~30 divalent aryl or carbon number 2~30 divalent alkenyl.

R¹⁶For example, methylene, ethylidene, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octene Base, nonenyl, decene base, undecenyl, dodecenyl succinic, melene base, cyclopropanyl, cyclobutane base, cyclopentenyl, Cyclohexenyl group, cycloheptenyl, cyclo-octene base, cyclonoene base, cyclodecene base, ring undecenyl, cyclododecene base, ring 30 Carbene base, the norborny of divalent, the adamantyl of divalent, the phenyl of divalent, the naphthalene of divalent, the anthryl of divalent, the pyrenyl of divalent, 2 The xenyl of valence, the heptacene base of divalent, the vinyl of divalent, the allyl of divalent, divalent melene base.

Aforementioned R¹⁶Each example include isomers.For example, including normal-butyl, isobutyl group, sec-butyl, tert-butyl in butyl.

In previously described formula, R¹⁰~R¹³It is identical meanings, R with explanation in previously described formula (1-2)¹⁴Be each independently carbon number 1~ 30 straight-chain, branched or cricoid alkyl, the alkenyl of the aryl of carbon number 6~30 or carbon number 2~30, carbon number 1~30 alkane Oxygroup, halogen atom, sulfydryl, m¹⁴For 0~5 integer.m^14’For 0~4 integer, m¹⁴For 0~5 integer.

R¹⁴For example, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, 11 Alkyl, dodecyl, melissyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, the ring last of the ten Heavenly stems Base, ring undecyl, cyclo-dodecyl, ring melissyl, norborny, adamantyl, phenyl, naphthalene, anthryl, pyrenyl, connection Phenyl, heptacene base, vinyl, allyl, melene base, methoxyl group, ethyoxyl, melissane oxygroup, fluorine atom, chlorine are former Son, bromine atom, iodine atom, sulfydryl.

Aforementioned R¹⁴Each example include isomers.For example, including normal-butyl, isobutyl group, sec-butyl, tert-butyl in butyl.

In previously described formula, R⁰、R^4’、R^5’、m^4’、m^5’、m^10’、m^11’With aforementioned for identical meanings, R^1’For the group of carbon number 1~60.

In previously described formula, R¹⁰~R¹³It is identical meanings, R with explanation in previously described formula (1-2)¹⁴Be each independently carbon number 1~ 30 straight-chain, branched or cricoid alkyl, the alkenyl of the aryl of carbon number 6~30 or carbon number 2~30, carbon number 1~30 alkane Oxygroup, halogen atom, sulfydryl, m¹⁴For 0~5 integer, m^14’For 0~4 integer, m^14”For 0~3 integer.

In previously described formula, R¹⁰~R¹³It is identical meanings, R with explanation in previously described formula (1-2)¹⁵For the straight chain of carbon number 1~30 Shape, branched or cricoid alkyl, the alkenyl of the aryl of carbon number 6~30 or carbon number 2~30, the alkoxy of carbon number 1~30, halogen Plain atom, sulfydryl.

R¹⁵For example, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, 11 Alkyl, dodecyl, melissyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, the ring last of the ten Heavenly stems Base, ring undecyl, cyclo-dodecyl, ring melissyl, norborny, adamantyl, phenyl, naphthalene, anthryl, pyrenyl, connection Phenyl, heptacene base, vinyl, allyl, melene base, methoxyl group, ethyoxyl, melissane oxygroup, fluorine atom, chlorine are former Son, bromine atom, iodine atom, sulfydryl.

Aforementioned R¹⁵Each example include isomers.For example, including normal-butyl, isobutyl group, sec-butyl, tert-butyl in butyl.

In previously described formula, R¹⁰~R¹³It is identical meanings with explanation in previously described formula (1-2).

From the viewpoint of raw material it is acquired, previously described formula (0) compound represented is more preferably as shown below Compound.

In turn, for previously described formula (0) compound represented, from the viewpoint of elching resistant, previously described formula is preferably below Structure.

In previously described formula, R^0AWith previously described formula R^YFor identical meanings, R^1A’With R^ZFor identical meanings, R¹⁰~R¹³With previously described formula (1-2) Middle explanation is identical meanings.

In previously described formula, R^0AWith previously described formula R^YFor identical meanings, R^1A’With R^ZFor identical meanings, R¹⁰~R¹³With previously described formula (1-2) Middle explanation is identical meanings.R¹⁴Be each independently straight-chain, branched or the cricoid alkyl of carbon number 1~30, carbon number 6~ 30 aryl or the alkenyl of carbon number 2~30, the alkoxy of carbon number 1~30, halogen atom, sulfydryl, m^14’For 0~4 integer.

R¹⁴For example, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, 11 Alkyl, dodecyl, melissyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, the ring last of the ten Heavenly stems Base, ring undecyl, cyclo-dodecyl, ring melissyl, norborny, adamantyl, phenyl, naphthalene, anthryl, heptacene Base, vinyl, allyl, melene base, methoxyl group, ethyoxyl, melissane oxygroup, fluorine atom, chlorine atom, bromine atom, iodine Atom, sulfydryl.

R¹⁵For example, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, 11 Alkyl, dodecyl, melissyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, the ring last of the ten Heavenly stems Base, ring undecyl, cyclo-dodecyl, ring melissyl, norborny, adamantyl, phenyl, naphthalene, anthryl, heptacene Base, vinyl, allyl, melene base, methoxyl group, ethyoxyl, melissane oxygroup, fluorine atom, chlorine atom, bromine atom, iodine Atom, sulfydryl.

In previously described formula, R¹⁰~R¹³It is identical meanings, R with explanation in previously described formula (1-2)¹⁶For the straight chain of carbon number 1~30 Shape, branched or cricoid alkylidene, carbon number 6~30 divalent aryl or carbon number 2~30 divalent alkenyl.

R¹⁶For example, methylene, ethylidene, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octene Base, nonenyl, decene base, undecenyl, dodecenyl succinic, melene base, cyclopropanyl, cyclobutane base, cyclopentenyl, Cyclohexenyl group, cycloheptenyl, cyclo-octene base, cyclonoene base, cyclodecene base, ring undecenyl, cyclododecene base, ring 30 Carbene base, the norborny of divalent, the adamantyl of divalent, the phenyl of divalent, the naphthalene of divalent, the anthryl of divalent, divalent heptacene Base, the vinyl of divalent, the allyl of divalent, divalent melene base.

In previously described formula, R¹⁰~R¹³It is identical meanings, R with explanation in previously described formula (1-2)¹⁴Be each independently carbon number 1~ 30 straight-chain, branched or cricoid alkyl, the alkenyl of the aryl of carbon number 6~30 or carbon number 2~30, carbon number 1~30 alkane Oxygroup, halogen atom, sulfydryl, m^14’For 0~4 integer.

In previously described formula, R¹⁰~R¹³It is identical meanings, R with explanation in previously described formula (1-2)¹⁴Be each independently carbon number 1~ 30 straight-chain, branched or cricoid alkyl, the alkenyl of the aryl of carbon number 6~30 or carbon number 2~30, carbon number 1~30 alkane Oxygroup, halogen atom, sulfydryl, m¹⁴For 0~5 integer.

From the viewpoint of heat resistance, aforesaid compound preferably has dibenzo xanthene skeleton.

In previously described formula, R¹⁰~R¹³It is identical meanings with explanation in previously described formula (1-2).It is preceding from the viewpoint of heat resistance Stating formula preferably has the compound of dibenzo xanthene skeleton.

From the viewpoint of raw material is acquired, compound documented by previously described formula (0) is preferably with flowering structure.

In previously described formula, R^0AWith previously described formula R^YFor identical meanings, R^1A’With R^ZFor identical meanings, R¹⁰~R¹³With previously described formula (1-2) Middle explanation is identical meanings.From the viewpoint of heat resistance, previously described formula preferably has the compound of xanthene skeleton.

In previously described formula, R¹⁰~R¹³It is identical meanings, R with explanation in previously described formula (1-2)¹⁴、R¹⁵、R¹⁶、m¹⁴、m^14’With it is preceding It states as identical meanings.

(formula (5) compound represented)

As the raw material of previously described formula (0) compound represented, polyphenol raw material can be used for example, can be used for example following Formula (5) compound represented.

m¹⁰It is each independently 1~3 integer,

The polyphenol raw material of compound as above-mentioned formula (5), can be used catechol, resorcinol, pyrogallol, example It can such as enumerate with flowering structure.

In previously described formula, R^1A’With R^ZFor identical meanings, R¹⁴、R¹⁵、R¹⁶、m¹⁴、m^14’With aforementioned for identical meanings.

[manufacturing method of formula (0) compound represented]

Formula used in present embodiment (0) compound represented can suitably be synthesized using well known method, be closed It is not particularly limited at gimmick.For example, formula (0) compound represented can close as follows when by taking formula (1) compound represented as an example At.

For example, formula (1) compound represented by make under normal pressure bisphenols, dinaphthalene phenols or dianthranide phenols with it is corresponding Aldehydes or ketone carry out polycondensation reaction, available previously described formula (1) compound represented under an acid catalysis.Furthermore it is possible to sharp The group containing vinyl phenylmethyl is imported at least one phenolic hydroxyl group of the compound with well known method.In addition, according to need It wants, can carry out under elevated pressure.

As aforementioned biphenyl phenols, for example, xenol, methyl biphenyl phenol, methoxyl group dinaphthol etc., but not It is particularly limited to these.They can be used alone, or two or more can be applied in combination.In these, in the steady of raw material Determine the aspect of supplyability, more preferably uses bis-phenol.

As aforementioned dinaphthalene phenols, for example, dinaphthol, methyl dinaphthol, methoxyl group dinaphthol etc., but not It is particularly limited to these.They can be used alone or two or more is applied in combination.In these, improving, carbon atom is dense Degree, the aspect for improving heat resistance, more preferably use dinaphthol.

As aforementioned dianthranide phenols, for example, dianthranide phenol, methyl dianthranide phenol, methoxyl group dianthranide phenol etc., but not It is particularly limited to these.They can be used alone or two or more is applied in combination.In these, improving, carbon atom is dense Degree, the aspect for improving heat resistance more preferably use dianthranide phenol.

As aforementioned aldehydes, for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propionic aldehyde, phenyl second Aldehyde, hydrocinnamicaldehyde, hydroxy benzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, tolyl aldehyde, ethylo benzene formaldehyde, butyl benzaldehyde, Biphenylcarboxaldehyde, naphthaldehyde, anthraldehyde, formaldehyde, pyrene formaldehyde, furfural etc., but it is not particularly limited in these.They can be used alone 1 kind or two or more is applied in combination.In these, from imparting high-fire resistance aspect, it is preferable to use benzaldehyde, phenyl second Aldehyde, hydrocinnamicaldehyde, hydroxy benzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, tolyl aldehyde, ethylo benzene formaldehyde, butyl benzaldehyde, Cyclohexyl benzene formaldehyde, biphenylcarboxaldehyde, naphthaldehyde, anthraldehyde, formaldehyde, pyrene formaldehyde, furfural use benzaldehyde, hydroxy benzaldehyde, chlorine Benzaldehyde, nitrobenzaldehyde, tolyl aldehyde, ethylo benzene formaldehyde, butyl benzaldehyde, cyclohexyl benzene formaldehyde, biphenylcarboxaldehyde, naphthalene Elching resistant is high when aldehyde, anthraldehyde, formaldehyde, pyrene formaldehyde, furfural, more preferably.

As aforementioned ketone, for example, acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norborneol Ketone, three cyclohexanone, tricyclic decanone, Buddha's warrior attendant alkanone, Fluorenone, benzfluorenone, acenaphthenequinone, acenaphthene ketone, anthraquinone, acetophenone, diacetyl benzene, Triacetyl benzene, acetonaphthone, diphenyl carbonyl naphthalene, phenylcarbonyl group biphenyl, diphenyl carbonyl biphenyl, benzophenone, diphenyl carbonyl Base benzene, triphenyl carbonyl benzene, benzoyl naphthalene (benzonaphthone), diphenyl carbonyl naphthalene, phenylcarbonyl group biphenyl, diphenyl carbonyl Base biphenyl etc., but it is not particularly limited in these.They can be used alone or two or more is applied in combination.In these, Assign high-fire resistance aspect, it is preferable to use cyclopentanone, cyclohexanone, norborneol ketone, three cyclohexanone, tricyclic decanone, Buddha's warrior attendant alkanone, Fluorenone, benzfluorenone, acenaphthenequinone, acenaphthene ketone, anthraquinone, acetophenone, diacetyl benzene, triacetyl benzene, acetonaphthone, diphenyl carbonyl Naphthalene, phenylcarbonyl group biphenyl, diphenyl carbonyl biphenyl, benzophenone, diphenyl carbonyl benzene, triphenyl carbonyl benzene, benzoyl naphthalene, two Phenylcarbonyl group naphthalene, phenylcarbonyl group biphenyl, diphenyl carbonyl biphenyl use acetophenone, diacetyl benzene, triacetyl benzene, naphthalene second Ketone, diphenyl carbonyl naphthalene, phenylcarbonyl group biphenyl, diphenyl carbonyl biphenyl, benzophenone, diphenyl carbonyl benzene, triphenyl carbonyl Elching resistant is high when benzene, benzoyl naphthalene, diphenyl carbonyl naphthalene, phenylcarbonyl group biphenyl, diphenyl carbonyl biphenyl, more preferably.

As aforementioned aldehydes or ketone, using with aromatic aldehyde or when there is aromatic ketone have both high-fire resistance and High elching resistant, therefore preferably.

The acid catalyst used in previous reaction can suitably select to use from well known catalyst, without spy It does not limit.As such acid catalyst, widely known inorganic acid, organic acid, for example: hydrochloric acid, sulfuric acid, phosphoric acid, The inorganic acids such as hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, succinic acid, adipic acid, decanedioic acid, citric acid, fumaric acid, maleic acid, Formic acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzene sulfonic acid, naphthalene sulfonic acids, naphthalene The lewis acids such as the organic acids such as disulfonic acid, zinc chloride, aluminium chloride, iron chloride, boron trifluoride or silico-tungstic acid, phosphotungstic acid, silicomolybdic acid Or solid acids such as phosphomolybdic acid etc., but it is not particularly limited in these.In these, from the viewpoint of manufacture is upper, preferred organic acid And solid acid, it is preferable to use hydrochloric acid or sulfuric acid from the viewpoint of in the manufactures such as accessibility, ease of handling.It needs It is bright, about acid catalyst, it can be used alone or two or more is applied in combination.In addition, the dosage of acid catalyst can be with It is suitably set, is not particularly limited according to the type and reaction condition etc. of the raw material used and the catalyst used, relative to 100 mass parts of reaction raw materials, preferably 0.01~100 mass parts.

In previous reaction, reaction dissolvent can be used.As reaction dissolvent, as long as the aldehydes or ketone and connection that use The solvent that the reaction of phenol, dinaphthalene phenols or dianthranide glycol carries out, there is no particular limitation, can be fitted from well known solvent When selection uses.Such as it may be exemplified out: water, methanol, ethyl alcohol, propyl alcohol, butanol, tetrahydrofuran, dioxane, second two Diethylene glycol dimethyl ether, ethylene glycol diethyl ether or their mixed solvent etc..It should be noted that solvent can be used alone or can Two or more is applied in combination.

In addition, the dosage of these solvents can be according to the type and reaction item of the raw material used and the catalyst used Part etc. is suitably set, and is not particularly limited, relative to 100 mass parts of reaction raw materials, the preferably range of 0~2000 mass parts. In turn, the reaction temperature in previous reaction can suitably be selected according to the reactivity of reaction raw materials, be not particularly limited, usually For 10~200 DEG C of range.

Formula (1) compound represented of present embodiment in order to obtain, preferable reaction temperature are high, and specifically preferably 60~200 DEG C range.It should be noted that reaction method can suitably select well known method, it is not particularly limited, has xenol The method that class, dinaphthalene phenols or dianthranide glycol, aldehydes or ketone, catalyst are disposably put into；By biphenyl phenols, dinaphthalene phenols or The method that dianthranide glycol, aldehydes or ketone are gradually added dropwise in the presence of a catalyst.After polycondensation reaction, obtained compound Separation can be carried out according to usual way, be not particularly limited.For example, in order to remove system memory unreacting material, Catalyst etc. can remove volatile ingredient by making the temperature of reaction kettle rise to 130~230 DEG C, and in 1~50mmhg or so Usual ways are waited to obtain the compound as object.

Biphenyl phenols, dinaphthalene phenols or dianthranide are used relative to aldehydes or 1 mole of ketone as preferred reaction condition 1.0 moles~excess quantity of glycol and 0.001~1 mole of acid catalyst, react under normal pressure, with 50~150 DEG C 20 minutes~ It 100 hours or so, thus carries out.

After reaction, object can be separated by well known method.For example, can carry out as follows: reaction solution is dense Contracting, pure water, which is added, is precipitated reaction product, and after being cooled to room temperature, being filtered makes its separation, and obtained solid matter is filtered And after drying, by column chromatography, isolated and purified with by-product, carries out solvent distillation removal, filtering, drying, obtain conduct Previously described formula (1) compound represented of object.

The method for importing the group containing vinyl phenylmethyl at least one phenolic hydroxyl group of polyphenolic substance is known 's.For example, can carry out as follows, the group containing vinyl phenylmethyl is imported at least one phenolic hydroxyl group of polyphenolic substance. Compound for importing the group containing vinyl phenylmethyl can use well known method to synthesize or be easy to get, such as Vinyl chloride, vinyl benzyl bromide, vinyl benzyl iodine can be enumerated, but is not particularly limited.

For example, making polyphenolic substance and the above-mentioned compound dissolution or outstanding for importing the group containing vinyl phenylmethyl It floats in the non-protonic solvents such as acetone, tetrahydrofuran (THF), propylene glycol methyl ether acetate.Then, in sodium hydroxide, hydrogen In the presence of the base catalysts such as potassium oxide, sodium methoxide, sodium ethoxide, react 6~72 hours under normal pressure, in 20~150 DEG C.With acid Neutralization reaction liquid is added in distilled water after white solid is precipitated, is cleaned or made solvent to isolated solid with distilled water It evaporates solid and is cleaned as needed with distilled water, is dried, it is hereby achieved that the hydrogen atom of hydroxyl is contained ethylene Compound replaced the group of base phenyl methyl.

It should be noted that about the opportunity for importing the group containing vinyl phenylmethyl, it not only can be in dinaphthalene phenols It, can also be in the last stage of condensation reaction after condensation reaction with aldehydes or ketone.Alternatively, it is also possible to carry out aftermentioned resin Manufacture after carry out.

In addition, importing hydroxy alkyl at least one phenolic hydroxyl group of polyphenolic substance to import vinyl to the hydroxyl The method of phenyl methyl is also well known.Hydroxy alkyl is also imported into phenolic hydroxyl group by oxygroup alkyl sometimes.For example, importing Hydroxy alkyl oxygroup alkyl, hydroxy alkyl oxygroup alkyloxyalkyl.

For example, can operate as follows, hydroxy alkyl is imported at least one phenolic hydroxyl group of aforesaid compound thus to the hydroxyl Base imports vinyl phenylmethyl.

Compound for importing hydroxy alkyl can use well known method synthesis or be readily available, such as can lift Out: chlorethanol, bromoethanol, acetic acid -2- chloroethene ester, acetic acid -2- bromine ethyl ester, acetic acid -2- iodo-ethyl ester, ethylene oxide, propylene oxide, Epoxy butane, ethylene carbonate, propylene carbonate, butylene carbonate, are not particularly limited.

For example, polyphenolic substance and the compound for importing hydroxy alkyl is made to be dissolved or suspended in acetone, tetrahydrofuran (THF), in the non-protonic solvents such as propylene glycol methyl ether acetate.Then, in sodium hydroxide, potassium hydroxide, sodium methoxide, ethyl alcohol In the presence of the base catalysts such as sodium, react 6~72 hours under normal pressure, in 20~150 DEG C.Reaction solution is neutralized with acid, is added After being precipitated white solid in distilled water, isolated solid is cleaned with distilled water or solvent is made to evaporate solid and basis It needs wash with distilled water, to be dried, it is hereby achieved that the hydrogen atom of hydroxyl compound replaced hydroxy alkyl.

For example, importing acetyl oxygen in the case where using acetic acid -2- chloroethene ester, acetic acid -2- bromine ethyl ester, acetic acid -2- iodo-ethyl ester After base ethyl, the reaction of deacylation base is generated, hydroxyethyl is thus imported.

In addition, making alkylene carbonates in the case where for example using ethylene carbonate, propylene carbonate, butylene carbonate Addition generates decarburization acid reaction, thus imports hydroxy alkyl.

Then, aforesaid compound and the compound for importing the group containing vinyl phenylmethyl are dissolved or suspended in In the non-protonic solvents such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether.Then, in sodium hydroxide, hydrogen-oxygen In the presence of the base catalyst for changing potassium, sodium methoxide, sodium ethoxide etc., react 6~72 hours under normal pressure, in 20~150 DEG C.With acid Reaction solution is neutralized, is added in distilled water after white solid is precipitated, isolated solid is cleaned with distilled water or is made molten Agent evaporation is solid and is cleaned as needed with distilled water, is dried, it is hereby achieved that the hydrogen atom of hydroxyl is contained second Compound replaced the group of alkenyl phenyl methyl.

In present embodiment, the group containing vinyl phenylmethyl reacts in the presence of free radical or acid/base, for applying The dissolubility of acid used in cloth solvent, developer solution, alkali or organic solvent changes.For the base containing vinyl phenylmethyl Group is formed in order to the highly sensitive high-resolution pattern of further progress, preferably has depositing in free radical or acid/base Cause the property of chain reaction under.

[using formula (0) compound represented as resin obtained from monomer]

Previously described formula (0) compound represented can be used as photoetching and directly be used with film formation composition.Alternatively, it is also possible to make To be used using previously described formula (0) compound represented as resin obtained from monomer.In other words, the resin of present embodiment is tool There is the resin of the cellular construction from aforementioned formula (0).For example, it is also possible to as previously described formula (0) compound represented and tool is made Resin obtained from crosslinking reactive compound reaction and use.

As using previously described formula (0) compound represented as resin obtained from monomer, for example, having following formula (3) resin of structure shown in.That is, the composition of present embodiment can contain the tree with structure shown in following formula (3) Rouge.

R⁰With aforementioned R^YFor identical meanings,

R¹For the group or singly-bound of the n valence of carbon number 1~60,

m²And m³It is each independently 0~8 integer,

m⁴And m⁵It is each independently 0~9 integer,

N and aforementioned N are identical meanings, and herein, when the integer that n is 2 or more, the structural formula in n [] is optionally identical or not With,

p²~p⁵It is identical meanings with aforementioned r.)

In formula (3), L be the alkylidene of the optional carbon number 1~30 with substituent group, the carbon number 6 optionally with substituent group~ The alkylene oxide group or singly-bound of 30 arlydene, the optionally carbon number 1~30 with substituent group.It is aforementioned alkylidene, aforementioned arlydene, preceding Stating alkylene oxide group optionally includes ehter bond, ketonic bond or ester bond.Aforementioned alkylidene, alkylene oxide group are optionally straight-chain, branched or ring The group of shape.

In formula (3), R⁰、R¹、R²~R⁵、m²And m³、m⁴And m⁵、p²~p⁵, in n and previously described formula (1) be identical meanings.Its In, m²、m³、m⁴And m⁵It is not simultaneously 0, R²~R⁵At least one be hydroxyl hydrogen atom by the group containing vinyl phenylmethyl Replaced group.

[using formula (0) compound represented as the manufacturing method of resin obtained from monomer]

The resin of present embodiment can be by making previously described formula (0) compound represented and the chemical combination with crosslinking reactivity Object reaction obtains.As the compound with crosslinking reactivity, as long as can be oligomeric by previously described formula (0) compound represented Materialization or polymerization, so that it may use well known substance without particular limitation.As its concrete example, for example, Aldehyde, carboxylic acid, carboxylic acid halide, halogen contained compound, amino-compound, imino-compound, isocyanates, contains unsaturation at ketone The compound etc. of alkyl, but it is not particularly limited to these.

As using previously described formula (0) compound represented as the concrete example of resin obtained from monomer, for example, logical Cross with the condensation reaction of the compound with crosslinking reactivity i.e. aldehyde and/or ketone etc. and by previously described formula (0) compound represented into The resins of novolaks is gone.

Herein, it as the aldehyde used when previously described formula (0) compound represented has been carried out novolaks, such as can lift Formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propionic aldehyde, ethylalbenzene, hydrocinnamicaldehyde, hydroxy benzaldehyde, chlorobenzene first out Aldehyde, nitrobenzaldehyde, tolyl aldehyde, ethylo benzene formaldehyde, butyl benzaldehyde, biphenylcarboxaldehyde, naphthaldehyde, anthraldehyde, formaldehyde, pyrene Formaldehyde, furfural etc., but it is not particularly limited to these.As ketone, aforementioned ketone can be enumerated.In these, more preferable formaldehyde. It should be noted that these aldehyde and/or ketone can be used alone or two or more are applied in combination.In addition, aforementioned aldehyde and/or The dosage of ketone is not particularly limited, relative to 1 mole of compound represented of previously described formula (0), preferably 0.2~5 mole, more preferably 0.5~2 mole.

In the condensation reaction of previously described formula (0) compound represented and aldehyde and/or ketone, catalyst also can be used.About this The acid catalyst that place uses can suitably be selected from well known catalyst, is not particularly limited.As this acid catalyst, Widely known inorganic acid, organic acid, for example: the inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, Malonic acid, succinic acid, adipic acid, decanedioic acid, citric acid, fumaric acid, maleic acid, formic acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trifluoro The organic acids such as acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzene sulfonic acid, naphthalene sulfonic acids, naphthalenedisulfonic acid, zinc chloride, chlorination Solid acids such as the lewis acids such as aluminium, iron chloride, boron trifluoride or silico-tungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid etc., it is not special These are not defined in it.In these, from the viewpoint of manufacture is upper, preferably organic acid and solid acid, from the easiness obtained, from From the perspective of managing in the manufactures such as easiness, preferably hydrochloric acid or sulfuric acid.It should be noted that about acid catalyst, it can be independent Using a kind or two or more is applied in combination.

In addition, the dosage of acid catalyst can be according to the type and reaction item of the raw material used and the catalyst used Part etc. is suitably set, and is not particularly limited, relative to 100 mass parts of reaction raw materials, preferably 0.01~100 mass parts.Wherein, With indenes, hydroxyl indenes, benzofuran, hydroxyl anthracene, acenaphthene, biphenyl, bis-phenol, triphenol, bicyclopentadiene, tetrahydroindene, 4- ethylene basic ring Hexene, norbornadiene, 5- vinyl norbornene -2- alkene, australene, nopinene, limonene etc. have the change of unconjugated double bond In the case where the copolyreaction for closing object, it is not necessarily required to as aldehydes.

In the condensation reaction of previously described formula (0) compound represented and aldehyde and/or ketone, reaction dissolvent also can be used.As Reaction dissolvent in the polycondensation can suitably be selected to use from well known solvent, is not particularly limited, such as may be exemplified Water, methanol, ethyl alcohol, propyl alcohol, butanol, tetrahydrofuran, dioxane or their mixed solvent etc..It should be noted that Solvent can be used alone or two or more is applied in combination.

In addition, the dosage of these solvents can be according to the type and reaction item of the raw material used and the catalyst used Part etc. is suitably set, and is not particularly limited, relative to 100 mass parts of reaction raw materials, the preferably range of 0~2000 mass parts. In turn, reaction temperature can be not particularly limited according to the appropriate selection of reactivity of reaction raw materials, and usually 10~200 DEG C Range.It should be noted that reaction method can suitably select well known method to come using being not particularly limited, having will be aforementioned The method that formula (0) compound represented, aldehyde and/or ketone, catalyst are disposably put into；Before being gradually added dropwise in the presence of a catalyst State formula (0) compound represented, the method for aldehyde and/or ketone.

After polycondensation reaction, the separation of obtained compound can be carried out according to usual way, be not particularly limited. For example, in order to remove system memory unreacting material, catalyst etc., can be by using rising to the temperature of reaction kettle 130~230 DEG C and the progress as object is obtained in 1~50mmhg or so general method of removal volatile ingredient etc. The resin of novolaks.

Herein, the resin with structure shown in previously described formula (3) can be the homopolymerization of previously described formula (0) compound represented Object is also possible to the copolymer with other phenols.Herein, it as the phenols that can be copolymerized, such as can enumerate: phenol, cresols, two Methylphenol, pseudocuminol, butylphenol, phenylphenol, diphenyl phenol, naphthalene phenol, resorcinol, methylresorcinol two Phenol, catechol, butyl-catechol, metoxyphenol, metoxyphenol, propylphenol, pyrogallol, thymol etc., but It is not particularly limited to these.

In addition, having the resin of structure shown in previously described formula (3) other than other above-mentioned phenols, being also possible to and can gather Resin made of the monomer copolymerization of conjunction.It as the comonomer, such as can enumerate: naphthols, methyl naphthols, methoxynaphthalene Phenol, dihydroxy naphthlene, indenes, hydroxyl indenes, benzofuran, hydroxyl anthracene, acenaphthene, biphenyl, bis-phenol, triphenol, bicyclopentadiene, tetrahydroindene, 4- Vinylcyclohexene, norbornadiene, vinyl norbornene, firpene, limonene etc., but it is not particularly limited in these.It needs Illustrate, the resin with structure shown in previously described formula (3) can be previously described formula (1) compound represented and above-mentioned phenols 2 yuan or more (such as 2~4 yuan be) copolymer, is also possible to the 2 of previously described formula (1) compound represented and above-mentioned comonomer First above (such as 2~4 yuan be) copolymer, is also possible to previously described formula (1) compound represented and above-mentioned phenols and above-mentioned copolymerization (such as 3~4 yuan be) copolymer of 3 yuan or more of monomer.

It should be noted that the molecular weight of the resin with structure shown in previously described formula (3) is not particularly limited, polyphenyl second The weight average molecular weight (Mw) preferably 500~30000, more preferable 750~20000 of alkene conversion.In addition, from improve cross-linking efficiency and From the perspective of inhibiting the volatile ingredient in baking, the preferred dispersion degree of resin with structure shown in previously described formula (3) (is divided equally again Son amount Mw/ number-average molecular weight Mn) be 1.2~7 in the range of resin.It should be noted that aforementioned Mn can be by aftermentioned The method recorded in embodiment is found out.

The viewpoints such as become easier to from the application of wet process, the resin with structure shown in previously described formula (3) is excellent Select the resin high to the dissolubility of solvent.More particularly, for these compounds and/or resin, with 1- methoxy-2-propanol (PGME) when and/or propylene glycol monomethyl ether (PGMEA) is solvent, the solubility to the solvent is preferably 10 mass % More than.Herein, " the quality ÷ (quality+solvent quality of resin) of resin is defined as to the solubility of PGME and/or PGMEA × 100 (quality %) ".For example, when aforementioned resin 10g is dissolved relative to PGMEA 90g, solubility of the aforementioned resin to PGMEA As " 10 mass % or more ", when not dissolving, become " lower than 10 mass % ".

[formula (2) compound represented]

The compound of present embodiment is it is also preferred that following formula (2) compound represented.The following structure of formula (2) compound represented At therefore, heat resistance is high, solvent solubility is also high.

(in formula (2), R^0AWith aforementioned R^YFor identical meanings,

R^1AFor the n of carbon number 1~30^AThe group or singly-bound of valence,

X^AIt is identical meanings with aforementioned X,

q^AIt is each independently 0 or 1.)

In formula (2), R^0AWith aforementioned R^YFor identical meanings.

R^1AFor the n of carbon number 1~60^AThe group or singly-bound of valence.n^AIt is identical meanings with aforementioned N, is 1~4 integer.Formula (2) in, n^AFor 2 or more integer when, n^AStructural formula in a [] is optionally identical or different.

It should be noted that for aforementioned n^AThe group of valence: in n^AThe alkyl that carbon number 1~60 is indicated when=1, in n^AWhen=2 The alkylidene for indicating carbon number 1~30, in n^AThree base of alkane of carbon number 2~60, n are indicated when=3^AThe alkane of carbon number 3~60 is indicated when=4 Four bases.As the group of aforementioned n valence, for example, the base with straight-chain alkyl, branched alkyl or alicyclic type hydrocarbon Group etc..It herein, also include bridge joint alicyclic type hydrocarbon about aforementioned alicyclic type hydrocarbon.In addition, aforementioned n valency alkyl optionally has rouge Ring type alkyl, double bond, hetero atom or carbon number 6~60 aromatic group.

R^2ABe each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally have the carbon number 6 of substituent group~ 30 aryl, optionally the carbon number 2~30 with substituent group alkenyl, optionally have substituent group carbon number 1~30 alkoxy, halogen Plain atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom group replaced vinyl phenylmethyl, Aforesaid alkyl, aforesaid aryl, foregoing alkenyl, aforementioned alkoxy optionally include ehter bond, ketonic bond or ester bond, herein, R^2AAt least one For hydrogen atom group replaced the group containing vinyl phenylmethyl of hydroxyl.It should be noted that aforesaid alkyl, alkenyl And alkoxy is optionally straight-chain, branched or cricoid group.

X^AIt is identical meanings with aforementioned X, each independently represents oxygen atom, sulphur atom or for no bridge joint.Herein, X^AFor oxygen In the case where atom or sulphur atom, have the tendency that showing high-fire resistance, therefore it is preferred that, more preferably oxygen atom.From deliquescent Viewpoint is set out, X^APreferably without bridge joint.

m^2AIt is each independently 0~6 integer.Wherein, at least one m^2AFor 1~6 integer.q^ABe each independently 0 or 1.In addition, the position indicated by naphthalene structure is in q in formula (2)^AIt is single ring architecture when=0, in q^AIt is bicyclic ring structures when=1.It is above-mentioned m^2AAccording to by q^AThe ring structure of decision determines its numberical range.

Previously described formula (2) although compound represented be relatively low molecular weight, due to its structure rigidity and have height Therefore heat resistance is able to use under the conditions of high-temperature baking.In addition, in molecule have tertiary carbon or quaternary carbon, crystallinity by To inhibition, the photoetching that can be used in photoetching is manufactured with film is suitable as with film and forms composition.

In addition, the dissolubility for safety solvent is high, heat resistance and elching resistant are good, and the photoetching of present embodiment is used anti- It loses dosage form and provides good corrosion-resisting pattern shape at composition.

In turn, due to for lower molecular weight and be low viscosity, even if (especially micro- for the substrate with difference in height Thin space, sectional hole patterns etc.), it is also easy to fill uniformly with to each corner of its difference in height, and be easy to improve the flat of film Property, as a result, embedment and planarization characteristics can advantageously be improved by forming composition using its lower layer film for lithography.Separately Outside, due to the compound for concentration of carbon with higher, high elching resistant can also be assigned.

Since aromatic series density is high, so refractive index is high and by from low temperature to and the heat treatment of the wide scope of high temperature It can inhibit to colour, therefore, it is also useful for forming composition as various optical components.From the oxidation point for inhibiting the compound Solution from the perspective of inhibiting coloring, heat resistance height, solvent solubility to improve, preferably has quaternary carbon.Optical component is in addition to film Except shape, sheet use, as plastic lens, (prismatic lens, grating lens, lenticule, Fresnel lens, viewing angle control are saturating Mirror, contrast improve lens etc.), phase-contrast film, electromagnetic wave shielding film, prism, fiber optics, flexible printed wiring hinder Solder flux, resistance plating agent, multilayer board interlayer dielectric, photonasty light-guide wave path are also useful.

Dissolubility from the viewpoint of the easiness of crosslinking and in organic solvent, previously described formula (2) compound represented It is preferred that following formula (2-1) compound represented.

In formula (2-1), R^0A、R^1A、n^AAnd q^AAnd X^AIt is identical meanings with explanation in previously described formula (2).R^3AOptionally have Straight-chain, branched or the cricoid alkyl of the carbon number 1~30 of substituent group, optionally with substituent group carbon number 6~30 aryl, Optionally alkenyl, halogen atom, nitro, amino, carboxylic acid group, the sulfydryl of the carbon number 2~30 with substituent group, in identical naphthalene nucleus or It is optionally identical or different in phenyl ring.

R^4AIt is each independently hydrogen atom or the group containing vinyl phenylmethyl, herein, R^4AAt least one be containing second The group of alkenyl phenyl methyl, m^6AIt is each independently 0~5 integer.

Use previously described formula (2-1) compound represented as alkali development positive-workingresist use or organic development negative resist When forming composition with photoetching film, R^4AAt least one be the group containing vinyl phenylmethyl.On the other hand, using formula (2- 1) compound represented forms composition, lower membrane photoetching film formation group as alkali development negative resist photoetching film When closing object or optical component formation composition, R^4AAt least one be hydrogen atom.

In addition, following formula (2-1) compound represented is preferably following formula (2a) from the viewpoint of the supply of raw material Compound represented.

In previously described formula (2a), X^A、R^0A~R^2A、m^2AAnd n^AIt is identical meanings with explanation in previously described formula (2).

In addition, previously described formula (2-1) compound represented is more preferably from the viewpoint of dissolubility in organic solvent Following formula (2b) compound represented.

In previously described formula (2b), X^A、R^0A、R^1A、R^3A、R^4A、m^6AAnd n^AIt is identical meanings with explanation in previously described formula (2-1).

In addition, previously described formula (2-1) compound represented is further excellent from the viewpoint of dissolubility in organic solvent It is selected as following formula (2c) compound represented.

In previously described formula (2c), X^A、R^0A、R^1A、R^3A、R^4A、m^6AAnd n^AIt is identical meanings with explanation in previously described formula (2-1).

From the viewpoint of dissolubility further in organic solvent, previously described formula (2) compound represented is particularly preferred For following formula (bisn-1)~(bisn-4), (xbisn-1)~(xbisn-3), (bin-1)~(bin-4) or (xbin-1)~ (xbin-3) compound represented.(the R in concrete example^4AWith above-mentioned for identical meanings).

[manufacturing method of formula (2) compound represented]

Formula used in present embodiment (2) compound represented can be suitable for synthesis using well known method, close It is not particularly limited at method.

For example, under normal pressure, by making phenol, aphthols contract under an acid catalysis with corresponding ketone or aldehydes Poly- reaction obtains polyphenolic substance, then, imports at least one phenolic hydroxyl group of polyphenolic substance and contains vinyl phenylmethyl Group, thus obtain.

In addition, aforementioned synthesis can also carry out under elevated pressure as needed.

It as aforementioned aphthols, is not particularly limited, for example, naphthols, methyl naphthols, methoxynaphthol, naphthalene two Phenol etc. more preferably uses naphthalenediol from that can be easy production xanthene structure aspect.

It as aforementioned phenol, is not particularly limited, for example, phenol, methylphenol, methoxybenzene, adjacent benzene two Phenol, resorcinol, hydroquinone, Trimethyl Hydroquinone etc..

As aforementioned aldehydes, for example: formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propionic aldehyde, phenyl Acetaldehyde, hydrocinnamicaldehyde, hydroxy benzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, tolyl aldehyde, ethylo benzene formaldehyde, butyl benzene first Aldehyde, biphenylcarboxaldehyde, naphthaldehyde, anthraldehyde, formaldehyde, pyrene formaldehyde, furfural etc., but it is not particularly limited in these.They can be independent Using a kind or two or more is applied in combination.In these, it is preferable to use benzaldehyde, phenyl second in terms of assigning high-fire resistance Aldehyde, hydrocinnamicaldehyde, hydroxy benzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, tolyl aldehyde, ethylo benzene formaldehyde, butyl benzaldehyde, Cyclohexyl benzene formaldehyde, biphenylcarboxaldehyde, naphthaldehyde, anthraldehyde, formaldehyde, pyrene formaldehyde, furfural use benzaldehyde, hydroxy benzaldehyde, chlorine Benzaldehyde, nitrobenzaldehyde, tolyl aldehyde, ethylo benzene formaldehyde, butyl benzaldehyde, cyclohexyl benzene formaldehyde, biphenylcarboxaldehyde, naphthalene Elching resistant is high when aldehyde, anthraldehyde, formaldehyde, pyrene formaldehyde, furfural, more preferably.

As aforementioned ketone, for example, acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norborneol Ketone, three cyclohexanone, tricyclic decanone, Buddha's warrior attendant alkanone, Fluorenone, benzfluorenone, acenaphthenequinone, acenaphthene ketone, anthraquinone, acetophenone, diacetyl benzene, Triacetyl benzene, acetonaphthone, diphenyl carbonyl naphthalene, phenylcarbonyl group biphenyl, diphenyl carbonyl biphenyl, benzophenone, diphenyl carbonyl Base benzene, triphenyl carbonyl benzene, benzoyl naphthalene, diphenyl carbonyl naphthalene, phenylcarbonyl group biphenyl, diphenyl carbonyl biphenyl etc., not especially It is defined in these.They can be used alone or two or more is applied in combination.In these, in the side for assigning high-fire resistance Face is, it is preferable to use cyclopentanone, cyclohexanone, norborneol ketone, three cyclohexanone, tricyclic decanone, Buddha's warrior attendant alkanone, Fluorenone, benzfluorenone, acenaphthene Quinone, acenaphthene ketone, anthraquinone, acetophenone, diacetyl benzene, triacetyl benzene, acetonaphthone, diphenyl carbonyl naphthalene, phenylcarbonyl group biphenyl, two Phenylcarbonyl group biphenyl, benzophenone, diphenyl carbonyl benzene, triphenyl carbonyl benzene, benzoyl naphthalene, diphenyl carbonyl naphthalene, phenyl carbonyl Base biphenyl, diphenyl carbonyl biphenyl use acetophenone, diacetyl benzene, triacetyl benzene, acetonaphthone, diphenyl carbonyl naphthalene, benzene Base carbonyl biphenyl, diphenyl carbonyl biphenyl, benzophenone, diphenyl carbonyl benzene, triphenyl carbonyl benzene, benzoyl naphthalene, diphenyl Elching resistant is high when carbonyl naphthalene, phenylcarbonyl group biphenyl, diphenyl carbonyl biphenyl, more preferably.

As ketone, high-fire resistance and high elching resistant are had both when using ketone with aromatic rings, therefore it is preferred that.

Aforementioned acid catalyst is not particularly limited, and can suitably select from well known inorganic acid, organic acid.Such as it can be with It enumerates: the inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid；Oxalic acid, formic acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trifluoro second The organic acids such as acid, trifluoromethanesulfonic acid, benzene sulfonic acid, naphthalene sulfonic acids, naphthalenedisulfonic acid；Zinc chloride, aluminium chloride, iron chloride, boron trifluoride etc. Lewis acid；Or the solid acids such as silico-tungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid.It is manufactured from accessibility, ease of handling etc. , it is preferable to use hydrochloric acid or sulfuric acid from the perspective of upper.In addition, can be used one kind or two or more about acid catalyst.

When manufacturing previously described formula (2) compound represented, reaction dissolvent can be used.As reaction dissolvent, as long as using Aldehydes or ketone will do it with reacting for aphthols etc., there is no particular limitation, water, methanol, ethyl alcohol, third can be used for example Alcohol, butanol, tetrahydrofuran, dioxane or their mixed solvent.The amount of aforementioned solvents is not particularly limited, such as phase It is the range of 0~2000 mass parts for 100 mass parts of reaction raw materials.

When manufacturing aforementioned polyphenolic substance, reaction temperature is not particularly limited, can be according to the reactivity of reaction raw materials It suitably selects, preferably 10~200 DEG C of range.In order to which selectivity is synthesized well shown in the formula (2) of present embodiment Compound, effect is high when temperature is low, more preferable 10~60 DEG C of range.

The manufacturing method of previously described formula (2) compound represented is not particularly limited, such as has aphthols etc., aldehydes or ketone The method that class, catalyst are disposably put into；The method of aphthols, ketone is gradually added dropwise in the presence of a catalyst.Polycondensation reaction knot Shu Hou, in order to remove system memory unreacting material, catalyst etc., can also make the temperature of reaction kettle rise to 130~ 230 DEG C, volatile ingredient is removed in 1~50mmhg or so.

The amount of raw material when manufacturing previously described formula (2) compound represented is not particularly limited, such as relative to aldehydes or ketone 1 mole of class, using the 2 moles~excess quantity such as aphthols and 0.001~1 mole of acid catalyst, under normal pressure, with 20~60 DEG C Thus reaction 20 minutes~100 hours or so carries out.

When manufacturing previously described formula (2) compound represented, after previous reaction, target is separated using well known method Object.The separation method of object is not particularly limited, for example, following method: reaction solution is concentrated, be added pure water and Reaction product is precipitated, after being cooled to room temperature, is filtered and separates, after obtained solid matter is filtered and dried, utilizes Column chromatography is isolated and purified with by-product, solvent distillation removal, filtering, drying is carried out, to obtain target compound.

The group replaced the group containing vinyl phenylmethyl is imported at least one phenolic hydroxyl group of polyphenolic substance Method be well known.For example, can operate as follows, is imported at least one phenolic hydroxyl group of polyphenolic substance and contained vinyl Group replaced the group of phenyl methyl.For importing the chemical combination of the group replaced the group containing vinyl phenylmethyl Object can use well known method synthesis or be readily available, for example, vinyl chloride, vinyl benzyl bromide, second Alkenyl benzyl iodide, is not particularly limited.

Such as make polyphenolic substance and the chemical combination for importing the group replaced the group containing vinyl phenylmethyl Object is dissolved or suspended in the non-protonic solvents such as acetone, tetrahydrofuran (THF), propylene glycol methyl ether acetate.Then, in hydrogen In the presence of the base catalysts such as sodium oxide molybdena, potassium hydroxide, sodium methoxide, sodium ethoxide, 6~72 are reacted under normal pressure, in 20~150 DEG C Hour.It with sour neutralization reaction liquid, is added in distilled water, after white solid is precipitated, isolated solid is carried out clearly with distilled water Wash or make solvent evaporation it is solid and as needed wash with distilled water, be dried, it is hereby achieved that the hydrogen atom quilt of hydroxyl Compound replaced group containing vinyl phenylmethyl.

It should be noted that about the opportunity for importing the group replaced the group containing vinyl phenylmethyl, not only It can be after the condensation reaction for dinaphthol class and aldehydes or ketone, or the leading portion rank of condensation reaction.Alternatively, it is also possible to It is carried out after carrying out the manufacture of aftermentioned resin.

In addition, also known import hydroxy alkyl at least one phenolic hydroxyl group of polyphenolic substance, to import to the hydroxyl The method of vinyl phenylmethyl.

Hydroxy alkyl is also imported into phenolic hydroxyl group by oxygroup alkyl sometimes.For example, importing hydroxy alkyl oxygroup alkyl, hydroxyl Base alkyloxyalkyl oxygroup alkyl.For example, can operate as follows, hydroxyl is imported at least one phenolic hydroxyl group of aforesaid compound Base alkyl, to import the group replaced vinyl phenylmethyl to the hydroxyl.

For example, can operate as follows, hydroxy alkyl is imported at least one phenolic hydroxyl group of aforesaid compound, thus to this Hydroxyl imports vinyl phenylmethyl.

For importing the compound of hydroxy alkyl, it can be synthesized or be readily available with well known method, such as can lifted Out chlorethanol, bromoethanol, acetic acid -2- chloroethene ester, acetic acid -2- bromine ethyl ester, acetic acid -2- iodo-ethyl ester, ethylene oxide, propylene oxide, Epoxy butane, ethylene carbonate, propylene carbonate, butylene carbonate, but be not particularly limited.

Such as aforementioned polyphenolic substance and the compound for importing hydroxy alkyl is made to dissolve or be suspended in acetone, tetrahydro furan It mutters in the non-protonic solvents such as (THF), propylene glycol methyl ether acetate.Then, in sodium hydroxide, potassium hydroxide, sodium methoxide, second In the presence of the base catalyst of sodium alkoxide etc., react 6~72 hours under normal pressure, with 20~150 DEG C.With sour neutralization reaction liquid, add Enter into distilled water, after white solid is precipitated, isolated solid is cleaned with distilled water or keeps solvent evaporation solid simultaneously As needed wash with distilled water, it is dried, it is hereby achieved that the compound that the hydrogen atom of hydroxyl is replaced by hydroxy alkyl.

Such as when using acetic acid -2- chloroethene ester, acetic acid -2- bromine ethyl ester, acetic acid -2- iodo-ethyl ester, acetoxyl group second is imported After base, hydroxyethyl is imported by generating the reaction of deacylation base.

In addition, for example make alkylene carbonates addition when using ethylene carbonate, propylene carbonate, butylene carbonate, Decarburization acid reaction is generated, hydroxy alkyl is thus imported.

Later, aforesaid compound and the compound for importing the group containing vinyl phenylmethyl are dissolved or suspended in In the non-protonic solvents such as acetone, tetrahydrofuran (THF), propylene glycol methyl ether acetate.Then, in sodium hydroxide, hydroxide In the presence of the base catalysts such as potassium, sodium methoxide, sodium ethoxide, react 6~72 hours under normal pressure, with 20~150 DEG C.It is neutralized with acid Reaction solution is added in distilled water, after white solid is precipitated, is cleaned or made solvent to isolated solid with distilled water Evaporate it is solid and as needed wash with distilled water, be dried, it is hereby achieved that the hydrogen atom of hydroxyl by contain vinyl benzene Compound replaced the group of ylmethyl.

In present embodiment, the group containing vinyl phenylmethyl reacts in the presence of free radical or acid/base, for applying The dissolubility of acid used in cloth solvent, developer solution, alkali or organic solvent changes.It is highly sensitive in order to further progress It spends high-resolution pattern to be formed, the group containing vinyl phenylmethyl preferably has in the presence of free radical or acid/base Cause the property of chain reaction.

[using formula (2) compound represented as the manufacturing method of resin obtained from monomer]

Previously described formula (2) compound represented can be used as photoetching and directly be used with film formation composition.Alternatively, it is also possible to make For using previously described formula (2) compound represented as resin obtained from monomer come using.For example, it is also possible to as previously described formula (2) are made Compound represented with crosslinking reactivity compound react obtained from resin come using.

As using previously described formula (2) compound represented as resin obtained from monomer, for example, having following formula (4) resin of structure shown in.That is, the composition of present embodiment can contain the tree with structure shown in following formula (4) Rouge.

In formula (4), L be the alkylidene of the optional carbon number 1~30 with substituent group, the carbon number 6 optionally with substituent group~ The alkylene oxide group or singly-bound of 30 arlydene, the optionally carbon number 1~30 with substituent group, it is aforementioned alkylidene, aforementioned arlydene, preceding Stating alkylene oxide group optionally includes ehter bond, ketonic bond or ester bond,

R^0A、R^1A、R^2A、m^2A、n^A、q^AAnd X^ABe identical meanings in previously described formula (2),

n^AFor 2 or more integer when, n^AStructural formula in a [] is optionally identical or different.

Wherein, R^2AAt least one include hydroxyl hydrogen atom group replaced the group containing vinyl phenylmethyl.

The resin of present embodiment can be by making previously described formula (2) compound represented and the chemical combination with crosslinking reactivity Object reaction obtains.

As the compound with crosslinking reactivity, if can by previously described formula (2) compound represented oligomeric materialization or Polymerization, so that it may use well known compound without particular limitation.As its concrete example, for example, aldehyde, ketone, Carboxylic acid, carboxylic acid halides, halogen contained compound, amino-compound, imino-compound, isocyanates, the compound containing unsaturated alkyl Deng, but it is not particularly limited to these.

As the concrete example of the resin with structure shown in previously described formula (2), for example, passing through previously described formula (2) institute The compound that shows and the condensation reaction of aldehyde and/or ketone as the compound with crosslinking reactivity etc. and carried out novolaks The resin of change.

Herein, as the aldehyde used when previously described formula (2) compound represented is carried out novolaks, for example, Formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propionic aldehyde, ethylalbenzene, hydrocinnamicaldehyde, hydroxy benzaldehyde, chlorobenzaldehyde, Nitrobenzaldehyde, tolyl aldehyde, ethylo benzene formaldehyde, butyl benzaldehyde, biphenylcarboxaldehyde, naphthaldehyde, anthraldehyde, formaldehyde, pyrene first Aldehyde, furfural etc., but it is not particularly limited in these.As ketone, aforementioned ketone can be enumerated.In these, more preferable formaldehyde.It needs Illustrate, these aldehyde and/or ketone can be used alone or two or more are applied in combination.In addition, aforementioned aldehyde and/or ketone Dosage be not particularly limited, relative to 1 mole of compound represented of previously described formula (2), preferably 0.2~5 mole, more preferably 0.5~2 mole.

In the condensation reaction of previously described formula (2) compound represented and aldehyde and/or ketone, catalyst also can be used.About this The acid catalyst that place uses can suitably be selected from well known catalyst, is not particularly limited.As this acid catalyst, Widely known inorganic acid, organic acid, for example, the inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, Malonic acid, succinic acid, adipic acid, decanedioic acid, citric acid, fumaric acid, maleic acid, formic acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trifluoro The organic acids such as acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzene sulfonic acid, naphthalene sulfonic acids, naphthalenedisulfonic acid, zinc chloride, chlorination Solid acids such as the lewis acids such as aluminium, iron chloride, boron trifluoride or silico-tungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid etc., but it is not special These are not defined in it.In these, from the viewpoint of manufacture is upper, preferably organic acid or solid acid, from accessibility, processing From the perspective of in the manufactures such as easiness, preferably hydrochloric acid or sulfuric acid.It should be noted that can individually make about acid catalyst With a kind or two or more is applied in combination.In addition, the dosage of acid catalyst can be according to the raw material used and the catalyst used Type and reaction condition etc. are suitably set, and are not particularly limited, relative to 100 mass parts of reaction raw materials, preferably 0.01~ 100 mass parts.Wherein, with indenes, hydroxyl indenes, benzofuran, hydroxyl anthracene, acenaphthene, biphenyl, bis-phenol, triphenol, bicyclopentadiene, four Hydrogen indenes, 4 vinyl cyclohexene, norbornadiene, 5- vinyl norbornene -2- alkene, australene, nopinene, limonene etc. have In the case where the copolyreaction of the compound of unconjugated double bond, aldehydes is not necessarily required.

In the condensation reaction of previously described formula (2) compound represented and aldehyde and/or ketone, reaction dissolvent also can be used.As Reaction dissolvent in the polycondensation can suitably be selected from well known solvent and be used, is not particularly limited, for example, Water, methanol, ethyl alcohol, propyl alcohol, butanol, tetrahydrofuran, dioxane or their mixed solvent etc..It should be noted that Solvent can be used alone or two or more is applied in combination.

In addition, type and reaction condition etc. of the dosage of these solvents according to the raw material used and the catalyst used It suitably sets, is not particularly limited, relative to 100 mass parts of reaction raw materials, the preferably range of 0~2000 mass parts.In turn, Reaction temperature can be not particularly limited, usually 10~200 DEG C of range according to the appropriate selection of reactivity of reaction raw materials. It should be noted that reaction method can suitably select well known method to come using being not particularly limited, have: by previously described formula (2) The method that compound represented, aldehyde and/or ketone, catalyst are disposably put into；Previously described formula is gradually added dropwise in the presence of a catalyst (2) method of compound represented, aldehyde and/or ketone.

After polycondensation reaction, the separation of gained compound can be carried out according to usual way, be not particularly limited.Example Such as, in order to will be present in the removal such as the unreacting material in system, catalyst, using make the temperature of reaction kettle be increased to 130~ 230 DEG C, will volatilize with 1~50mmhg or so the usual ways such as ingredient removal, it is hereby achieved that the progress as object The resins of novolaks.

Herein, the resin with structure shown in previously described formula (4) can be the homopolymerization of previously described formula (2) compound represented Object, or the copolymer with other phenols.Herein, as the phenols that can be copolymerized, for example, phenol, cresols, two Methylphenol, pseudocuminol, butylphenol, phenylphenol, diphenyl phenol, naphthalene phenol, resorcinol, methylresorcinol two Phenol, catechol, butyl-catechol, metoxyphenol, metoxyphenol, propylphenol, pyrogallol, thymol etc., but It is not particularly limited in these.

In addition, having the resin of structure shown in previously described formula (4) other than other above-mentioned phenols, being also possible to and can gather Resin made of the monomer copolymerization of conjunction.As the comonomer, for example, naphthols, methyl naphthols, methoxynaphthol, two Hydroxyl naphthalene, indenes, hydroxyl indenes, benzofuran, hydroxyl anthracene, acenaphthene, biphenyl, bis-phenol, triphenol, bicyclopentadiene, tetrahydroindene, 4- vinyl Cyclohexene, norbornadiene, vinyl norbornene, firpene, limonene etc., but it is not particularly limited in these.It needs to illustrate Be, the resin with structure shown in previously described formula (2) can for 2 yuan of previously described formula (2) compound represented and above-mentioned phenols with On (such as 2~4 yuan be) copolymer, or 2 yuan or more of previously described formula (2) compound represented and above-mentioned comonomer 3 yuan or more of (such as 2~4 yuan be) copolymer, previously described formula (2) compound represented and above-mentioned phenols and above-mentioned comonomer (such as 3~4 yuan be) copolymer.

It should be noted that the molecular weight of the resin with structure shown in previously described formula (4) is not particularly limited, polyphenyl second The weight average molecular weight (Mw) of alkene conversion is preferably 500~30000, more preferably 750~20000.In addition, from crosslinking effect is improved Rate and from the perspective of inhibiting volatile ingredient in baking, the preferred dispersion degree of resin with structure shown in previously described formula (4) (weight average molecular weight Mw/ number-average molecular weight Mn) is the resin in the range of 1.2~7.It should be noted that aforementioned Mn can pass through The method recorded in aftermentioned embodiment and find out.

The viewpoints such as become easier to from the application of wet process, the resin with structure shown in previously described formula (4) is excellent Choosing is to the high person of the dissolubility of solvent.More specifically, these compounds and/or resin are preferably, with 1- methoxy-2-propanol (PGME) and/or propylene glycol methyl ether acetate (PGMEA) be solvent in the case where, preferably to the solubility of the solvent be 10 matter Measure % or more.Herein, " quality ÷ (quality+solvent matter of resin of resin is defined as to the solubility of PGME and/or PGMEA Amount) × 100 (quality %) ".For example, aforementioned resin is to PGMEA in the case that aforementioned resin 10g is dissolved relative to PGMEA 90g Solubility become " 10 mass % or more ", undissolved situation becomes " be lower than 10 mass % ".

[purification process of compound and/or resin]

Previously described formula (0) compound represented and using its as resin obtained from monomer can by purification process below come Purifying.That is, the compound of present embodiment and/or the purification process of resin comprise the following steps: making to change shown in previously described formula (0) Close object and using its for resin obtained from monomer (for example, be selected from previously described formula (1) compound represented, shown in previously described formula (1) Compound is resin obtained from monomer, previously described formula (2) compound represented and using previously described formula (2) compound represented as monomer Obtained from one or more of resin) be dissolved in solvent and the process that obtains solution (S)；With, make acquired solution (S) and acid Property aqueous solution contact, the process (the first abstraction process) of aforesaid compound and/or the impurity in aforementioned resin is extracted, before obtaining Stating solvent used in the process of solution (S) includes the organic solvent not mixed arbitrarily with water.

In first abstraction process, aforementioned resin preferably for example passes through previously described formula (1) compound represented and/or formula (2) compound represented and resin obtained from the reacting of compound with crosslinking reactivity.It, can according to aforementioned purification process Content to reduce the various metals that may include in the form of impurity in the compound or resin with above-mentioned specific structure.

More specifically, in aforementioned purification process, it is dissolved in aforesaid compound and/or aforementioned resin arbitrarily not mixed with water The organic solvent of sum and obtain solution (S), and then contact the solution (S) with acidic aqueous solution, processing can be extracted.By This, after migrating metal component contained in previous solu (S) to water phase, organic phase is separated from the water, available metal The compound and/or resin that content reduces.

Used in aforementioned purification process, compound and resin can be used alone, two or more use can also be mixed. In addition, aforesaid compound, resin can contain various surfactants, various crosslinking agents, various acid agents, various stabilizers Deng.

As the solvent not mixed arbitrarily with water used in aforementioned purification process, it is not particularly limited, it preferably can be safe Applied to the organic solvent of semiconductor fabrication process, specifically, it is preferable that for the having lower than 30% to the solubility of water at room temperature Solvent, more preferably less than 20%, especially preferably less than 10% organic solvent.The dosage of the organic solvent is relative to using The total amount of compound and resin is preferably 1~100 mass times.

As the concrete example for the solvent not mixed arbitrarily with water, be not limited to hereinafter, for example: diethyl ether, two The esters such as the ethers such as isopropyl ether, ethyl acetate, n-butyl acetate, isoamyl acetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), second The ketones such as base isobutyl ketone, cyclohexanone, cyclopentanone, 2-HEPTANONE, 2 pentanone；Ethylene glycol monoethylether acetate, ethylene glycol monobutyl ether The glycol ethers acetate esters such as acetic acid esters, propylene glycol methyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate；N-hexane, just The aliphatic hydrocarbons such as heptane；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；Halogenated hydrocarbons such as methylene chloride, chloroform etc..In these, It is preferred that toluene, 2-HEPTANONE, cyclohexanone, cyclopentanone, methyl iso-butyl ketone (MIBK), propylene glycol methyl ether acetate, ethyl acetate etc., more excellent Select methyl iso-butyl ketone (MIBK), ethyl acetate, cyclohexanone, propylene glycol methyl ether acetate, still more preferably methyl iso-butyl ketone (MIBK), second Acetoacetic ester.Due to the saturation solubility of aforesaid compound and the resin for comprising the compound as constituent is higher, boiling point compared with It is low, therefore, methyl iso-butyl ketone (MIBK), ethyl acetate etc. can reduce industrially by solvent distill the case where removing, by it is dry into Load in the process of row removal.These solvents can use individually, and can also mix two or more use.

As aqueous solution acid used in aforementioned purification process, commonly known organic system chemical combination is dissolved with from water It is suitably selected in object or the aqueous solution of inorganic compound.It is not limited to hereinafter, for example, dissolved with hydrochloric acid, sulphur in water In the inorganic acid aqueous solution or water of the inorganic acids such as acid, nitric acid, phosphoric acid dissolved with acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, The organic acids such as fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-methyl benzenesulfonic acid, trifluoroacetic acid it is organic Aqueous acid.These acid aqueous solutions can use individually, and can also combine two or more use.These acid water In solution, it is preferably selected from the inorganic acid aqueous solution or choosing of one or more of group being made of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid Free acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, The aqueous solutions of organic acids of one or more of the group of p-methyl benzenesulfonic acid and trifluoroacetic acid composition, more preferable sulfuric acid, nitric acid and acetic acid, The aqueous solution of the carboxylic acids such as oxalic acid, tartaric acid, citric acid, further preferred sulfuric acid, oxalic acid, tartaric acid, citric acid aqueous solution, more The aqueous solution of further preferred oxalic acid.The polybasic carboxylic acids such as oxalic acid, tartaric acid, citric acid are coordinated in metal ion, generate chelating effect Fruit, it is therefore contemplated that having the tendency that more effectively removing metal.In addition, the purifying of water used herein according to the present embodiment The purpose of method, it is preferable to use the few water of tenor, such as ion exchange water.

The pH of acid aqueous solution used in aforementioned purification process is not particularly limited, it is considered preferred to aforementioned chemical combination The influence of object, resin adjusts the acid degree of aqueous solution.In general, pH range is 0~5 or so, preferably pH 0~3 or so.

The dosage of acid aqueous solution used in aforementioned purification process is not particularly limited, from reducing for removing metal Extraction time viewpoint and from the perspective of considering whole liquid measure and ensuring operability, preferably adjust the dosage.In the past It states viewpoint to set out, the dosage of acid aqueous solution is preferably 10~200 mass %, more relative to 100 mass % of previous solu (S) Preferably 20~100 mass %.

In aforementioned purification process, by contacting the aqueous solution of aforementioned acid with previous solu (S), so as to from solution (S) metal component is extracted in the aforesaid compound or aforementioned resin in.

In aforementioned purification process, previous solu (S) preferably also includes the organic solvent arbitrarily mixed with water.Comprising appointing with water When the organic solvent for mixing of anticipating, the input amount of aforesaid compound and/or resin can be increased, in addition, liquid separation improves, having can The tendency purified with high kettle efficiency.The method for adding the organic solvent arbitrarily mixed with water is not particularly limited.For example, It can be the method made an addition in the solution comprising organic solvent in advance, make an addition to the side in water or acid aqueous solution in advance Any one of method, the method being added after contacting the solution comprising organic solvent with the aqueous solution of water or acidity.This Among a little, from the workability of operation, the management easiness aspect of input amount, preferably made an addition in advance comprising organic solvent Solution in method.

It as the organic solvent arbitrarily mixed used in aforementioned purification process with water, is not particularly limited, preferably may be used With the organic solvent of the security application in semiconductor fabrication process.As long as the dosage solution of the organic solvent arbitrarily mixed with water The range that can be mutually separated with water phase, there is no particular limitation, relative to the total amount of the compound and resin that use, preferably 0.1~100 mass times, more preferably 0.1~50 mass times, further preferably 0.1~20 mass times.

As the concrete example of the organic solvent arbitrarily mixed used in aforementioned purification process with water, be not limited to hereinafter, It can enumerate: the ethers such as tetrahydrofuran, 1,3- dioxolanes；The alcohols such as methanol, ethyl alcohol, isopropanol；Acetone, N- crassitude The ketones such as ketone；The glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), dihydroxypropane single-ether Equal aliphatic hydrocarbons.In these, preferably N-Methyl pyrrolidone, propylene glycol monomethyl ether etc., more preferably N- crassitude Ketone, propylene glycol monomethyl ether.These solvents can use individually, and can also mix two or more use.

Temperature when extracting processing is usually 20~90 DEG C, preferably 30~80 DEG C of range.Extraction operation is for example It stands after being sufficiently mixed by stirring etc. to carry out.Metal contained in solution (S) point is migrated into water phase as a result,.In addition, logical Cross this operation, the acid degree of solution reduces, and is able to suppress the rotten of compound and/or resin.

Aforementioned mixed solution is separated by standing comprising compound and/or the solution phase of resin and solvent, Yi Jishui Phase, therefore solution phase is recycled by decantation etc..The time of standing is not particularly limited, from making to wrap solvent-laden solution Xiang Yushui From the perspective of the separation of phase is better, the time of the standing is preferably adjusted.In general, the time stood is 1 minute or more, preferably It is 10 minutes or more, more preferably 30 minutes or more.In addition, extraction process can only carry out 1 time, but it is repeated several times and is mixed It closes, stand, the such operation of separation is also effective.

In aforementioned purification process, preferably after aforementioned first abstraction process further include: make comprising aforesaid compound or aforementioned The solution of resin is mutually further contacted with water, to extract the process of the impurity in aforesaid compound or aforementioned resin, (second is mentioned Take process).Specifically, for example, it is preferable that, it, will be water-soluble from this after carrying out aforementioned extraction process using acid aqueous solution Extracted in liquid and recycle, comprising the solution of compound and/or resin and solvent mutually further for using water extraction process. It is aforementioned to be not particularly limited using the extraction process of water, such as can be by sufficiently mixed by previous solu phase and water conservancy stirring etc. After conjunction, resulting mixed solution is stood to carry out.Mixed solution after the standing be separated into comprising compound and/or resin and The solution phase and water phase of solvent, therefore solution phase can be recycled by decantation etc..

In addition, the purpose of water used herein according to the present embodiment, the preferably few water of tenor, such as ion are handed over Change water etc..Extraction process can only carry out 1 time, but it is also effective for being repeated several times and mixed, stood, separating such operation 's.In addition, the condition of the use ratio of the two in extraction process, temperature, time etc. are not particularly limited, it can also be with before The case where with the contact treatment of acid aqueous solution, is identical.

For obtain in the solution comprising compound and/or resin and solvent in this way can mixed moisture, can pass through Implement the operation such as vacuum distillation and is readily removable.In addition, as needed, solvent can be added in previous solu, by chemical combination The concentration of object and/or resin is adjusted to any concentration.

The method for separating compound and/or resin from the resulting solution comprising compound and/or resin and solvent Be not particularly limited, can by decompression removal, based on method well known to the separation of reprecipitation and their combination etc. come into Row.It can according to need and carry out processing well known to concentration operation, filter operation, centrifuge separation operation, drying process etc..

" composition "

The composition of present embodiment contains a kind in the group of the compound and resin composition selected from above-mentioned present embodiment More than.The composition of present embodiment can further contain solvent, acid agent, crosslinking agent, crosslinking accelerator, free radical polymerization Initiator etc..The composition of present embodiment can be used for photoetching film and form purposes (that is, photoetching film forms composition), light Department of the Chinese Academy of Sciences's part forms purposes.

[photoetching forms composition with film]

1 kind in group that the composition of present embodiment can contain the compound of above-mentioned present embodiment and resin forms Above (for example, being set selected from previously described formula (1) compound represented, using previously described formula (1) compound represented as obtained from monomer In rouge, previously described formula (2) compound represented and the group that is formed using previously described formula (2) compound represented as resin obtained from monomer 1 kind or more) be used as resist substrate.

[photoetching towards chemically amplified photoresist purposes forms composition with film]

The composition of present embodiment may be used as the photoetching towards chemically amplified photoresist purposes and form combination with film Object (hereinafter also referred to as anti-corrosion agent composition).Anti-corrosion agent composition contains such as compound and resin selected from present embodiment One or more of group of composition.

In addition, aforementioned anti-corrosion agent composition preferably comprises solvent.As solvent, it is not particularly limited, for example: Ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol propyl ether acetic acid esters, ethylene glycol mono-n-butyl ether acetic acid The ethylene glycol monoalkyl ether acetates class such as ester；The ethylene glycol monoalkyl ethers class such as glycol monoethyl ether, ethylene glycol monoethyl ether；Propylene glycol Methyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol list positive propyl ether acetic acid esters, propylene glycol mono-n-butyl ether second The propylene-glycol monoalky lethers acetate esters such as acid esters；The propylene-glycol monoalky lethers such as propylene glycol monomethyl ether (PGME), dihydroxypropane single-ether Class；The lactic acid esters such as methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, N_amyl lactate；Methyl acetate, acetic acid The aliphatic carboxylic such as ethyl ester, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate Esters of gallic acid；3- methoxy methyl propionate, 3- methoxypropionate, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, 3- Methoxyl group -2 Methylpropionic acid methyl esters, 3- methoxybutyl acetic acid esters, 3- methyl -3- methoxybutyl acetic acid esters, 3- methoxyl group - 3- methylpropanoic acid butyl ester, 3- methoxyl group -3 Methylbutanoic acid butyl ester, methyl acetoacetate, methyl pyruvate, ethyl pyruvate etc. its His esters；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；2-HEPTANONE, 3- heptanone, 4- heptanone, cyclopentanone (CPN), cyclohexanone (CHN) etc. Ketone；The amides such as N,N-dimethylformamide, N- methylacetamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone； Lactones such as gamma lactone etc., are not particularly limited.These solvents can be used alone or use two or more.

Solvent used in present embodiment is preferably safety solvent, more preferably selected from PGMEA, PGME, CHN, CPN, It is at least one kind of in 2-HEPTANONE, methyl phenyl ethers anisole, butyl acetate, ethyl propionate and ethyl lactate, further preferably selected from PGMEA, At least one of PGME and CHN.

In present embodiment, the amount of solid component and the amount of solvent are not particularly limited, relative to solid component amount and The 100 mass % of total quality of solvent, preferably 20~99 mass % of 1~80 mass % of solid component and solvent, it is more preferably 50~99 mass % of 1~50 mass % of solid component and solvent, further preferably 2~40 mass % of solid component and solvent 60 ~98 mass %, particularly preferably 90~98 mass % of 2~10 mass % of solid component and solvent.

It, can be containing selected from acid agent (C), acid crosslinking agent as other solid components in aforementioned anti-corrosion agent composition (G), at least one of the group of acid diffusion controlling agent (E) and other compositions (F) composition.It should be noted that in this specification, Solid component refers to the ingredient other than solvent.

Herein, it about acid agent (C), acid crosslinking agent (G), acid diffusion controlling agent (E) and other compositions (F), can be used Well known substance, is not particularly limited, such as the substance recorded in preferred International Publication No. 2013/024778.

[the compounding ratio of each ingredient]

In aforementioned anti-corrosion agent composition, the compound of the above-mentioned present embodiment used as resist substrate and resin Content is not particularly limited, preferably solid component gross mass (comprising resist substrate, acid agent (C), acid crosslinking agent (G), The summation of the acid diffusion solid component of arbitrarily used ingredient such as controlling agent (E) and other compositions (F), below equally.) 50~ 99.4 mass %, more preferably 55~90 mass %, further preferably 60~80 mass %, particularly preferably 60~70 matter Measure %.In the case where aforementioned content, resolution ratio is further increased, line edge roughness (LER) further becomes smaller.

It should be noted that aforementioned content is containing both compound and resin as in the case where resist substrate The total amount of two-component.

[other compositions (F)]

In aforementioned anti-corrosion agent composition, in the range of not hindering the purpose of the present invention, as needed, as resist-based Ingredient other than material, acid agent (C), acid crosslinking agent (G) and acid diffusion controlling agent (E) can add one kind or two or more molten Solve oxyacid of promotor, dissolution controlling agent, sensitizer, surfactant, organic carboxyl acid or phosphorus or derivatives thereof, heat and/or Light-cured catalyst, polymerization inhibitor, fire retardant, filler, coupling agent, heat-curing resin, light-cured resin, dyestuff, pigment, Thickener, lubricant, defoaming agent, levelling agent, ultraviolet absorbing agent, surfactant, colorant, nonionic surfactants Etc. various additives.It should be noted that other compositions (F) are known as any ingredient (F) sometimes in this specification.

In aforementioned anti-corrosion agent composition, resist substrate (hereinafter also referred to as ingredient (A)), acid agent (C), acid crosslinking agent (G), acid spreads the content (ingredient (A)/acid agent (C)/acid crosslinking agent (G)/acid diffusion control of controlling agent (E), any ingredient (F) Preparation (E)/any ingredient (F)) in terms of the quality % of solid matter benchmark,

Preferably 50~99.4/0.001~49/0.5~49/0.001~49/0~49,

More preferably 55~90/1~40/0.5~40/0.01~10/0~5,

Further preferably 60~80/3~30/1~30/0.01~5/0~1,

Particularly preferably 60~70/10~25/2~20/0.01~3/0.

The compounding ratio of each ingredient is selected from each range in such a way that its summation becomes 100 mass %.For aforementioned proportion When, sensitivity, resolution ratio, developability etc. are had excellent performance.

Each ingredient is usually dissolved in solvent when in use and homogeneous solution is made by aforementioned anti-corrosion agent composition, then basis It needs to be filtered such as the filter with 0.2 μm or so of aperture, thus prepare.

Aforementioned anti-corrosion agent composition can in the range of not hindering the object of the invention comprising present embodiment compound, Other resins other than resin.The resin is not particularly limited, for example: novolac resin, polyvinylphenols, Polyacrylic acid, polyvinyl alcohol, phenylethylene-maleic anhydride resin and include acrylic acid, vinyl alcohol or vinyl phenol as single The polymer of body unit or their derivative etc..The content of aforementioned resin is not particularly limited, can be according to the ingredient (A) used Type be suitably adjusted, relative to 100 mass parts of ingredient (A), preferably 30 below the mass, more preferably 10 mass parts Below, be more preferably 5 below the mass, particularly preferably 0 mass parts.

[physical property etc. of anti-corrosion agent composition]

Aforementioned anti-corrosion agent composition can form amorphous film by spin coating.Furthermore it is possible to apply in common semiconductor In manufacturing process.It can be according to the compound of above-mentioned present embodiment and the type of the type of resin and/or the developer solution used And any one of eurymeric corrosion-resisting pattern and minus corrosion-resisting pattern are prepared respectively.

In the case where eurymeric corrosion-resisting pattern, the aforementioned anti-corrosion agent composition of spin coating and the amorphous film that is formed are at 23 DEG C to development The solution rate of liquid is preferablyBelow, more preferablyFurther preferably The solution rate isWhen following, developer solution is not dissolved in, resist is capable of forming.In addition, havingMore than Solution rate when, sometimes resolution ratio improve.Speculate the exposure this is because: compound and resin due to above-mentioned present embodiment Deliquescent variation before and after light is dissolved in exposure portion and the comparison at the interface in the unexposed portion insoluble in developer solution of developer solution Degree becomes larger.In addition, there are also the effects for reducing LER, reducing defect.

In the case where minus corrosion-resisting pattern, the aforementioned anti-corrosion agent composition of spin coating and the amorphous film that is formed are at 23 DEG C to development The solution rate of liquid is preferablyMore than.The solution rate isWhen above, it is soluble in developer solution, is more suitable for In resist.In addition, havingWhen the above solution rate, resolution ratio is also improved sometimes.Speculate this is because: above-mentioned The microcosmic surface portion dissolution of the compound and resin of present embodiment, reduces LER.In addition, being reduced the effect of defect.

About aforementioned solution rate, amorphous film can be impregnated into the stipulated time in developer solution at 23 DEG C, by visual observation, Method well known to ellipsometer or QCM method etc. measures the film thickness of its dipping front and back, so that it is determined that.

In the case where eurymeric corrosion-resisting pattern, the aforementioned anti-corrosion agent composition of spin coating and the amorphous film that is formed pass through krf standard point The part that sub- laser, extreme ultraviolet, electron beam or X-ray israds are exposed is at 23 DEG C to the dissolution speed of developer solution Degree is preferablyMore than.The solution rate isWhen above, it is soluble in developer solution, more suitable for resist.Separately Outside, haveWhen the above solution rate, resolution ratio is also improved sometimes.Speculate this is because: above-mentioned present embodiment The microcosmic surface portion dissolution of compound and resin, reduces LER.In addition, being reduced the effect of defect.

In the case where minus corrosion-resisting pattern, the aforementioned anti-corrosion agent composition of spin coating and the amorphous film that is formed pass through krf standard point The part that sub- laser, extreme ultraviolet, electron beam or X-ray israds are exposed is at 23 DEG C to the dissolution speed of developer solution Degree is preferablyBelow, more preferablyFurther preferablyThe solution rate ForWhen following, developer solution is not dissolved in, resist is capable of forming.In addition, havingAbove solution rate When, resolution ratio also improves sometimes.Speculate this is because: by the inclusion of the compound and resin of above-mentioned present embodiment as composition Deliquescent variation before and after the exposure of the resin of ingredient, be dissolved in developer solution unexposed portion and the undissolved exposure in developer solution The contrast at the interface in light portion becomes larger.In addition, there are also the effects for reducing LER, reducing defect.

[photoetching towards non-chemical amplification type anti-corrosion agent purposes forms composition with film]

The composition of present embodiment may be used as the photoetching film formation group towards non-chemical amplification type anti-corrosion agent purposes It closes object (hereinafter also referred to as radiation-sensitive composition).Contain in aforementioned radiation line sensitive compositions ingredient (A) (on State the compound and resin of present embodiment) as the positive-workingresist formed as follows with substrate be useful: with it is aftermentioned heavy Quinoline quinone Photoactive compounds (B) are applied in combination, and pass through irradiation g ray, h ray, i ray, krf excimer laser, arf standard point Sub- laser, extreme ultraviolet, electron beam or X-ray and become be soluble in developer solution compound positive-workingresist substrate.It is logical Cross g ray, h ray, i ray, krf excimer laser, arf excimer laser, extreme ultraviolet, electron beam or X-ray, ingredient (A) although property will not significantly change, the diazo naphthoquinone Photoactive compounds (B) for being insoluble in developer solution become readily soluble change Object is closed, thus, it is possible to make corrosion-resisting pattern by developing procedure.

The ingredient (A) contained in aforementioned radiation line sensitive compositions is the lower compound of molecular weight, and therefore, gained is anti- The roughness of corrosion figure case is very small.In addition, being preferably selected from previously described formula (1) by R⁰~R⁵At least one in the group of composition is packet Group containing iodine atom in previously described formula (2), is preferably selected from by R^0A、R^1AAnd R^2AAt least one in the group of composition is comprising iodine original The group of son.Aforementioned anti-corrosion agent composition application this preferred embodiment i.e. there is ingredient (A) of the group comprising iodine atom when, It can increase the absorption to electron beam, extreme ultraviolet (EUV), X-ray israds, be excellent as a result, it is possible to improve sensitivity Choosing.

The glass transition temperature of the ingredient (A) (resist substrate) contained in aforementioned radiation line sensitive compositions is preferred It is 100 DEG C or more, more preferably 120 DEG C or more, further preferably 140 DEG C or more, particularly preferably 150 DEG C or more.Ingredient (A) upper limit value of glass transition temperature is not particularly limited, and for example, 400 DEG C.By the glass transition for making ingredient (A) Temperature is in aforementioned range, to have the heat resistance that can maintain pattern form, high-resolution etc. in semiconductor lithography process Performance improves.

The differential scanning calorimetry of the glass transition temperature of the ingredient (A) contained in aforementioned radiation line sensitive compositions point It analyses the crystallization exotherm amount found out and is preferably shorter than 20J/g.In addition, (crystallization temperature)-(glass transition temperature) be preferably 70 DEG C with Above, more preferably 80 DEG C or more, further preferably 100 DEG C or more, particularly preferably 130 DEG C or more.Crystallization exotherm amount is lower than When 20J/g or (crystallization temperature)-(glass transition temperature) are in aforementioned range, pass through spin coating radiation-sensitive composition Amorphous film easy to form, and film forming needed for capable of keeping for a long time resist, can be improved resolution ratio.

In present embodiment, aforementioned crystalline thermal discharge, crystallization temperature and glass transition temperature can be by using Shimadzus It makes the differential scanning calorimetric analysis of made DSC/TA-50WS and finds out.Sample about 10mg is added to aluminum non-sealed containers In, (50ml/ minutes) are warming up to fusing point or more with 20 DEG C/min of heating rate in stream of nitrogen gas.After quenching, again in nitrogen (30ml/ minutes) are warming up to fusing point or more with 20 DEG C/min of heating rate in gas air-flow.In turn, after quenching, again in nitrogen (30ml/ minutes) are warming up to 400 DEG C with 20 DEG C/min of heating rate in air-flow.By the difference in height of the baseline of step-like variation Midpoint (when specific heat becomes half) temperature as glass transition temperature (Tg), the temperature of the exothermic peak occurred thereafter is made For crystallization temperature.Thermal discharge is found out according to the area in the region surrounded by exothermic peak and baseline, as crystallization exotherm amount.

The ingredient (A) contained in aforementioned radiation line sensitive compositions is preferably: under normal pressure, 100 DEG C or less, preferably 120 DEG C or less, more preferable 130 DEG C or less, further preferred 140 DEG C or less, it is particularly preferred 150 DEG C hereinafter, sublimability is low.Distillation Property low expression: in thermogravimetric analysis, weight when being kept for 10 minutes at the specified temperature is reduced to 10% or less, preferably 5% Below, it is more preferably 3% or less, further preferably 1% or less, particularly preferably 0.1% or less.By keeping sublimability low, The pollution of the exposure device caused by degassing when so as to prevent because of exposure.In addition, low roughness and good can be obtained Pattern form.

The ingredient (A) contained in aforementioned radiation line sensitive compositions selected from propylene glycol methyl ether acetate (PGMEA), Propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-HEPTANONE, methyl phenyl ethers anisole, butyl acetate, ethyl propionate and Ethyl lactate and ingredient (A) is shown in the solvent of highest solvability, 1 mass % or more, more excellent is preferably dissolved at 23 DEG C Choosing dissolution 5 mass % or more, further preferably dissolution 10 mass % or more, it is therefore particularly preferred that selected from PGMEA, PGME, CHN and to (A) resist substrate show highest solvability solvent in, 20 mass % or more are dissolved at 23 DEG C, it is especially excellent 20 mass % or more are dissolved in choosing for PGMEA, at 23 DEG C.By meeting aforementioned condition, can be realized in actual production Use in semiconductor fabrication sequence.

[diazo naphthoquinone Photoactive compounds (B)]

The diazo naphthoquinone Photoactive compounds (B) contained in aforementioned radiation line sensitive compositions be include it is polymer and The diazo naphthoquinone substance of non-polymeric physical property diazo naphthoquinone Photoactive compounds, is used as long as being that typically in eurymeric anti-corrosion agent composition The substance for making photonasty ingredient (emulsion) is just not particularly limited, and can arbitrarily select using one kind or two or more.

As this emulsion, preferably make two nitrine sulfonic acid chloride of naphthoquinones, two nitrine sulfonic acid chloride of benzoquinones etc., with have can With compound obtained from the low molecular compound of the functional group of these acyl chlorides generation condensation reaction or high-molecular compound reaction. Herein, it as the functional group that can be condensed with acyl chlorides, is not particularly limited, for example: hydroxyl, amino etc., it is special It is not suitably hydroxyl.As the compound that can be condensed with acyl chlorides comprising hydroxyl, it is not particularly limited, such as can lift Out: hydroquinone, resorcinol, 2,4 dihydroxyl benzophenone, 2,3,4- trihydroxybenzophenone, 2,4,6- trihydroxy hexichol Ketone, 2,4,4 '-trihydroxybenzophenones, 2,3,4,4 '-tetrahydroxybenzophenones, 2,2 ', 4,4 '-tetrahydroxybenzophenones, The hydroxy benzophenones ketone such as 2,2 ', 3,4,6 '-pentahydroxybenzophenones；Bis- (2,4- dihydroxy phenyl) methane, bis- (2,3,4- tri- Hydroxy phenyl) the hydroxy phenyls alkanes such as methane, bis- (2,4- dihydroxy phenyl) propane；4,4 ', 3 ", 4 "-tetrahydroxys -3,5,3 ', 5 '-tetramethyl triphenyl methanes, 4,4 ', 2 ", 3 ", 4 "-penta hydroxy groups -3,5,3 ', the hydroxyls triphen such as 5 '-tetramethyl triphenyl methanes Methylmethane class etc..

In addition, as acyl chlorides such as two nitrine sulfonic acid chloride of naphthoquinones, two nitrine sulfonic acid chlorides of benzoquinones, for example, 1,2- naphthoquinones Two nitrine -5- sulfonic acid chlorides, two nitrine -4- sulfonic acid chloride of 1,2- naphthoquinones etc. are used as preferred example.

Aforementioned radiation line sensitive compositions for example preferably each ingredient is dissolved in solvent when in use be made uniformly it is molten Then liquid is filtered such as the filter with 0.2 μm or so of aperture as needed, thus prepare.

[characteristic of radiation-sensitive composition]

Aforementioned radiation line sensitive compositions can form amorphous film by spin coating.Furthermore it is possible to apply common In semiconductor fabrication process.Eurymeric corrosion-resisting pattern can be prepared respectively according to the type of used developer solution and minus is against corrosion Any one of pattern.

In the case where eurymeric corrosion-resisting pattern, spin coating aforementioned radiation line sensitive compositions and the amorphous film that is formed is right at 23 DEG C The solution rate of developer solution is preferablyBelow, more preferablyFurther preferably The solution rate isWhen following, developer solution is not dissolved in, resist is capable of forming.In addition, havingMore than Solution rate when, resolution ratio also improves sometimes.Speculate compound and tree this is because: by the inclusion of above-mentioned present embodiment Rouge is dissolved in the exposure portion of developer solution and insoluble in development as the deliquescent variation before and after the exposure of the resin of constituent The contrast at the interface in the unexposed portion of liquid becomes larger.In addition, there are also the effects for reducing LER, reducing defect.

In the case where minus corrosion-resisting pattern, spin coating aforementioned radiation line sensitive compositions and the amorphous film that is formed are at 23 DEG C Solution rate to developer solution is preferablyMore than.The solution rate isWhen above, it is soluble in developer solution, more It is suitable for resist.In addition, havingWhen the above solution rate, resolution ratio is also improved sometimes.Speculate this is because: The microcosmic surface portion dissolution of compound and resin comprising above-mentioned present embodiment as the resin of constituent, reduces LER.In addition, being reduced the effect of defect.

In the case where eurymeric corrosion-resisting pattern, spin coating aforementioned radiation line sensitive compositions and the amorphous film that is formed pass through After being heated after krf excimer laser, extreme ultraviolet, electron beam or X-ray israds are irradiated or at 20~500 DEG C , the part exposed be preferably to the solution rate of developer solution at 23 DEG CAbove, more preferablyFurther preferablyThe solution rate isWhen above, it is soluble in aobvious Shadow liquid, more suitable for resist.In addition, havingWhen solution rate below, resolution ratio is also improved sometimes.Speculate This is because: compound and resin comprising above-mentioned present embodiment are molten as the microcosmic surface portion of the resin of constituent Solution reduces LER.In addition, there is the effect for reducing defect.

In the case where minus corrosion-resisting pattern, spin coating aforementioned radiation line sensitive compositions and the amorphous film that is formed pass through After being heated after krf excimer laser, extreme ultraviolet, electron beam or X-ray israds are irradiated or at 20~500 DEG C The part exposed it is preferred to the solution rate of developer solution at 23 DEG CBelow, more preferably Further preferablyThe solution rate isWhen following, developer solution is not dissolved in, is capable of forming against corrosion Agent.In addition, havingWhen the above solution rate, resolution ratio is also improved sometimes.Speculate this is because: by upper State the deliquescent variation before and after the exposure of the compound and resin of present embodiment, be dissolved in the unexposed portion of developer solution with not The contrast for being dissolved in the interface of the exposure portion of developer solution becomes larger.In addition, there are also the effects for reducing LER, reducing defect.

[the compounding ratio of each ingredient]

In aforementioned radiation line sensitive compositions, the content of ingredient (A) is relative to feline amount (ingredient (A), again The summation of the arbitrarily used solid component such as quinoline quinone Photoactive compounds (B) and other compositions (D), it is same as below.) preferably 1~99 mass %, more preferably 5~95 mass %, further preferably 10~90 mass %, particularly preferably 25~75 matter Measure %.High sensitivity can be obtained when the content of ingredient (A) is in aforementioned range for aforementioned radiation line sensitive compositions And the pattern that roughness is small.

In aforementioned radiation line sensitive compositions, the content of diazo naphthoquinone Photoactive compounds (B) is relative to solid component Total weight (the arbitrarily used solid component such as ingredient (A), diazo naphthoquinone Photoactive compounds (B) and other compositions (D) it is total With it is same as below.) be preferably 1~99 mass %, more preferably 5~95 mass %, further preferably 10~90 mass %, Particularly preferably 25~75 mass %.The diazo naphthoquinone Photoactive compounds of the radiation-sensitive composition of present embodiment (B) when content is in aforementioned range, highly sensitive and small roughness pattern can be obtained.

[other compositions (D)]

In aforementioned radiation line sensitive compositions, in the range of not damaging the purpose of the present invention, as needed, as at Divide the ingredient other than (A) and diazo naphthoquinone Photoactive compounds (B), one kind or two or more acid agent, acid crosslinking can be added Agent, acid diffusion controlling agent, dissolution accelerator, the oxyacid for dissolving controlling agent, sensitizer, surfactant, organic carboxyl acid or phosphorus Or derivatives thereof, heat and/or light-cured catalyst, polymerization inhibitor, fire retardant, filler, coupling agent, heat-curing resin, light it is solid The property changed resin, dyestuff, pigment, thickener, lubricant, defoaming agent, levelling agent, ultraviolet absorbing agent, surfactant, coloring The various additives such as agent, nonionic surfactants.It should be noted that other compositions (D) is claimed sometimes in this specification For any ingredient (D).

In aforementioned radiation line sensitive compositions, the compounding ratio (ingredient (A)/diazo naphthoquinone photolytic activity chemical combination of each ingredient Object (B)/any ingredient (D)) in terms of the quality % of solid component benchmark,

Preferably 1~99/99~1/0~98,

More preferably 5~95/95~5/0~49,

Further preferably 10~90/90~10/0~10,

Particularly preferably 20~80/80~20/0~5,

Most preferably 25~75/75~25/0.

The compounding ratio of each ingredient can be selected in such a way that its summation becomes 100 mass % from each range.For Aforementioned radiation line sensitive compositions, when the compounding ratio of each ingredient is set as aforementioned range, not only roughness is excellent, Er Qieling The performances such as sensitivity, resolution ratio are also excellent.

Aforementioned radiation line sensitive compositions can within the scope without prejudice to the object of the present invention comprising present embodiment with Outer compound, resin.As such resin, can enumerate: novolac resin, polyacrylic acid, gathers polyvinylphenols Vinyl alcohol, phenylethylene-maleic anhydride resin and the polymer comprising acrylic acid, vinyl alcohol or vinyl phenol as monomeric unit Or their derivative etc..The compounding amount of these resins can suitably be adjusted according to the type of used ingredient (A), relative to 100 mass parts of ingredient (A), preferably 30 below the mass, more preferably 10 below the mass, further preferably 5 mass parts Below, 0 mass parts are particularly preferably.

[forming method of corrosion-resisting pattern]

The forming method of corrosion-resisting pattern based on present embodiment has following process: using the group of above-mentioned present embodiment After closing object (aforementioned anti-corrosion agent composition or radiation-sensitive composition) formation photoresist layer, to aforementioned photoresist layer Predetermined region illumination radiation line, the process developed.Specifically, the forming method of the corrosion-resisting pattern based on present embodiment Have following process: forming the process of etchant resist on substrate；The process that the etchant resist of formation is exposed；Resist with to aforementioned Lose the process that film is developed and forms corrosion-resisting pattern.Corrosion-resisting pattern in present embodiment can also be used as in multilayer technology Upper layer resist is formed.

As the method for forming corrosion-resisting pattern, it is not particularly limited, for example, following methods.Firstly, utilizing rotation Turn the coatings means such as coating, cast coat, roller coating cloth and is coated with aforementioned anti-corrosion agent composition or radiation on known substrate Line sensitive compositions, are consequently formed etchant resist.Known substrate is not particularly limited, such as can exemplify electronic component Substrate, the substrate for being formed on defined wiring pattern etc..More specifically, can enumerate: Silicon Wafer, copper, chromium, The metal substrate such as iron, aluminium, glass substrate etc..It as the material of wiring pattern, such as can enumerate: copper, aluminium, nickel, gold etc..Separately Outside, it also can according to need the film that inorganic system and/or organic system are set on aforesaid base plate.As the film of inorganic system, can enumerate Inorganic anti-reflective film (inorganic BARC) out.As the film of organic system, organic anti-reflective film (organic BARC) can be enumerated.It can also be with It is surface-treated using hexa-methylene disilazane etc..

Then, coated substrate is heated as needed.Heating condition is according to the compounding group of anti-corrosion agent composition Change at equal, preferably 20~250 DEG C, more preferably 20~150 DEG C.By heating, make resist to substrate sometimes Adaptation improves, therefore it is preferred that.Then, using selected from by visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), any number of radiation in the group that X-ray and ion beam form, etchant resist is exposed into desired pattern.Expose item Part etc. can suitably be selected according to the compounding of anti-corrosion agent composition or radiation-sensitive composition composition etc..This embodiment party In formula, for the high-precision fine pattern being stably formed in exposure, preferably heated after irradiation with radiation.Fire-bar Part changes, preferably 20~250 DEG C, more excellent according to the compounding of anti-corrosion agent composition or radiation-sensitive composition composition etc. It is selected as 20~150 DEG C.

Then, developed using developer solution to exposed etchant resist, thus corrosion-resisting pattern as defined in being formed.As preceding State developer solution, preferably select solubility parameter (SP value) close to the above-mentioned present embodiment used compound and resin it is molten Ketone series solvent, ester series solvent, alcohol series solvent, acid amides series solvent, ether series solvent isopolarity solvent, hydrocarbon system solvent can be used in agent Or aqueous alkali.

As ketone series solvent, for example, 1- octanone, methyln-hexyl ketone, 1- nonanone, methyl n-heptyl ketone, acetone, 4- heptanone, 1- oneself Ketone, methyl-n-butyl ketone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenylacetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetyl group third Ketone, acetonyl acetone, ionone, diacetone alcohol, acetyl group carbitol, acetophenone, methyl naphthyl ketone, isophorone, carbonic acid are sub- Propyl ester etc..

As ester series solvent, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, acetic acid penta Ester, propylene glycol methyl ether acetate, ethylene glycol monoethylether acetate, butyl carbitol acetate, diethylene glycol monoethyl ether Acetic acid esters, ethyl -3- ethoxy-c acid esters, 3- methoxybutyl acetic acid esters, 3- methyl -3- methoxybutyl acetic acid esters, formic acid Methyl esters, Ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate etc..

As alcohol series solvent, for example, methanol, ethyl alcohol, normal propyl alcohol, isopropanol (2- propyl alcohol), n-butanol, Zhong Ding Alcohol, ethylene glycol, the diethyls two such as alcohol, the tert-butyl alcohol, isobutanol, n-hexyl alcohol, 4- methyl -2- amylalcohol, n-heptanol, n-octyl alcohol, Decanol Two alcohol series solvent such as alcohol, triethylene glycol, glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, dihydroxypropane single-ether, Glycol ether series solvents such as diethylene glycol monomethyl ether, Triethylene glycol ethyl ether, methoxy butanol etc..

As ether series solvent, for example, foregoing glycols ether series solvent and dioxane, tetrahydrofuran Deng.

As acid amides series solvent, n-methyl-2-pyrrolidone, n,N-dimethylacetamide, N, N- bis- can be used for example Methylformamide, hexamethyl phosphoramide, 1,3- dimethyl -2- imidazolidinone etc..

As hydrocarbon system solvent, for example: the aromatic hydrocarbon series solvents such as toluene, dimethylbenzene, pentane, hexane, octane, The aliphatic hydrocarbons series solvent such as decane.

Aforementioned solvents can mix it is a variety of, can also in the range of with performance with solvent, water in addition to the foregoing It is used in mixed way.Wherein, in order to give full play to effect of the invention, the moisture content as developer solution entirety is lower than 70 mass %, excellent Choosing is particularly preferably substantially free of water lower than 50 mass %, more preferably less than 30 mass %, even more preferably below 10 mass % Point.That is, content of the organic solvent relative to developer solution, the total amount relative to developer solution is 30 mass % or more and 100 mass % Below, be preferably 50 mass % or more and 100 mass % or less, more preferably 70 mass % or more and 100 mass % or less, into One step is preferably 90 mass % or more and 100 mass % or less, particularly preferably 95 mass % or more and 100 mass % or less.

As aqueous alkali, for example, single alkanamine class, dioxane amine or three alkanamine classes, monoalkanolamine class, dioxane The alkali compounds such as alcamines or tri-alkanolamine class, hetero ring type amine, tetramethylammonium hydroxide (TMAH), choline.

In particular, as developer solution, from the viewpoint of the etch resistant properties such as resolution ratio, the roughness for improving corrosion-resisting pattern, Preferably comprise at least one kind of solvent in ketone series solvent, ester series solvent, alcohol series solvent, acid amides series solvent and ether series solvent Developer solution.

The vapour pressure of developer solution is preferably 5kPa or less, further preferably 3kPa or less at 20 DEG C, is particularly preferably 2kPa or less.By the way that the vapour pressure of developer solution is set as 5kPa hereinafter, can inhibit steaming of the developer solution on substrate or in Shadow showing cup It sends out, the temperature uniformity in wafer face improves, and as a result the dimensional homogeneity in wafer face improves.

As the concrete example with 5kPa vapour pressure below, can enumerate 1- octanone, methyln-hexyl ketone, 1- nonanone, methyl n-heptyl ketone, The ketone series solvents such as 4- heptanone, methyl-n-butyl ketone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenylacetone, methyl iso-butyl ketone (MIBK)；Second Acid butyl ester, pentyl acetate, propylene glycol methyl ether acetate, ethylene glycol monoethylether acetate, butyl carbitol acetate, two Ethylene glycol monoethylether acetate, ethyl -3- ethoxy-c acid esters, 3- methoxybutyl acetic acid esters, 3- methyl -3- methoxybutyl The ester series solvents such as acetic acid esters, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate；Normal propyl alcohol, isopropanol, The alcohol systems such as n-butanol, sec-butyl alcohol, the tert-butyl alcohol, isobutanol, n-hexyl alcohol, 4- methyl -2- amylalcohol, n-heptanol, n-octyl alcohol, Decanol are molten Agent；Two alcohol series solvent such as ethylene glycol, diethylene glycol, triethylene glycol；Glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol list second The glycol ether series solvents such as ether, dihydroxypropane single-ether, diethylene glycol monomethyl ether, Triethylene glycol ethyl ether, methoxy butanol；Four The ether series solvents such as hydrogen furans；The amides such as n-methyl-2-pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide system Solvent；The aromatic hydrocarbon series solvents such as toluene, dimethylbenzene；The aliphatic hydrocarbons series solvent such as octane, decane.

As the concrete example with particularly preferred range 2kPa vapour pressure below, can enumerate 1- octanone, methyln-hexyl ketone, The ketone series solvents such as 1- nonanone, methyl n-heptyl ketone, 4- heptanone, methyl-n-butyl ketone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenylacetone； Butyl acetate, pentyl acetate, propylene glycol methyl ether acetate, ethylene glycol monoethylether acetate, butyl carbitol acetate, Diethylene glycol monoethyl ether acetic acid esters, ethyl -3- ethoxy-c acid esters, 3- methoxybutyl acetic acid esters, 3- methyl -3- methoxyl group fourth The ester series solvents such as yl acetate, ethyl lactate, butyl lactate, propyl lactate；N-butanol, sec-butyl alcohol, the tert-butyl alcohol, isobutanol, just The alcohol series solvents such as hexanol, 4- methyl -2- amylalcohol, n-heptanol, n-octyl alcohol, Decanol；Ethylene glycol, diethylene glycol, triethylene glycol etc. Two alcohol series solvents；Glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, dihydroxypropane single-ether, diethylene glycol list first The glycol ether series solvents such as ether, Triethylene glycol ethyl ether, methoxy butanol；N-methyl-2-pyrrolidone, N, N- dimethyl second The aromatic hydrocarbon series solvents such as the acid amides series solvents such as amide, N,N-dimethylformamide, dimethylbenzene；The aliphatic hydrocarbons such as octane, decane Series solvent.

In developer solution, the suitable surfactant of addition can according to need.

It as surfactant, is not particularly limited, ionic, nonionic fluorine system and/or silicon can be used for example It is surfactant etc..As these fluorine and/or silicon-based surfactant, for example: Japanese Unexamined Patent Application 62-36663 Number bulletin, Japanese Unexamined Patent Application 61-226746 bulletin, Japanese Unexamined Patent Application 61-226745 bulletin, Japanese Unexamined Patent Application 62- No. 170950 bulletins, Japanese Unexamined Patent Application 63-34540 bulletin, Japanese Unexamined Patent Publication 7-230165 bulletin, Japanese Unexamined Patent Publication 8- No. 62834 bulletins, Japanese Unexamined Patent Publication 9-54432 bulletin, Japanese Unexamined Patent Publication 9-5988 bulletin, U.S. Patent No. 5405720 Number specification, No. 5360692 specifications of United States Patent (USP), No. 5529881 specifications of United States Patent (USP), United States Patent (USP) 5296330 say Bright book, No. 5436098 specifications of United States Patent (USP), No. 5576143 specifications of United States Patent (USP), No. 5294511 specifications of United States Patent (USP), The surfactant that No. 5824451 specifications of United States Patent (USP) are recorded, the preferably surfactant of nonionic.As nonionic Property surfactant, be not particularly limited, further preferably use fluorine system surfactant or silicon-based surfactant.

The dosage of surfactant is usually 0.001~5 mass %, preferably 0.005~2 relative to the total amount of developer solution Quality %, further preferably 0.01~0.5 mass %.

It as developing method, such as can apply: substrate is impregnated to the method for certain time in the slot for filling developer solution (infusion process)；Developer solution and static certain time are carried on the surface of the substrate using surface tension, thus the method developed (paddle method)；To the method (spray-on process) of substrate surface spray development liquid；On the substrate rotated with constant speed, make on one side Developer solution is applied delivery nozzle and is scanned with constant speed, persistently applies out method (dynamic allocation method) of developer solution etc. on one side.Figure The time that case is developed is not particularly limited, and preferably 10 seconds~90 seconds.

In addition, other solvents can be replaced on one side after the process developed, implement the process for stopping development on one side.

It is preferred that after development including the process cleaned using the flushing liquor comprising organic solvent.

As flushing liquor used in the flushing process after development, as long as insoluble by being crosslinked cured corrosion-resisting pattern It is just not particularly limited, solution or water comprising common organic solvents can be used.As aforementioned flushing liquor, it is preferable to use containing It is at least one kind of organic in hydrocarbon system solvent, ketone series solvent, ester series solvent, alcohol series solvent, acid amides series solvent and ether series solvent The flushing liquor of solvent.More preferably after development using containing selected from molten by ketone series solvent, ester series solvent, alcohol series solvent, amide system The flushing liquor of at least one kind of organic solvent in the group of agent composition is come the process cleaned.In turn, it more preferably uses after development Flushing liquor containing alcohol series solvent or ester series solvent is come the process cleaned.In turn, it more preferably uses after development and contains 1 yuan The flushing liquor of alcohol is come the process cleaned.The flushing liquor of 1 yuan of alcohol containing 5 or more carbon number is particularly preferably used after development The process cleaned.The time that pattern is rinsed is not particularly limited, preferably 10 seconds~90 seconds.

Herein, as 1 yuan of alcohol used in the flushing process after development, straight-chain, branched, cricoid 1 can be enumerated First alcohol, specifically can be used: n-butyl alcohol, 2- butanol, 3- methyl-1-butanol, tert-butyl alcohol, 1- amylalcohol, 2- amylalcohol, 1- oneself Alcohol, 4- methyl -2- amylalcohol, 1-heptanol, 1- octanol, 2- hexanol, cyclopentanol, 2- enanthol, sec-n-octyl alcohol, 3- hexanol, 3- enanthol, 3- are pungent Alcohol, 4- octanol etc. can be used as 1 yuan of alcohol of particularly preferred 5 or more carbon number: 1- hexanol, 2- hexanol, 4- methyl -2- penta Alcohol, 1- amylalcohol, 3- methyl-1-butanol etc..

Aforesaid components can mix a variety of, can also be used in mixed way with the organic solvent other than aforesaid ingredients.

Moisture content in flushing liquor is preferably 10 mass % or less, more preferably 5 mass % or less, particularly preferably 3 matter Measure % or less.By making 10 mass % of moisture content hereinafter, available more good developing property.

The vapour pressure of the flushing liquor used after development is preferably 0.05kPa or more and 5kPa or less, further at 20 DEG C Preferably 0.1kPa or more and 5kPa or less, most preferably 0.12kPa or more and 3kPa or less.By the vapour pressure for making flushing liquor For 0.05kPa or more and 5kPa hereinafter, the temperature uniformity in wafer face further increases, in turn, further suppress by rinsing Liquid is impregnated with caused swelling, and the dimensional homogeneity in wafer face is better.

Can also be added in flushing liquor suitable surfactant come using.

It rinses in process, using the flushing liquor comprising above-mentioned organic solvent, the wafer to be developed is carried out at cleaning Reason.The method of cleaning treatment is not particularly limited, such as can apply: persistently applying out and rushes on the substrate rotated with constant speed The method (method of spin coating) of washing lotion；Substrate is impregnated to the method (infusion process) of certain time in the slot for filling flushing liquor；It is right Substrate surface is sprayed method (spray-on process) of flushing liquor etc., wherein it is started the cleaning processing preferably by rotating coating, and It rotates substrate with the revolving speed of 2000rpm~4000rpm, flushing liquor is removed from substrate.

After forming corrosion-resisting pattern, pattern wiring substrate is obtained by etching.About the method for etching, can by using etc. The dry ecthing of plasma gas and using method well known to wet etching of aqueous slkali, copper chloride solution, ferric chloride solution etc. etc. come It carries out.

Plating can also be carried out after forming corrosion-resisting pattern.As aforementioned plating method, for example, have copper facing, solder plating, nickel plating, It is gold-plated etc..

Residual corrosion-resisting pattern after etching can use organic solvent and be removed.As aforementioned organic solvents, can enumerate Out: PGMEA (propylene glycol methyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) etc..As aforementioned removing side Method, such as dipping method, spray pattern can be enumerated etc..In addition, the circuit board for being formed with corrosion-resisting pattern can be laminates Line substrate, it is possible to have path through-hole.

Circuit board obtained in present embodiment can also by after corrosion-resisting pattern is formed in a vacuum evaporation metal, Then it is formed with the method for solution dissolution corrosion-resisting pattern, i.e. removing (lift-off) method.

[photoetching towards lower membrane purposes forms composition with film]

The composition of present embodiment be also used as the photoetching towards lower membrane purposes with film formed composition (hereinafter, Also referred to as lower layer's film formation material).Lower layer's film formation material contains compound and resin composition selected from above-mentioned present embodiment Group at least one kind of substance.In present embodiment, from coating and quality stability aspect, aforementioned substances are under In tunic forming material, preferably 1~100 mass %, more preferably 10~100 mass %, further preferably 50~100 matter Measure %, particularly preferably 100 mass %.

Aforementioned lower layer's film formation material can be applied to wet process, and heat resistance and elching resistant are excellent.In turn, this embodiment party Due to using aforementioned substances, the deterioration of film when high-temperature baking is suppressed lower layer's film formation material of formula, is capable of forming To the elching resistant of oxygen plasma etch etc. also excellent lower membrane.In turn, aforementioned lower layer's film formation material and resist layer Adaptation is also excellent, therefore can obtain excellent corrosion-resisting pattern.It should be noted that aforementioned lower layer's film formation material is will not It damages in the range of effect of the invention, also may include known lower layer film for lithography forming material etc..

[solvent]

Aforementioned lower layer's film formation material can contain solvent.As solvent used in aforementioned lower layer's film formation material, only At least to dissolve above-mentioned substance can be suitable for using well known solvent.

As the concrete example of solvent, be not particularly limited, such as can enumerate: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), The ketone series solvents such as cyclohexanone；The cellosolves series solvent such as propylene glycol monomethyl ether, propylene glycol methyl ether acetate；Ethyl lactate, acetic acid The esters such as methyl esters, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methoxy methyl propionate, hydroxy-methyl isobutyl acid Series solvent；The alcohol series solvents such as methanol, ethyl alcohol, isopropanol, 1- ethyoxyl -2- propyl alcohol；The aromatic series such as toluene, dimethylbenzene, methyl phenyl ethers anisole It is hydrocarbon etc..These solvents can be used alone or two or more is applied in combination.

In aforementioned solvents, from safety aspect, particularly preferred cyclohexanone, propylene glycol monomethyl ether, propylene glycol list first Ether acetic acid ester, ethyl lactate, hydroxy-methyl isobutyl acid, methyl phenyl ethers anisole.

The content of solvent is not particularly limited, from the viewpoint of dissolubility and film are upper, relative to aforementioned lower membrane shape At 100 mass parts of material, preferably 100~10000 mass parts, more preferably 200~5000 mass parts are more preferably 200~1000 mass parts.

[crosslinking agent]

It can also contain as needed from viewpoints, aforementioned lower layer's film formation materials such as inhibition mixing (intermixing) Crosslinking dose.The crosslinking agent that can be used in present embodiment is not particularly limited, and International Publication No. 2013/ can be used for example The acid crosslinking agent recorded in No. 024779.

As the concrete example for the crosslinking agent that can be used in present embodiment, for example, phenolic compounds, epoxidation Close object, cyanate esters, amino-compound, benzoxazine compound, acrylate compounds, melamine compound, guanidine Amine compounds, glycoluril compounds, carbamide compound, isocyanate compound, azido compound etc., but it is not particularly limited in these. These crosslinking agents can be used alone or combine two or more use.Among them, preferably benzoxazine compound, epoxy Compound or cyanate esters, from the viewpoint of elching resistant raising, more preferable benzoxazine compound.

Active group possessed by these crosslinking agents (phenolic hydroxyl group, epoxy group, cyanic acid ester group, amino or benzoxazine Phenolic hydroxyl group made of the open loop of alicyclic ring position) it is sent out in addition to carrying out addition reaction with the carbon-to-carbon double bond for constituting dimaleoyl imino Except raw crosslinking, 2 carbon-to-carbon double bonds possessed by the bismaleimide compound of present embodiment can polymerize and hand over Connection.

As aforementioned epoxy compound, well known substance can be used, there can be 2 or more epoxy groups from 1 molecule It is selected in person.It is 5,5 '-tetramethyls-Bisphenol F, bisphenol S, fluorenes bis-phenol, 2,2 '-bis- for example, bisphenol-A, Bisphenol F, 3,3 ' Phenol, 3,3 ', the epoxides of 2 yuan of phenols, three-such as 5,5 '-tetramethyls -4,4 '-dihydroxy bis-phenol, resorcinol, naphthalene glycols (4- hydroxy phenyl) methane, 1,1,2,2- tetra- (4- hydroxy phenyl) ethane, three (2,3- glycidyl) isocyanuric acid esters, three hydroxyl first Methylmethane triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, trihydroxyethyl ethane triglycidyl ether, phenol novolac The ring of the condensation copolymerization resin of the epoxides of 3 yuan of varnish, o-cresol novolak etc. or more of phenols, bicyclopentadiene and phenols Oxide, the epoxides of the phenol aralkyl resin class synthesized by phenols and paraxylene dichloride etc., by phenols and double The epoxides of the biphenyl aralkyl-type phenol resin of the synthesis such as chloromethyl biphenyl, by aphthols and paraxylene dichloride etc. The epoxides etc. of the naphthols aralkyl resin class of synthesis.These epoxy resin may be used alone, can also be used in combination 2 kinds More than.Wherein, from the viewpoint of heat resistance and dissolubility, preferably by phenol aralkyl resin class, biphenyl aralkyl resin class Solid-like epoxy resin under the room temperature such as obtained epoxy resin.

As aforementioned cyanate esters, as long as, with the compound of 2 or more cyanic acid ester groups, not have in 1 molecule Especially limitation, can be used well known compound.In present embodiment, as preferred cyanate esters, it can enumerate 1 The hydroxyl of compound in molecule with 2 or more hydroxyls is replaced into the cyanate esters of the structure of cyanic acid ester group.In addition, cyanogen Ester compound preferably has aromatic group, can be suitble to the structure being directly connected to using cyanic acid ester group and aromatic group Compound.As this cyanate esters, for example: bisphenol-A, Bisphenol F, bis-phenol M, bis-phenol P, bis-phenol E, phenol phenol Novolac resin, cresol novolac resin, dicyclopentadiene novolac resin, tetramethyl Bisphenol F, bisphenol A novolac Resin, brominated bisphenol A, brominated phenol novolac resin, 3 function phenol, 4 function phenol, naphthalene type phenol, biphenyl type phenol, phenol aralkyl Base resin, biphenyl aralkyl resin, naphthols aralkyl resin, bicyclopentadiene aralkyl resin, ester ring type phenol, phosphorous phenol Deng hydroxyl be replaced into the structure person of cyanic acid ester group.These cyanate esters can be used alone or two or more is applied in combination. In addition, aforementioned cyanate esters can be any form of monomer, oligomer and resin.

As aforesaid amide, it may be exemplified m-phenylene diamine (MPD), p-phenylenediamine, 4,4 '-diaminodiphenyl-methanes, 4, 4 '-diamino-diphenyl propane, 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, 3,3 '-diaminodiphenyl ethers, 4, 4 '-diamino diphenyl sulfones, 3,4 '-diamino diphenyl sulfones, 3,3 '-diamino diphenyl sulfones, 4,4 '-diamino-diphenyl sulphur Bis- (4- amino-benzene oxygen) benzene of ether, 3,4 '-diamino diphenyl sulfides, 3,3 '-diamino diphenyl sulfides, 1,4-, 1,3- are bis- Bis- (3- amino-benzene oxygen) benzene of (4- amino-benzene oxygen) benzene, 1,4-, bis- (3- amino-benzene oxygen) benzene of 1,3-, bis- [4- (4- aminobenzenes Oxygroup) phenyl] sulfone, bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2,2-, bis- [4- (3- amino-benzene oxygen) phenyl] third of 2,2- Alkane, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 4,4 '-bis- (3- amino-benzene oxygen) biphenyl, bis- [4- (4- amino-benzene oxygen) benzene Base] ether, bis- [4- (3- amino-benzene oxygen) phenyl] ethers, bis- (4- aminophenyl) fluorenes of 9,9-, 9,9- bis- (4- amino -3- chlorphenyls) Bis- (4- amino -3- fluorophenyl) fluorenes of fluorenes, 9,9-, o-tolidine, tolidine, 4,4 '-diaminobenzene anilids, 2, 2 '-bis- (trifluoromethyl) -4,4 '-benzidines, 4- aminophenyl -4-aminobenzoic acid ester, 2- (4- aminophenyl) -6- ammonia Base benzoxazoles etc..In turn, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino-diphenyl propane, 4,4 '-two can be enumerated Amino-diphenylethers, 3,4 '-diaminodiphenyl ethers, 3,3 '-diaminodiphenyl ethers, 4,4 '-diamino diphenyl sulfones, 3,3 '-diaminos Bis- (4- amino-benzene oxygen) benzene of base diphenyl sulfone, 1,4-, bis- (4- amino-benzene oxygen) benzene of 1,3-, 1,4- bis- (3- amino-benzene oxygens) Bis- (3- amino-benzene oxygen) benzene of benzene, 1,3-, bis- [4- (4- amino-benzene oxygen) phenyl] sulfones, the bis- [4- (4- amino-benzene oxygen) of 2,2- Phenyl] it is propane, bis- [4- (3- amino-benzene oxygen) phenyl] propane of 2,2-, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, 4,4 '-bis- The virtues such as (3- amino-benzene oxygen) biphenyl, bis- [4- (4- amino-benzene oxygen) phenyl] ethers, bis- [4- (3- amino-benzene oxygen) phenyl] ethers Fragrant race's amine, diaminocyclohexane, diamino-dicyclohexyl methane, dimethyl-diamino-dicyclohexyl methane, tetramethyl-two Amino bicyclic hexyl methane, diaminocyclohexyl propane, diamino bicyclic [2.2.1] heptane, bis- (amino methyls)-are bicyclic [2.2.1] heptane, 3 (4), 8 (9)-bis- (amino methyl) tricyclic [5.2.1.02,6] decane, the bis- aminomethyl cyclohexanes of 1,3-, The ester ring types such as isophorone diamine amine, ethylenediamine, hexamethylene diamine, eight methylene diamines, decamethylene diamine, two sub- second Aliphatic amine such as base triamine, trien etc..

As aforementioned benzoxazine compound, the P-d obtained by two functionality Diamines and simple function phenols can be enumerated Type benzoxazine, the F-a type benzoxazine obtained by mono-functional's Diamines and two functionality phenols etc..

As the concrete example of aforementioned melamine compound, for example, hexamethylolmelamine, hexa methoxy Methyl melamine, hexamethylolmelamine 1~6 methylol through or mixtures thereof methoxymethylated compound, Hexa methoxy ethyl melamine, six pivaloyloxymethyl melamines, hexamethylolmelamine 1~6 of methylol warp Or mixtures thereof compound of pivaloyloxymethyl etc..

As the concrete example of aforementioned guanamines compound, for example, tetra methylol guanamines, tetramethoxymethyl guanamines, 1~4 methylol of tetra methylol guanamines is through or mixtures thereof methoxymethylated compound, tetramethoxy ethyl guanidine Or mixtures thereof amine, four acyloxy guanamines, compound through pivaloyloxymethyl of 1~4 methylol of tetra methylol guanamines Deng.

As the concrete example of aforementioned glycoluril compounds, for example, tetramethylol glycoluril, tetramethoxy glycoluril, tetramethyl Oxygroup methyl glycoluril, 1~4 of methylol of tetramethylol glycoluril through or mixtures thereof methoxymethylated compound, four Or mixtures thereof 1~4 compound through pivaloyloxymethyl of the methylol of methylol glycoluril etc..

As the concrete example of aforementioned urea compound, for example, tatramethylol urea, tetramethoxymethyl urea, four hydroxyl first 1~4 methylol of base urea is through or mixtures thereof methoxymethylated compound, tetramethoxy ethyl carbamide etc..

In addition, from the viewpoint of bridging property raising, can be used at least one allyl in present embodiment Crosslinking agent.As the concrete example of the crosslinking agent at least one allyl, the bis- (3- allyl -4- hydroxy benzenes of 2,2- can be enumerated Base) propane, bis- (3- allyl -4- hydroxy phenyl) propane of 1,1,1,3,3,3- hexafluoro -2,2-, bis- (3- allyl -4- hydroxy benzenes Base) the allyls phenols, 2,2- such as sulfone, bis- (3- allyl -4- hydroxy phenyl) thioethers, bis- (3- allyl -4- hydroxy phenyl) ethers Bis- (3- allyl -4- cyanato- phenyl) propane, 1,1,1,3,3,3- hexafluoro -2,2- bis- (3- allyl -4- cyanato- phenyl) Propane, bis- (3- allyl -4- cyanato- diphenyl) sulfones, bis- (3- allyl -4- cyanato- phenyl) thioethers, bis- (3- allyls - 4- cyanato- phenyl) the allyl cyanides esters of gallic acid such as ether, diallyl phthalate, diallyl isophthalate, to benzene two Formic acid diallyl, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythrite allyl ether etc., but do not limit In these examples.They can be for individually or mixture of more than two kinds.Among these, bis- (the 3- allyls of preferably 2,2- Base -4- hydroxy phenyl) propane, 1,1,1,3,3,3- hexafluoro -2,2- bis- (3- allyl -4- hydroxy phenyl) propane, bis- (3- allyls Base -4- hydroxy phenyl) allyls such as sulfone, bis- (3- allyl -4- hydroxy phenyl) thioethers, bis- (3- allyl -4- hydroxy phenyl) ethers Base phenols.

The content of crosslinking agent in composition is not particularly limited, relative to the group comprising above compound and/or resin It closes object and adds up to 100 mass parts of quality, preferably 0.1~100 mass parts, more preferably 5~50 mass parts, further preferred 10~ 40 mass parts.By making the content aforementioned range of crosslinking agent, to there is inclining for the generation of the mixing phenomena of inhibition and resist layer To in addition, having the tendency that can be improved anti-reflection effect, can be improved the film formative after crosslinking.

[crosslinking accelerator]

In the lower membrane film formation material of present embodiment, it can according to need using for promoting crosslinking, curing reaction Crosslinking accelerator.

As aforementioned crosslinking accelerator, as long as promoting crosslinking, curing reaction, there is no particular limitation, for example, Amine, imidazoles, organic phosphine, lewis acid etc..These crosslinking accelerators can be used alone or be applied in combination 2 kinds with On.In these, preferably imidazoles or organic phosphine, from the viewpoint of the low temperature of crosslinking temperature, more preferable imidazoles.

As aforementioned crosslinking accelerator, it is not limited to hereinafter, for example, 1,8- diazabicyclo (5,4,0) 11 Carbon -7- alkene, triethylenediamine, benzyl dimethylamine, triethanolamine, dimethylaminoethanol, three (dimethylaminomethyl) benzene The tertiary amines such as phenol, 2-methylimidazole, 2- phenylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl -4-methylimidazole, 2- heptadecyl The imidazoles such as imidazoles, 2,4,5- triphenylimidazolyl, tributylphosphine, methyldiphenyl base phosphine, triphenylphosphine, diphenylphosphine, Phenylphosphine Etc. organic phosphine, tetraphenylphosphoniphenolate tetraphenylborate, tetraphenylphosphoniphenolate ethyl triphenyl borate, the 4-butyl-phosphonium tetrabutyl The four Qu Dai Phosphonium such as borate, four substituted boracic acid ester, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine four Tetraphenyls boron salt such as phenyl boronate etc..

As the content of crosslinking accelerator, in general, preferably 0.1 when total quality of composition is set as 100 mass parts ~10 mass parts, from the viewpoint of the easiness of control and economy, more preferably 0.1~5 mass parts are more preferably 0.1~3 mass parts.

[radical polymerization initiator]

It can according to need compounding radical polymerization initiator in lower layer's film formation material of present embodiment.As freedom Base polymerization initiator can be the Photoepolymerizationinitiater initiater being polymerize by Light lnduced Free Radicals, or caused freely by heat The thermal polymerization of base polymerization.As radical polymerization initiator, such as can be for selected from ketone system Photoepolymerizationinitiater initiater, organic It is at least one kind of in the group of peroxide system polymerization initiator and azo system polymerization initiator composition.

It as this radical polymerization initiator, is not particularly limited, can be suitable for using the substance used in the past.Such as 1- hydroxycyclohexylphenylketone, benzil dimethyl ketal, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 1- can be enumerated [4- (2- hydroxyl-oxethyl)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, 2- hydroxyl -1- { 4- [4- (2- hydroxyl -2- first Base-propiono)-benzyl] phenyl } it is -2- methylpropane -1- ketone, 2,4,6- trimethylbenzoy-dipheny-phosphine oxide, double Ketone system Photoepolymerizationinitiater initiater, methyl ethyl ketone peroxide, the peroxidating hexamethylenes such as (2,4,6- trimethylbenzoyl)-phenyl phosphine oxide Bis- (the tertiary hexyl peroxides of ketone, methyl cyclohexanone, methyl acetoacetic ester, acetyl peroxide yl acetate, 1,1- Change) -3,3,5- trimethyl-cyclohexane, bis- (the tert-hexyl peroxide)-hexamethylenes of 1,1-, bis- (tert-butyl hydroperoxide) -3,3 1,1-, Bis- (the tert-butyl hydroperoxide) -2- hexahydrotoluenes of 5- trimethyl-cyclohexane, 1,1-, bis- (the tert-butyl hydroperoxide)-hexamethylenes of 1,1-, Bis- (tert-butyl hydroperoxide) cyclododecanes of 1,1-, bis- (tert-butyl hydroperoxide) butane of 1,1-, bis- (the 4,4- di-t-butyl peroxides of 2,2- Change cyclohexyl) propane, hydrogen peroxide is to terpane, hydrogen peroxide diisopropyl benzene, 1,1,3,3- tetramethyl butyl hydroperoxidation Object, hydrogen peroxide cumene, tert-hexyl peroxide hydrogen, tert-butyl hydroperoxide, α, bis- (tert-butyl hydroperoxide) diisopropyls of α '- Bis- (tert-butyl hydroperoxide) hexanes of benzene, dicumyl peroxide, 2,5- dimethyl -2,5-, tert-butyl cumyl peroxide, two uncles Bis- (tert-butyl hydroperoxide) hexins -3 of butylperoxide, 2,5- dimethyl -2,5-, isobutyryl peroxide, 3,5,5- tri- Methyl hexanoyl base peroxide, sim peroxides, lauroyl peroxide, stearyl peroxide, succinic acid mistake Oxide, toluyl benzoyl base peroxide, benzoyl peroxide, peroxy dicarbonate di-n-propyl ester, mistake Aoxidize bis- (4- tert-butylcyclohexyl) esters of two diisopropyl carbonates, dicetyl peroxydicarbonate, two -2- ethyoxyl second of dicetyl peroxydicarbonate Ester, the own ester of two -2- ethyoxyl of dicetyl peroxydicarbonate, two -3- methoxybutyl of dicetyl peroxydicarbonate, dicetyl peroxydicarbonate two-secondary Butyl ester, dicetyl peroxydicarbonate two (3- methyl -3- methoxybutyl) ester, α, bis- (the new capryl peroxidating) diisopropyl benzenes of α ' -, The withered ester of peroxidating neodecanoic acid, peroxidating neodecanoic acid 1,1,3,3- tetramethyl butyl ester, peroxidating neodecanoic acid 1- cyclohexyl -1- methyl second The tertiary own ester of ester, peroxidating neodecanoic acid, new peroxide tert-butyl caprate, talkyl peropivalate, the tertiary fourth of peroxidating pivalic acid Ester, 1,1,3,3- tetramethyl butyl peroxidating -2 ethyl hexanoic acid ester, bis- (the 2- ethylhexanoylperoxies of 2,5- dimethyl -2,5- Change) capronate, 1- cyclohexyl -1- Methylethyl peroxidating -2 ethyl hexanoic acid ester, tert-hexyl peroxide -2 ethyl hexanoic acid ester, uncle Butyl peroxy -2 ethyl hexanoic acid ester, single carbon acid tert-hexyl peroxide isopropyl ester, peroxidating tert-butyl isobutyrate, peroxidating horse Come tert-butyl acrylate, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, the peroxylauric acid tert-butyl ester, single carbon acid tert-butyl mistake Aoxidize isopropyl ester, single carbon acid tert-butyl hydroperoxide -2- ethylhexyl, peroxide acetic acid butyl ester, tert-butyl hydroperoxide-toluene Formylbenzoate ester, diphenyl peroxide t-butyl formate, bis- (tert-butyl hydroperoxide) isophthalic acid esters, 2,5- dimethyl- Bis- (toluyl groups peroxidating) hexanes of 2,5-, the tertiary own ester of diphenyl peroxide formic acid, the bis- (benzoyls of 2,5- dimethyl -2,5- Base peroxidating) hexane, single carbon acid tert-butyl hydroperoxide allyl ester, tert-butyl trimethyl silyl peroxide, 3,3 ', 4, The polymerization of the organic peroxides systems such as 4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2,3- dimethyl -2,3- diphenyl butane Initiator.

Furthermore it is also possible to enumerate 2- phenylazo -4- methoxyl group -2,4- methyl pentane nitrile, 1- [(1- cyano -1- methyl second Base) azo] formamide, 1,1 '-azos bis- (hexamethylene -1- formonitrile HCNs), 2,2 '-azos bis- (2- methylbutyronitriles), 2,2 '-azos two Isobutyronitrile, 2,2 '-azos bis- (2,4- methyl pentane nitriles), 2,2 '-azos bis- (2- methyl-prop amidine) dihydrochlorides, 2,2 '-azos Bis- (the third amidine of 2- Methyl-N-phenyl) dihydrochlorides, 2,2 '-azos bis- [N- (4- chlorphenyl) -2- methyl-prop amidine] dihydrochlorides, 2, 2 '-azos bis- [N- (4- hydrogen phenyl) -2- methyl-prop amidine] dihydrochlorides, the bis- [2- methyl-N- (phenyl methyl) third of 2,2 '-azos Amidine] dihydrochloride, bis- [2- methyl-N- (2- acrylic) the third amidine] dihydrochlorides of 2,2 '-azos, bis- [N- (the 2- hydroxyls of 2,2 '-azos Base ethyl) -2- methyl-prop amidine] dihydrochloride, 2,2 '-azos bis- [2- (5- methyl -2- imidazoline -2- base) propane] two hydrochloric acid Salt, 2,2 '-azos bis- [2- (2- imidazoline -2- base) propane] dihydrochlorides, the bis- [2- (4,5,6,7- tetrahydro -1H- of 2,2 '-azos 1,3- diazepine -2- base) propane] dihydrochloride, bis- [2- (3,4,5,6- tetrahydropyrimidine -2- base) propane] two of 2,2 '-azos Bis- [2- (5- hydroxyl -3,4,5,6- tetrahydropyrimidine -2- base) propane] dihydrochlorides of hydrochloride, 2,2 '-azos, 2,2 '-azos are double [2- [1- (2- hydroxyethyl) -2- imidazoline -2- base] propane] dihydrochloride, the bis- [2- (2- imidazoline -2- base) of 2,2 '-azos Propane], 2,2 '-azos bis- [2- methyl-N- [bis- (the hydroxymethyl) -2- hydroxyethyls of 1,1-] propionamides], 2,2 '-azos it is double [2- methyl-N- [bis- (hydroxymethyl) ethyls of 1,1-] propionamide], bis- [2- methyl-N- (2- hydroxyethyl) propionyl of 2,2 '-azos Amine], 2,2 '-azos bis- (2- methyl propanamides), 2,2 '-azos bis- (2,4,4- trimethylpentanes), bis- (the 2- first of 2,2 '-azos Base propane), dimethyl -2,2- azo bis- (2 Methylpropionic acid esters), 4,4 '-azos bis- (4- cyanopentanoic acids), 2,2 '-azos it is double Azos system polymerization initiators such as [2- (hydroxymethyl) propionitrile].It, can be with as the radical polymerization initiator in present embodiment It is used alone a kind in them, two or more use can also be combined, other well known polymerizations can also be further combined and caused Agent and use.

As the content of aforementioned radical polymerization initiator, as long as required amount in stoichiometry, will include upper It is preferably 0.05~25 mass parts, more excellent when stating total quality of the composition of compound and/or resin and being set as 100 mass parts It is selected as 0.1~10 mass parts.When the content of radical polymerization initiator is 0.05 mass parts or more, having can prevent solidification from becoming Insufficient tendency, on the other hand, the content of radical polymerization initiator be 25 below the mass when, lower membrane can be prevented by having The impaired tendency of the long-term storing stability of forming material at room temperature.

[acid agent]

Promote as needed may be used using viewpoints, aforementioned lower layer's film formation materials such as the cross-linking reactions of heat from further To contain acid agent.As acid agent, it is known to generate the substance of acid by being pyrolyzed, generate the substance of acid by light irradiation Deng, any one can be used.The acid agent recorded in International Publication No. 2013/024779 can be used for example.

In aforementioned lower layer's film formation material, the content of acid agent is not particularly limited, relative to lower layer's film formation material 100 Mass parts, preferably 0.1~50 mass parts, more preferably 0.5~40 mass parts.By being set as preferred scope above-mentioned, there is production Sour quantitative change is more and tendency that cross-linking reaction is improved, in addition, having what the generation with the mixing phenomena of resist layer was suppressed to incline To.

[alkali compounds]

In turn, from the viewpoints such as storage stability are improved, aforementioned lower layer's film formation material can also contain alkaline chemical combination Object.

Alkali compounds is played for preventing quencher by the acid progress cross-linking reaction of the micro generation of acid agent, to acid Effect.It as such alkali compounds, is not particularly limited, for example, International Publication No. 2013/024779 The alkali compounds of middle record.

In aforementioned lower layer's film formation material, the content of alkali compounds is not particularly limited, and forms material relative to lower membrane Expect 100 mass parts, preferably 0.001~2 mass parts, more preferably 0.01~1 mass parts.By being set as preferred model above-mentioned It encloses, has the tendency that storage stability can be improved in the case where not excess destruction cross-linking reaction.

[other additives]

In addition, the lower membrane shape for the purpose for assigning curability using heat, light, controlling absorbance, in present embodiment Other resins and/or compound can also be contained at material.As other such resins and/or compound, naphthalene can be enumerated The phenol-modified resin of the naphthol-modified resin of phenol resin, xylene resin, naphthalene resin；Polycarboxylated styrene, bicyclopentadiene tree Rouge, (methyl) acrylate, dimethylacrylate, trimethyl acrylic ester, tetramethyl acrylate, vinyl naphthalene, polyacenaphthylene Deng comprising cyclohexyl biphenyls, thiophene, the indenes such as naphthalene nucleus, phenanthrenequione, fluorenes etc. with heteroatomic heterocycle resin, without the tree of aromatic ring Rouge；They pure and mild derivative etc. of rosin series resin, cyclodextrin, adamantane (polynary) alcohol, tristane (polynary) includes alicyclic ring Resin or compound of structure etc., are not particularly limited in these.In turn, lower layer's film formation material in present embodiment can also be with Contain well known additive.It as aforesaid known additive, is not limited to hereinafter, can for example enumerate: heat and/or photocuring Catalyst, polymerization inhibitor, fire retardant, filler, coupling agent, thermosetting resin, photo-curable resin, dyestuff, pigment, thickener, profit Lubrication prescription, defoaming agent, levelling agent, ultraviolet absorbing agent, surfactant, colorant, nonionic surfactants etc..

[forming method of lower layer film for lithography and multilayer corrosion-resisting pattern]

Aforementioned lower layer's film formation material can be used to form lower layer film for lithography.

At this point it is possible to use the corrosion-resisting pattern forming method with following process: using aforementioned lower layer's film formation material (this The composition of embodiment) process (A-1) of formation lower membrane on substrate；At least 1 layer of light is formed in aforementioned lower membrane Cause the process (A-2) of resist layer；And after aforementioned 2nd formation process, spoke is irradiated to the predetermined region of aforementioned photoresist layer Ray and the process developed (A-3).

In turn, other pattern forming methods (circuit pattern forming method) of present embodiment have following process: using Aforementioned lower layer's film formation material (composition of present embodiment) forms the process (B-1) of lower membrane on substrate；Using against corrosion Interlayer film material forms the process (B-2) of interlayer film in aforementioned lower membrane；At least 1 layer is formed between in the foregoing on tunic Photoresist layer process (B-3)；After foregoing sequence (B-3), to the predetermined region illumination radiation of aforementioned photoresist layer Line simultaneously develops, to form the process (B-4) of corrosion-resisting pattern；After foregoing sequence (B-4), using aforementioned corrosion-resisting pattern as Mask and aforementioned interlayer film is etched, using obtained interlayer film pattern as etching mask and to aforementioned lower membrane into Row etching, obtained lower layer's film figure is etched substrate as etching mask, to form the work of pattern in substrate Sequence (B-5).Aforementioned interlayer film material against corrosion can contain silicon atom.

As long as the lower layer film for lithography in present embodiment is formed by aforementioned lower layer's film formation material, to its side of being formed Method is not particularly limited, and can apply well known gimmick.For example, can by lower layer's membrane material of present embodiment by spin coating, Rubbing method well known to silk-screen printing etc. or print process etc. are imparted on substrate, are then made organic solvent volatilization etc. and are removed, then It is crosslinked, solidified using well known method, form the lower layer film for lithography of present embodiment.As cross-linking method, Ke Yiju The methods of heat cure, photocuring out.

When the formation of lower membrane, in order to inhibit with the generation of the mixing phenomena of upper layer resist and in order to promote crosslinking anti- It answers, is preferably toasted.At this point, baking temperature is not particularly limited, in the range of preferably 80~450 DEG C, it is more preferably 200 ~400 DEG C.In addition, baking time is also not particularly limited, in the range of preferably 10~300 seconds.It should be noted that lower layer The thickness of film can be suitably selected according to performance is required, and is not particularly limited, it is often preferred that 30~20000nm or so, more It is preferably set to 50~15000nm.

Preferably, after making lower membrane, in the case where 2 layer process, siliceous resist layer or common is made on it Single layer resist containing hydrocarbon makes siliceous middle layer in the case where 3 layer process on it, and then makes on it again not Siliceous single layer resist layer.At this point, well known material can be used as the photo anti-corrosion agent material for being used to form the resist layer Material.

After making lower membrane on substrate, in the case where 2 layer process, siliceous resist layer can be made in the lower membrane Or the common single layer resist containing hydrocarbon.In the case where 3 layer process, siliceous middle layer can be made in the lower membrane, And then not siliceous single layer resist layer is made in the siliceous middle layer again.In the case of these, it is used to form the photic of resist layer Anticorrosive additive material can suitably selection uses from well known material, is not particularly limited.

As the siliceous anticorrosive additive material of 2 layer process, it is preferable to use eurymeric from the viewpoint of oxygen elching resistant The photo anti-corrosion agent material of photo anti-corrosion agent material, the eurymeric is derivative using polysilsesquioxane derivative or vinyl silanes The polymer of the silicon atoms such as object contains organic solvent, acid agent and alkalization as needed as basic polymer Close object etc..Herein, as the polymer of silicon atoms, the well known polymerization used in this anticorrosive additive material can be used Object.

As 3 layer process siliceous middle layer, it is preferable to use polysilsesquioxane basis middle layer.By making centre Layer has the effect of as antireflection film having the tendency that reflection can be effectively inhibited.For example, in 193nm exposure technique, Use and contain a large amount of aromatic groups and when the high material of substrate elching resistant is as lower membrane, there is k value to get higher, substrate reflection becomes High tendency, and by inhibiting reflection using middle layer, so as to so that substrate is reflected into 0.5% or less.As with this The middle layer of anti-reflection effect is not limited to hereinafter, it is preferable to use following polysilsesquioxanes: it has been imported as 193nm The phenyl of exposure or extinction group with silicon-silicon bond are crosslinked by acid or heat.

It is formed alternatively, it is also possible to use by Chemical Vapour Deposition (chemical vapor deposition, CVD) method Middle layer.For the middle layer high as the effect of antireflection film made using CVD method, it is not limited to hereinafter, for example Knowing has SiON film.In general, compared with CVD method, and tool easier using the wet process such as spin-coating method, silk-screen printing formation middle layer Have the advantages that in cost.It should be noted that the upper layer resist in 3 layer process can be eurymeric and be also possible to minus, in addition, Resist identical with usually used single layer resist can be used.

In turn, the lower membrane in present embodiment is also used as the antireflection film of usual single layer resist or for pressing down The primer that pattern collapses.The elching resistant for bottom processing of the lower membrane of present embodiment is excellent, therefore can also To the function to be used as the hard mask processed for bottom.

When forming resist layer by aforementioned photo anti-corrosion agent material, it is preferable to use rotations in the same manner as when forming aforementioned lower membrane The wet process such as coating, silk-screen printing.In addition, usually carrying out prebake conditions, this is pre- after being coated with anticorrosive additive material by spin-coating method etc. Baking is preferably carried out in the range of 10~300 seconds with 80~180 DEG C.Then, it is conventionally exposed, is exposed (PEB), development are toasted afterwards, it is hereby achieved that corrosion-resisting pattern.It should be noted that the thickness of etchant resist is not particularly limited, It is generally preferred to 30~500nm, more preferably 50~400nm.

In addition, exposure light suitably selects use according to used photo anti-corrosion agent material.Usually wavelength 300nm high-energy rays below, can specifically enumerate: the excimer laser of 248nm, 193nm, 157nm, 3~20nm Grenz ray, electron beam, X-ray etc..

The corrosion-resisting pattern formed by the above method, which becomes, inhibits pattern collapse by the lower membrane in present embodiment Corrosion-resisting pattern.Therefore, by using the lower membrane in present embodiment, available finer pattern, in addition, can drop Low corrosion-resisting pattern in order to obtain and required light exposure.

Then, it is etched using resulting corrosion-resisting pattern as mask.As the etching of the lower membrane in 2 layer process, It is preferable to use gas etches.It is suitably the etching for having used oxygen as gas etch.On the basis of oxygen, it can also add Enter the non-active gas such as He, Ar, CO, CO₂、NH₃、SO₂、N₂、NO₂、H₂Gas.Alternatively, it is also possible to without using oxygen and merely with CO、CO₂、NH₃、N₂、NO₂、H₂Gas carries out gas etch.Especially the gas of the latter can be in order to carry out preventing pattern sidewalls Undercutting side wall protection and it is preferable to use.

On the other hand, in the etching of the middle layer in 3 layer process, it is also preferred that using gas etches.As gas etch, Gas etch same as the gas etch illustrated in above-mentioned 2 layer process can be applied.In particular, middle layer in 3 layer process Processing is carried out it is preferable to use the gas of freon system and using corrosion-resisting pattern as mask.Then, as described above with middle layer Pattern carries out such as oxygen etch, it is possible thereby to carry out the processing of lower membrane as mask.

Herein, when forming inorganic hardmask interlayer film as middle layer, silicon oxidation can be formed by CVD method, ALD method etc. Film, silicon nitride film, silicon oxidation nitridation film (SiON film).As the forming method of nitride film, it is not limited to hereinafter, can for example make With the method recorded in Japanese Unexamined Patent Publication 2002-334869 bulletin (patent document 6), WO2004/066377 (patent document 7). Photoresist can be directly formed on such interlayer film, can also be formed on interlayer film by spin coating organic anti- Reflectance coating (BARC), is formed on photoresist.

As middle layer, the middle layer on polysilsesquioxane basis is further preferably used.By having resist interlayer film There is the effect as antireflection film, has the tendency that reflection can be effectively inhibited.Middle layer about polysilsesquioxane basis Specific material, be not limited to hereinafter, Japanese Unexamined Patent Publication No. 2007-226170 (patent document 8), Japanese Unexamined Patent Publication can be used for example The material recorded in No. 2007-226204 (patent document 9).

In addition, the etching of next substrate can use conventional method also to carry out, for example, substrate is SiO₂、SiN When, the etching based on freon system gas can be carried out, be p-Si, Al, W when, can carry out be with chlorine system, bromine system gas The etching of main body.When being etched using freon system gas to substrate, the siliceous resist and 3 layers of work of 2 layers of resist technique The siliceous middle layer of skill is stripped simultaneously with substrate processing.On the other hand, substrate is etched using chlorine system or bromine system gas When, the removing of siliceous resist layer or siliceous middle layer is additionally carried out, and generally carries out utilizing freon system gas after substrate processing Dry ecthing removing.

The feature that aforementioned lower membrane has the elching resistant of these substrates excellent.It should be noted that substrate can be appropriate Selection uses well known substrate, is not particularly limited, can enumerate Si, α-Si, p-Si, SiO₂、SiN、SiON、W、TiN、Al Deng.In addition, substrate is also possible to the laminated body on substrate (supporter) with machined membrane (processed substrate).As in this way Machined membrane, can enumerate: Si, SiO₂, SiON, SiN, p-Si, α-Si, the various Low-k such as W, W-Si, Al, Cu, Al-Si Film and its block film etc., the usually used film with substrate (supporter) unlike material.It should be noted that as processing object The thickness of substrate or machined membrane is not particularly limited, it is often preferred that 50~10000nm or so, more preferably 75~ 5000nm。

[permanent film against corrosion]

It should be noted that aforementioned composition, which also can be used, makes permanent film against corrosion.It is coated with the combination of present embodiment Permanent film against corrosion made of object be suitable as being formed corrosion-resisting pattern as needed after, also remaining permanent film in the final article. As the concrete example of permanent film, semiconductor devices correlation can be enumerated: solder resist, encapsulating material, underfill, circuit elements Part etc. encapsulates the adhesive layer of adhesive layer, integrated circuit component and circuit substrate；Thin display correlation can be enumerated: film crystal Protection of pipe film, liquid crystal color filter protecting layer, black matrix, spacer etc..Particularly, it is formed forever by the composition of present embodiment Long film also has the pollution as caused by distillation ingredient few very excellent in this way on the basis of heat resistance, moisture-proof are excellent Advantage.Especially in display material, become the image quality as caused by important pollution deteriorate it is few, have both it is highly sensitive, high resistance to The material of heat, moisture absorption reliability.

When the composition of present embodiment is used for permanent film purposes against corrosion, other than curing agent, it is added as needed The various additives such as other resins, surfactant, dyestuff, filler, crosslinking agent, dissolution accelerator, are dissolved in organic solvent, It is possible thereby to which permanent film composition against corrosion is made.

The photoetching film of present embodiment formed composition, permanent film composition against corrosion can by be compounded it is aforementioned respectively at Point, it is mixed using blender etc. to prepare.In addition, the resist composition for underlayer film of present embodiment, against corrosion permanent When film composition contains filler, pigment, the dispersal devices such as dissolvers, homogenizer, 3 rollers mill can be used and dispersed or mixed It closes to prepare.

Embodiment

Hereinafter, present embodiment is further described by synthesis example and embodiment, but the present invention is not by these examples Any restriction.

[molecular weight]

The molecular weight of compound using Water corporation Acquity UPLC/MALDI-Synapt HDMS, pass through LC-MS Analysis is measured.

In addition, carrying out gel permeation chromatography (GPC) analysis under the following conditions, dividing equally again for polystyrene conversion is found out Son amount (Mw), number-average molecular weight (Mn) and dispersion degree (Mw/Mn).

Device: Shodex GPC-101 type (Showa Denko K. K's system)

Column: KF-80M × 3

Eluent: THF1ml/ minutes

Temperature: 40 DEG C

[dissolubility]

At 23 DEG C, make compound relative to propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), first Base amyl ketone (MAK) or tetramethylurea (TMU) are stirred and are dissolved in a manner of becoming 3 mass % solution, are then passed through 1 week.It presses According to the dissolubility of following benchmark evaluation compound.

Evaluation A: precipitate is not generated in any solvent with visual confirmation.

Evaluation C: precipitate is generated in any solvent with visual confirmation.

[structure of compound]

The structure of compound uses Bruker corporation " Advance600II spectrometer ", in condition below Lower progress¹H-NMR is measured and is confirmed.

Frequency: 400MHz

Solvent: d6-DMSO

Internal standard: TMS

Measuring temperature: 23 DEG C

<the synthesis of synthesis example 1>XBisN-1

In the container of internal volume 100ml for having blender, cooling tube and buret, by 2,6- naphthalenediol (Sigma- Aldrich reagent) 3.20g (20mmol) and 4- biphenylcarboxaldehyde (Mitsubishi Gas Chemical Co., Ltd's system) 1.82g (10mmol) is put into 30ml methyl iso-butyl ketone (MIBK), and 95% sulfuric acid 5ml is added, and reaction solution is stirred 6 hours at 100 DEG C It is reacted.Then, reaction solution is concentrated, be added pure water 50g reaction product is precipitated, after being cooled to room temperature, be filtered and Separation.Obtained solid substance is filtered, after making it dry, is isolated and purified using column chromatography, obtains following formula (XBisN-1) institute The target compound 3.05g shown.Pass through 400MHz-¹H-NMR confirmed the chemical structure with following formula (XBisN-1).

¹H-NMR:(d-DMSO, internal standard TMS)

Δ (ppm) 9.7 (2H, O-H), 7.2~8.5 (19H, Ph-H), 6.6 (1H, C-H)

It should be noted that being bimodal according to the signal of 3 and 4 protons, it is thus identified that the substitution position of 2,6- naphthalene glycol It is set to 1.

<the synthesis of synthesis example 1A>E-XBisN-1

In the container of internal volume 100ml for having blender, cooling tube and buret, by above-mentioned formula (XBisN-1) institute The compound 10g (21mmol) and potassium carbonate 14.8g (107mmol) shown is put into 50ml dimethylformamide, and acetic acid-is added Reaction solution is stirred 12 hours at 90 DEG C and is reacted by 2- chloroethene ester 6.56g (54mmol).Then, by reaction solution in ice bath Middle cooling, is precipitated crystal, is filtered and separates.Then, in the internal volume for having blender, cooling tube and buret Aforementioned crystal 40g, methanol 40g, THF100g and 24% sodium hydrate aqueous solution are put into the container of 100ml, it under reflux will be anti- It answers liquid to stir 4 hours to be reacted.Later, cooling in ice bath, the solid matter of precipitation is filtered and is dried by concentration of reaction solution Afterwards, it is isolated and purified using column chromatography, obtains target compound 5.9g shown in following formula (E-XBisN-1).Pass through 400MHz-¹H-NMR confirmed the chemical structure with following formula (E-XBisN-1).

¹H-NMR:(d-DMSO, internal standard TMS)

Δ (ppm) 8.6 (2H, O-H), 7.2~7.8 (19H, Ph-H), 6.7 (1H, C-H), 4.0 (4H ,-O-CH₂-)、3.8 (4H,-CH₂-OH)

<the synthesis of synthesis example 2>BisF-1

Prepare the container with the internal volume 200ml of blender, cooling tube and buret.4,4- connection is put into the container Phenol (Tokyo is melted into Co. Ltd. system reagent) 30g (161mmol), 4- biphenylcarboxaldehyde (Mitsubishi Gas Chemical Co., Ltd's system) P-methyl benzenesulfonic acid (Kanto Kagaku K. K.'s reagent) 3.9g is added in 15g (82mmol) and butyl acetate 100ml (21mmol), prepares reaction solution.The reaction solution is stirred 3 hours at 90 DEG C and is reacted.Then, concentration of reaction solution is added Reaction product is precipitated in heptane 50g, after being cooled to room temperature, is filtered and separates.Keep the solid matter by being obtained by filtration dry It after dry, is isolated and purified using column chromatography, thus obtains target compound shown in following formula (BisF-1) 5.8g.

It should be noted that passing through 400MHz-¹H-NMR has found peak below, it is thus identified that with following formula (BisF-1) Chemical structure.

¹H-NMR:(d-DMSO, internal standard TMS)

Δ (ppm) 9.4 (4H, O-H), 6.8~7.8 (22H, Ph-H), 6.2 (1H, C-H)

About gained compound, molecular weight, result 536 are measured by preceding method.

<the synthesis of synthesis example 2A>E-BisF-1

It, will be shown in previously described formula (BisF-1) in the container of internal volume 100ml for having blender, cooling tube and buret Compound 11.2g (21mmol) and potassium carbonate 14.8g (107mmol) put into 50ml dimethylformamide, be added acetic acid- Reaction solution is stirred 12 hours at 90 DEG C and is reacted by 2- chloroethene ester 6.56g (54mmol).Then, by reaction solution in ice bath Crystal is precipitated in middle cooling, is filtered and separates.Then, in the internal volume 100ml for having blender, cooling tube and buret Container in put into aforementioned crystal 40g, methanol 40g, THF100g and 24% sodium hydrate aqueous solution, under reflux by reaction solution Stirring is reacted for 4 hours.Later, cooling in ice bath, concentration of reaction solution, after the solid matter of precipitation is filtered and is dried, It is isolated and purified using column chromatography, obtains target compound 5.9g shown in following formula (E-BisF-1).

Pass through 400MHz-¹H-NMR confirmed the chemical structure with following formula (E-BisF-1).

¹H-NMR:(d-DMSO, internal standard TMS)

Δ (ppm) 8.6 (4H, O-H), 6.8~7.8 (22H, Ph-H), 6.2 (1H, C-H), 4.0 (8H ,-O-CH₂-)、3.8 (8H,-CH₂-OH)

About gained compound, molecular weight, result 712 are measured by preceding method.

<the synthesis of synthetic example 1-1>SXBisN-1

In the container of internal volume 100ml for having blender, cooling tube and buret, by previously described formula (XBisN-1) institute The compound 10.0g (21mmol) and vinyl chloride (trade name CMS-P shown；SEIMICHEMICAL CO., LTD. system) 6.4g is put into 50ml dimethylformamide, in the state of being heated up to 50 DEG C and stirring, is added by dropping funel with 20 minutes Enter 28 mass % sodium methoxide (methanol solution) 8.0g, reaction solution is stirred 1 hour at 50 DEG C and is reacted.Then, 28 are added Reaction solution is heated up to 60 DEG C and stirred 3 hours, and then 85 mass % phosphoric acid are added by quality % sodium methoxide (methanol solution) 1.6g 1.2g, stirring after ten minutes, are cooled to 40 DEG C, reaction solution are added drop-wise in pure water, the solid matter of precipitation is filtered and dried Afterwards, it is isolated and purified using column chromatography, obtains target compound 4.0g shown in following formula (SXBisN-1).

Pass through 400MHz-¹H-NMR confirmed the chemical structure with following formula (SXBisN-1).

¹H-NMR:(d-DMSO, internal standard TMS)

Δ (ppm) 7.2~8.5 (27H, Ph-H), 5.2~6.7 (11H ,-CH2- ,-CH=CH2, C-H)

About gained compound, molecular weight, result 698 are measured by preceding method.

Pyrolysis temperature is 400 DEG C, glass transition point is 115 DEG C, fusing point is 225 DEG C, is able to confirm that high-fire resistance.

<the synthesis of synthetic example 1-2>SE-XBisN-1

Previously described formula (XBisN-1) compound represented is replaced using previously described formula (E-XBisN-1) compound represented, removes this Except, it is carried out similarly and reacts with synthetic example 1-1, obtain target compound shown in following formula (SE-XBisN-1) 4.0g。

Pass through 400MHz-¹H-NMR, it is thus identified that the chemical structure with following formula (SE-XBisN-1).

¹H-NMR:(d-DMSO, internal standard TMS)

Δ (ppm) 7.2~7.8 (19H, Ph-H), 6.7 (19H ,-CH₂-CH₂-、-CH₂,-CH=CH₂、C-H)

(SE-XBisN-1)

About gained compound, molecular weight, result 786 are confirmed by preceding method.

Pyrolysis temperature is 380 DEG C, glass transition point is 100 DEG C, fusing point is 205 DEG C, is able to confirm that high-fire resistance.

<the synthesis of synthetic example 2-1>SBisF-1

Previously described formula (XBisN-1) compound represented is replaced using previously described formula (BisF-1) compound represented, except this it Outside, it is reacted in the same manner as synthetic example 1-1, obtains target compound 3.2g shown in following formula (SBisF-1).

Pass through 400MHz-¹H-NMR confirmed the chemical structure with following formula (sbisf-1).

¹H-NMR:(d-DMSO, internal standard TMS)

Δ (ppm) 6.8~7.8 (38H, Ph-H), 6.2 (21H ,-CH₂,-CH=CH₂、C-H)

About gained compound, molecular weight, result 1000 are measured by preceding method.

Pyrolysis temperature is 400 DEG C, glass transition point is 90 DEG C, fusing point is 225 DEG C, it is thus identified that high-fire resistance.

<the synthesis of synthetic example 2-2>SE-BisF-1

Previously described formula (BisF-1) compound represented is replaced using previously described formula (E-BisF-1) compound represented, except this it Outside, it is reacted in the same manner as synthetic example 2-1, has obtained target compound 3.3g shown in following formula (SE-BisF-1).

Pass through 400MHz-¹H-NMR confirmed the chemical structure with following formula (SE-BisF-1).

¹H-NMR:(d-DMSO, internal standard TMS)

Δ (ppm) 6.8~7.8 (22H, Ph-H), 6.2 (37H ,-CH2-CH2- ,-CH2- ,-CH=CH2, C-H)

Pyrolysis temperature is 380 DEG C, glass transition point is 70 DEG C, fusing point is 200 DEG C, is able to confirm that high-fire resistance.

About gained compound, molecular weight, result 1177 are measured by preceding method.

Pyrolysis temperature is 375 DEG C, glass transition point is 65 DEG C, fusing point is 190 DEG C, is able to confirm that high-fire resistance.

<the synthesis of synthesis example 3>BiN-1

In the container of internal volume 300mL for having blender, cooling tube and buret, make beta naphthal (Sigma- Aldrich reagent) after 10g (69.0mmol) melts at 120 DEG C, sulfuric acid 0.27g is put into, 4- acetyl biphenyl is added (Sigma-Aldrich corporation reagent) 2.7g (13.8mmol), content is stirred 6 hours at 120 DEG C and is reacted, is obtained To reaction solution.Then, n-methyl-2-pyrrolidone (Kanto Kagaku K. K.'s system) 100mL, pure water is added into reaction solution Then 50mL is extracted by ethyl acetate.Then, pure water is added, until becoming neutral, is concentrated, is obtained after liquid separation Solution.

After acquired solution being separated using column chromatography, obtain target compound (BiN-1) shown in following formula (BiN-1) 1.0g。

About gained compound (BiN-1), molecular weight, result 466 are measured by the above method.

About gained compound (BiN-1), NMR measurement is carried out under the conditions of said determination, as a result, it has been found that following peak, confirmation Chemical structure with following formula (BiN-1).

δ (ppm) 9.69 (2H, O-H), 7.01~7.67 (21H, Ph-H), 2.28 (3H, C-H)

<the synthesis of synthesis example 3A>E-BiN-1

In the container of internal volume 100ml for having blender, cooling tube and buret, by previously described formula compound represented (BiN-1) 10.5g (21mmol) and potassium carbonate 14.8g (107mmol) are put into 50ml dimethylformamide, and acetic acid-is added Reaction solution is stirred 12 hours at 90 DEG C and is reacted by 2- chloroethene ester 6.56g (54mmol).Then, by reaction solution in ice bath Middle cooling, is precipitated crystal, is filtered and separates.Then, in the internal volume for having blender, cooling tube and buret Aforementioned crystal 40g, methanol 40g, THF100g and 24% sodium hydrate aqueous solution are put into the container of 100ml, it under reflux will be anti- It answers liquid to stir 5 hours, is reacted.Later, cooling in ice bath, the solid matter of precipitation is filtered and is done by concentration of reaction solution It after dry, is isolated and purified using column chromatography, obtains target compound 4.6g shown in following formula.Pass through 400MHz-¹H-NMR It confirmed the chemical structure with following formula.

¹H-NMR:(d-DMSO, internal standard TMS)

<the synthesis of synthetic example 3-1>SBiN-1

It, will be shown in previously described formula (BiN-1) in the container of internal volume 100ml for having blender, cooling tube and buret Compound 10.0g (21mmol) and vinyl chloride (trade name CMS-P；SEIMICHEMICAL CO., LTD. system) 6.4g It puts into 50ml dimethylformamide, in the state of being heated up to 50 DEG C and stirring, was added by dropping funel with 20 minutes 28 mass % sodium methoxide (methanol solution) 8.0g, reaction solution is stirred 1 hour at 50 DEG C and is reacted.Then, 28 matter are added % sodium methoxide (methanol solution) 1.6g is measured, reaction solution is heated up to 60 DEG C and is stirred 3 hours, and then 85 mass % phosphoric acid are added 1.2g, stirring after ten minutes, are cooled to 40 DEG C, reaction solution are added drop-wise in pure water, the solid matter of precipitation is filtered and dried Afterwards, it is isolated and purified using column chromatography, obtains target compound 4.0g shown in following formula (SBiN-1).

Pass through 400MHz-¹H-NMR confirmed the chemical structure with following formula (SBiN-1).

¹H-NMR:(d-DMSO, internal standard TMS)

δ (ppm) 7.2~7.8 (19H, Ph-H), 5.2~6.7 (10H ,-CH₂,-CH=CH₂、C-H)、2.3(3H,-CH₃)

Pyrolysis temperature is 375 DEG C, glass transition point is 105 DEG C, fusing point is 212 DEG C, is able to confirm that with high-fire resistance.

<the synthesis of synthetic example 3-2>SE-BiN-1

Previously described formula (BiN-1) compound represented is replaced using previously described formula (E-BiN-1) compound represented, except this it Outside, it is carried out similarly and reacts with synthetic example 3-1, obtain target compound 3.6g shown in following formula (SE-BiN-1).

Pass through 400MHz-¹H-NMR confirmed the chemical structure with following formula (SE-BiN-1).

¹H-NMR:(d-DMSO, internal standard TMS)

δ (ppm) 7.2~7.8 (19H, Ph-H), 6.7 (18H ,-CH2-CH2- ,-CH2- ,-CH=CH2, C-H), 2.3 (3H,-CH3)

About gained compound, molecular weight, result 786 are measured by preceding method.

Pyrolysis temperature is 361 DEG C, glass transition point is 112 DEG C, fusing point is 212 DEG C, is able to confirm that with high-fire resistance.

<the synthesis of synthesis example 4>BiP-1

Beta naphthal is replaced in addition to this to be carried out similarly and react with synthesis example 1, obtain following formula using o-phenyl phenol (BiP-1) target compound 1.0g shown in.

About gained compound (BiP-1), molecular weight, result 466 are measured by the above method.

About gained compound (BiP-1), NMR measurement is carried out under the conditions of said determination, as a result, it has been found that following peak, confirmation Chemical structure with following formula (BiP-1).

δ (ppm) 9.67 (2H, O-H), 6.98~7.60 (25H, Ph-H), 2.25 (3H, C-H)

It, will be shown in previously described formula (BiP-1) in the container of internal volume 100ml for having blender, cooling tube and buret Compound 11.2g (21mmol) and potassium carbonate 14.8g (107mmol) put into 50ml dimethylformamide, be added acetic acid- Reaction solution is stirred 12 hours at 90 DEG C and is reacted by 2- chloroethene ester 6.56g (54mmol).Then, by reaction solution in ice bath Middle cooling, is precipitated crystal, is filtered and separates.Then, in the internal volume for having blender, cooling tube and buret Aforementioned crystal 40g, methanol 40g, THF100g and 24% sodium hydrate aqueous solution are put into the container of 100ml, it under reflux will be anti- It answers liquid to stir 4 hours to be reacted.Later, cooling in ice bath, the solid matter of precipitation is filtered, makes it by concentration of reaction solution It after drying, is isolated and purified using column chromatography, obtains target compound 5.9g shown in following formula (E-BisP-1).

Pass through 400MHz-¹H-NMR confirmed the chemical structure with following formula (E-BiP-1).

¹H-NMR:(d-DMSO, internal standard TMS)

δ (ppm) 8.6 (4H, O-H), 6.8~7.6 (25H, Ph-H), 4.0 (4H ,-O-CH₂-)、3.8(4H,-CH₂-OH)、 2.2(3H,C-H)

About gained compound, molecular weight, result 606 are measured by preceding method.

<the synthesis of synthetic example 4-1>SBiP-1

Previously described formula (XBisN-1) compound represented is replaced using previously described formula (BiP-1) compound represented, except this it Outside, it is carried out similarly and reacts with synthetic example 1-1, obtain target compound 3.0g shown in following formula (SBiP-1).

Pass through 400MHz-¹H-NMR confirmed the chemical structure with following formula (SBiP-1).

¹H-NMR:(d-DMSO, internal standard TMS)

δ (ppm) 6.8~7.8 (25H, Ph-H), 5.2~6.7 (10H ,-CH₂,-CH=CH₂、C-H)、2.3(3H,-CH₃)

Pyrolysis temperature is 390 DEG C, glass transition point is 74 DEG C, fusing point is 202 DEG C, is able to confirm that with high-fire resistance.

About gained compound, molecular weight, result 750 are measured by preceding method.

<the synthesis of synthetic example 4-2>SE-BiP-1

Previously described formula (BiP-1) compound represented is replaced using previously described formula (E-BiP-1) compound represented, except this it Outside, it is reacted in the same manner as synthetic example 4-1, has obtained target compound 2.9g shown in following formula (SE-BiP-1).

Pass through 400MHz-¹H-NMR confirmed the chemical structure with following formula (SE-BiP-1).

¹H-NMR:(d-DMSO, internal standard TMS)

δ (ppm) 6.8~7.8 (25H, Ph-H), 6.7 (18H ,-CH₂-CH₂-、-CH₂,-CH=CH₂、C-H)、2.3 (3H,-CH₃)

About gained compound, molecular weight, result 838 are measured by preceding method.

Pyrolysis temperature is 365 DEG C, glass transition point is 82 DEG C, fusing point is 220 DEG C, is able to confirm that with high-fire resistance.

(synthesis example 5~17)

According to shown in table 1 change as synthesis example 3 raw material beta naphthal (raw material 1) and 4- acetyl biphenyl (raw material 2), In addition to this it is carried out similarly with synthesis example 3, obtains each object.

It is utilized respectively¹H-NMR is identified.

[table 1]

Synthesis example	Raw material 1	Raw material 2	Product
				5	2,6- dihydroxy naphthlenes	4- acetyl biphenyl	BiN-2
6	2,7- dihydroxy naphthlenes	4- acetyl biphenyl	BiN-3
				7	2,6- dihydroxy naphthlenes	4 '-cyclohexyl benzene ethyl ketones	BiN-4
8	P-phenyl phenol	4- acetyl biphenyl	BiP-2
				9	2,2 '-dihydroxybiphenyls	4- acetyl biphenyl	BiP-3
10	2,2 '-dihydroxybiphenyls	4 '-cyclohexyl benzene ethyl ketones	BiP-4
				11	Phenol	4- acetyl biphenyl	P-1
12	Phenol	4 '-cyclohexyl benzene ethyl ketones	P-2
				13	2,6- dihydroxy naphthlenes	4- acetyl biphenyl	XBiN-1
14	2,7- dihydroxy naphthlenes	4- acetyl biphenyl	XBiN-2
				15	2,6- dihydroxy naphthlenes	4 '-cyclohexyl benzene ethyl ketones	XBiN-3
16	Resorcinol	4- acetyl biphenyl	P-3
				17	Resorcinol	4 '-cyclohexyl benzene ethyl ketones	P-4

[table 2]

(synthesis example 18~20)

It is in addition to this, same with synthetic example 1 according to 4- biphenylcarboxaldehyde of the change as the raw material of synthesis example 1 shown in table 3 It carries out to sample, obtains each object.

It is utilized respectively¹H-NMR is identified.

[table 3]

Synthesis example	Raw material 1	Raw material 2	Product
				18	2,6- dihydroxy naphthlenes	Isobutyl-benzene formaldehyde	XBisN-2
19	2,6- dihydroxy naphthlenes	N-propylbenzene formaldehyde	XBisN-3
				20	2,6- dihydroxy naphthlenes	4- hydroxy benzaldehyde	XBisN-4

[table 4]

(synthesis example 21~22)

According to shown in table 5 change as synthesis example 3 raw material beta naphthal (raw material 1) and 4- acetyl biphenyl (raw material 2), Water 1.5mL, lauryl mercaptan 73mg (0.35mmol), 37% hydrochloric acid 2.3g (22mmol) is added, reaction temperature is changed to It 55 DEG C, in addition to this, is carried out similarly with synthesis example 31, obtains each object.

It is utilized respectively¹H-NMR is identified.

[table 5]

Synthesis example	Raw material 1	Raw material 2	Product
				21	Resorcinol	4- biphenylcarboxaldehyde	P-5
22	Resorcinol	Benzaldehyde	P-6

[table 6]

Synthesis example	Compound name	1H-NMR
			21	P-5	δ (ppm) 9.2~9.4 (4H, O-H), 6.6~7.2 (15H, Ph-H), 6.3 (1H, C-H)
22	P-6	δ (ppm) 9.3~9.4 (4H, O-H), 6.6~7.2 (11H, Ph-H), 6.2 (1H, C-H)

(synthesis example 5A~22A)

According to previously described formula (BiN-1) compound represented of change as the raw material of synthesis example 3A shown in table 7, remove this it Outside, it is synthesized under the conditions of same as synthesis example 3A, respectively obtains object.Utilize 400MHz-¹H-NMR(d-DMSO、 Internal standard TMS) and LC-MS confirmation molecular weight, thus identify the structure of each compound.

(synthetic example 5-1~22-1)

According to previously described formula (BiN-1) compound represented of change as the raw material of synthetic example 3-1 shown in table 7, remove Except this, is synthesized under the conditions of same as synthetic example 3-1, respectively obtain object.Utilize 400MHz-¹H-NMR (d-DMSO, internal standard TMS) and LC-MS confirm molecular weight, thus identify the structure of each compound.

(synthetic example 5-2~22-2)

According to shown in table 7 change as synthetic example 3-2 raw material previously described formula (E-BiN-1) compound represented, In addition to this, it is synthesized under the conditions of same as synthetic example 3-2, respectively obtains object.Utilize 400MHz-¹H- NMR (d-DMSO, internal standard TMS) and LC-MS confirms molecular weight, thus identifies the structure of each compound.

[table 7]

	No.	Raw material 1	Product	Element forms (LC-MS)	Molecular weight (LC-MS)
						Synthesis example	5A	BiN-2	E-BiN-2	C42H42O8	674.79
Synthetic example	5-1	BiN-2	SBiN-2	C70H58O4	963.23
						Synthetic example	5-2	BiN-2	SE-BiN-2	C78H74O8	1139.44
Synthesis example	6A	BiN-3	E-BiN-3	C42H42O8	674.79
						Synthetic example	6-1	BiN-3	SBiN-3	C70H58O4	963.23
Synthetic example	6-2	BiN-3	SE-BiN-3	C78H74O8	1139.44
						Synthesis example	7A	BiN-4	E-BiN-4	C42H48O8	680.84
Synthetic example	7-1	BiN-4	SBiN-4	C70H64O4	969.28
						Synthetic example	7-2	BiN4	SE-BiN-4	C78H30O8	1145.49
Synthesis example	8A	BiP-2	E-BiP-2	C46H46O8	726.87
						Synthetic example	8-1	BiP-2	SBiP-2	C74H62O4	1015.31
Synthetic example	8-2	BiP-2	SE-BiP-2	C82H78O8	1191.52
						Synthesis example	9A	BiP-3	E-BiP-3	C46H46O8	726.87
Synthetic example	9-1	BiP-3	SBiP-3	C74H62O4	1015.31
						Synthetic example	9-2	BiP-3	SE-BiP-3	C82H78O8	1191.52
Synthesis example	10A	BiP-4	E-BiP-4	C46H52O8	732.91
						Synthetic example	10-1	BiP-4	SBiP-4	C74H68O4	1021.35
Synthetic example	10-2	BiP-4	SE-BiP-4	C82H34O8	1197.57
						Synthesis example	11A	P-1	E-P-1	C30H30O4	454.57
Synthetic example	11-1	P-1	SP-1	C44H38O2	598.79
						Synthetic example	11-2	P-1	SE-P-1	C48H46O4	686.89
Synthesis example	12A	P-2	E-P-2	C30H36O4	460.61
						Synthetic example	12-1	P-2	SP-2	C44H44O2	604.83
Synthetic example	12-2	P-2	SE-P-2	C48H52O4	692.94
						Synthesis example	13A	XBiN-1	E-XBiN-1	C37H30O5	554.64
Synthetic example	13-1	XBiN-1	SXBiN-1	C51H38O3	698.86
						Synthetic example	13-2	XBiN-1	SE-XBiN-1	C55H46O5	786.97
Synthesis example	14A	XBiN-2	E-XBiN-2	C38H32O5	568.67
						Synthetic example	14-1	XBiN-2	SXBiN-2	C52H40O3	712.89
Synthetic example	14-2	XBiN-2	SE-XBiN-2	C56H48O5	801.00
						Synthesis example	15A	XBiN-3	E-XBiN-3	C38H38O5	574.72
Synthetic example	15-1	XBiN-3	SXBiN-3	C52H46O3	718.94
						Synthetic example	15-2	XBiN-3	SE-XBiN-3	C56H54O5	807.04
Synthesis example	16A	P-3	E-P-3	C30H28O5	468.55
						Synthetic example	16-1	P-3	SP-3	C44H36O3	612.77
Synthetic example	16-2	P-3	SE-P-3	C48H44O5	700.88
						Synthesis example	17A	P-4	E-P-4	C30H34O5	474.24
Synthetic example	17-1	P-4	SP-4	C44H42O3	618.82
						Synthetic example	17-2	P-4	SE-P-4	C48H50O5	706.92
Synthesis example	18A	XBisN-2	E-XBisN-2	C35H34O5	534.65
						Synthetic example	18-1	XBisN-2	SXBisN-2	C49H42O3	678.87
Synthetic example	18-2	XBisN-2	SE-XBisN-2	C53H50O5	766.98
						Synthesis example	19A	XBisN-3	E-XBisN-3	C34H32O5	520.63
Synthetic example	19-1	XBisN-3	SXBisN-3	C48H40O3	664.85
						Synthetic example	19-2	XBisN-3	SE-XBisN-3	C52H48O5	752.95
Synthesis example	20A	XBisN-4	E-XBisN-4	C31H26O6	494.54
						Synthetic example	20-1	XBisN-4	SXBisN-4	C45H34O4	638.76
Synthetic example	20-2	XBisN-4	SE-XBisN-4	C49H42O6	726.87
						Synthesis example	21A	P-5	E-P-5	C33H36O8	560.64
Synthetic example	21-1	P-5	SP-5	C61H52O4	849.08
						Synthetic example	21-2	P-5	SE-P-5	C69H58O8	1025.30
Synthesis example	22A	P-6	E-P-6	C27H32O8	484.55
						Synthetic example	22-1	P-6	SP-6	C55H48O4	772.99
Synthetic example	22-2	P-6	SE-P-6	C63H54O8	949.20

<the synthesis of synthesis example 23>resin (R1-XBisN-1)

Prepare that there is serpentine condenser, thermometer and stirring blade, the dismountable internal volume 1L in bottom four-hole boiling flask. In the four-hole boiling flask, compound (XBisN-1) 32.6g (70mmol, Mitsubishi obtained in synthesis example 1 are put into nitrogen stream Gas Chemical Co., Ltd. system), 40 mass % formlinata aquae concentratac 21.0g (280mmol, Mitsubishi's gas are calculated as with formaldehyde Learn Co. Ltd. system) and 98 mass % sulfuric acid (Kanto Kagaku K. K.'s system) 0.97mL, under normal pressure, while making it with 100 DEG C Flow back side reaction 7 hours.Then, as retarder thinner, ortho-xylene (Wako Pure Chemical Industries, Ltd. is added into reaction solution Reagent processed is superfine) 180.0g, the water phase of lower layer is removed after standing.In turn, it is neutralized and is washed, distillation removal is adjacent under reduced pressure Thus dimethylbenzene obtains resin (R1-XBisN-1) 34.1g of brown solid.

Gained resin (R1-XBisN-1) is Mn:1975, Mw:3650, Mw/Mn:1.84.

<the synthesis of synthesis example 24>resin (R2-XBisN-1)

Prepare that there is serpentine condenser, thermometer and stirring blade, the dismountable internal volume 1L in bottom four-hole boiling flask. In the four-hole boiling flask, compound (XBisN-1) 32.6g (70mmol, Mitsubishi obtained in synthesis example 1 are put into nitrogen stream Gas Chemical Co., Ltd. system), 4- biphenylcarboxaldehyde 50.9g (280mmol, Mitsubishi Gas Chemical Co., Ltd's system), methyl phenyl ethers anisole (close Eastern Chemical Co., Ltd. system) 100mL and oxalic acid dihydrate (Kanto Kagaku K. K.'s system) 10mL, under normal pressure, while with 100 React its side of flowing back 7 hours.Then, as retarder thinner, ortho-xylene (and Wako Pure Chemical Industries strain is added into reaction solution Formula commercial firm reagent is superfine) 180.0g, after standing, remove the water phase of lower layer.In turn, it is neutralized and is washed, steamed under reduced pressure The solvent and unreacted 4- biphenylcarboxaldehyde except organic phase are evaporated, resin (R2-XBisN-1) 34.7g of brown solid is thus obtained.

Gained resin (R2-XBisN-1) is Mn:1610, Mw:2567, Mw/Mn:1.59.

<the synthesis of synthesis example 23A>E-R1-XBisN-1

In the container of internal volume 500ml for having blender, condenser pipe and buret, by resin shown in above-mentioned formula (R1-XBisN-1) 30g and potassium carbonate 29.6g (214mmol) puts into 100ml dimethylformamide, and acetic acid -2- chloroethene is added Reaction solution is stirred 12 hours at 90 DEG C and is reacted by ester 13.12g (108mmol).Then, reaction solution is cold in ice bath But, crystal is precipitated, is filtered and separates.Then, the internal volume 100ml's for having blender, condenser pipe and buret Aforementioned crystal 40g, methanol 80g, THF100g and 24% sodium hydrate aqueous solution are put into container, under reflux stir reaction solution It mixes 4 hours and is reacted.Later, cooling in ice bath, the solid matter of precipitation is filtered and is dried, thus by concentration of reaction solution Obtain resin (E-R1-XBisN-1) 26.5g of brown solid.

Gained resin (E-R1-XBisN-1) is Mn:2176, Mw:3540, Mw/Mn:1.62.

<the synthesis of synthetic example 23-1>SR1-XBisN-1

In the container of internal volume 500ml for having blender, condenser pipe and buret, by previously described formula (R1-XBisN-1) Shown in resin 20.0g and vinyl chloride (trade name CMS-P；SEIMI CHEMICAL CO., LTD. system) 12.8g investment Into 200ml dimethylformamide, in the state of being heated up to 50 DEG C and stirring, by 20 minutes 28 matter of addition of dropping funel % sodium methoxide (methanol solution) 16.0g is measured, reaction solution is stirred 1 hour at 50 DEG C and is reacted.Then, 28 mass % are added Reaction solution is heated up to 60 DEG C and stirred 5 hours, and then 85 mass % phosphoric acid 2.4g are added by sodium methoxide (methanol solution) 3.2g, Stirring after ten minutes, is cooled to 40 DEG C, the dropwise reaction liquid into pure water, cooling after the solid matter of precipitation is filtered and dried To 50 DEG C, the dropwise reaction liquid into pure water after the solid matter of precipitation is filtered and dried, obtains (the SR1- of gray solid XBisN-1 resin 27.2g shown in).

Gained resin (SR1-XBisN-1) is Mn:1989, Mw:2840, Mw/Mn:1.43.

<the synthesis of synthetic example 23-2>SE-R1-XBisN-1

Previously described formula obtained in synthesis example 23 is replaced using previously described formula obtained in synthesis example 23A (E-R1-XBisN-1) (R1-XBisN-1) in addition to this resin shown in is carried out similarly with synthetic example 23-1 and reacts, obtain brown solid (SE-R1-XBisN-1) resin 31.3g shown in.

Gained resin (SE-R1-XBisN-1) is Mn:2378, Mw:3930, Mw/Mn:1.65.

<the synthesis of synthesis example 24A>E-R2-XBisN-1

In the container of internal volume 500ml for having blender, condenser pipe and buret, by above-mentioned resin (R2-XBisN- 1) 30g and potassium carbonate 29.6g (214mmol) are put into 100ml dimethylformamide, and acetic acid -2- chloroethene ester 13.12g is added Reaction solution is stirred 12 hours at 90 DEG C, is reacted by (108mmol).Then, reaction solution is cooling in ice bath, make crystalline substance Body is precipitated, and is filtered and separates.Then, it is thrown in the container for the internal volume 100ml for having blender, condenser pipe and buret Enter aforementioned crystal 40g, methanol 80g, THF100g and 24% sodium hydrate aqueous solution, under reflux by reaction solution stir 4 hours into Row reaction.Later, cooling in ice bath, the solid matter of precipitation is filtered and is dried by concentration of reaction solution, and it is solid thus to obtain brown Resin (E-R2-XBisN-1) 22.3g of body.

Gained resin (E-R2-XBisN-1) is Mn:2516, Mw:3960, Mw/Mn:1.62.

<the synthesis of synthetic example 24-1>SR2-XBisN-1

It is replaced in synthesis example 23 using above-mentioned formula (R2-XBisN-1) compound represented 30.5g obtained in synthesis example 24 Obtained above-mentioned formula (R1-XBisN-1) is in addition to this carried out similarly with synthetic example 23-1 and reacts, and obtains light grey solid Resin 35.1g shown in (SR2-XBisN-1) of body.

Gained resin (SR2-XBisN-1) is Mn:2344, Mw:4215, Mw/Mn:1.80.

<the synthesis of synthetic example 24-2>SE-R2-XBisN-1

Above-mentioned formula obtained in synthesis example 23 is replaced using above-mentioned formula (E-R2-XBisN-1) obtained in synthesis example 24A (R1-XBisN-1) in addition to this resin shown in is carried out similarly with synthetic example 23-1 and reacts, obtain brown solid (SE-R2-XBisN-1) resin 28.4g shown in.

Gained resin (SE-R2-XBisN-1) is Mn:2676, Mw:4730, Mw/Mn:1.77.

Preparation has serpentine condenser, thermometer and stirring blade, the dismountable internal volume 10L in bottom four mouthfuls of burnings Bottle.In the four-hole boiling flask, 1,5- dimethylnaphthalene 1.09kg (7mol, Mitsubishi Gas Chemical Co., Ltd are put into nitrogen stream System), 40 mass % formlinata aquae concentratac 2.1kg (28mol, Mitsubishi Gas Chemical Co., Ltd's system are calculated as with formaldehyde) and 98 matter % sulfuric acid (Kanto Kagaku K. K.'s system) 0.97ml is measured, under normal pressure, reacts it 7 hours when flowing back with 100 DEG C.So Afterwards, as retarder thinner, ethylo benzene (Wako Pure Chemical Industries, Ltd.'s reagent is superfine) 1.8kg is added into reaction solution, it is quiet Postpone the water phase of removal lower layer.In turn, it is neutralized and is washed, under reduced pressure distillation removal ethylo benzene and unreacted 1,5- bis- Thus methyl naphthalene obtains the dimethylnaphthalene formaldehyde resin 1.25kg of hazel-color solid.

The molecular weight of resulting dimethylnaphthalene formaldehyde is Mn:562.

Then, prepare the four-hole boiling flask for having the internal volume 0.5L of serpentine condenser, thermometer and stirring blade.This four In mouth flask, the dimethylnaphthalene formaldehyde resin 100g (0.51mol) obtained as described above is put under nitrogen flowing and to toluene sulphur Sour 0.05g is stirred after being allowed to warm to 190 DEG C of heating 2 hours.Later, 1- naphthols 52.0g is further added (0.36mol), and then be allowed to warm to 220 DEG C and react 2 hours.After solvent dilution, is neutralized and washed, removed under reduced pressure Thus solvent obtains modified resin (CR-1) 126.1g of dark brown solid.

Gained resin (CR-1) is Mn:885, Mw:2220, Mw/Mn:4.17.

[embodiment 1-1~24-2, comparative example 1]

It is recorded using the compound or resin recorded in aforementioned synthetic example 1-1~24-2, in synthesis comparative example 1 CR-1 carries out solubility test.Show the result in table 8.

In addition, preparing the lower layer film for lithography forming material formed shown in following table 8 respectively.Then, these photoetching are used Lower layer's film formation material rotary coating later, is toasted 60 seconds, and then toasted 120 seconds with 400 DEG C on silicon substrate with 240 DEG C, point Not Zhi Zuo film thickness 200nm lower membrane.About acid agent, crosslinking agent and organic solvent, following substance is used.

[embodiment 25~44]

Acid agent: nine fluoromethane sulfonate of Midori Kagaku Co., Ltd. di-t-butyl diphenyl iodine (DTDPI)

Crosslinking agent: SANWA Chemical Co., Ltd. NIKALAC MX270 (NIKALAC)

Organic solvent: propylene glycol methyl ether acetate (PGMEA)

Novolaks: group's honor Chemical Co., Ltd. PSM4357

In addition, preparing the lower layer film for lithography forming material formed shown in following table 9 respectively.Then, these photoetching are used Lower layer's film formation material rotary coating on a silicon substrate, later, toasts 60 seconds at 110 DEG C, after the solvent for removing film, utilizes High-pressure sodium lamp is with cumulative exposure amount 600mj/cm², solidified within irradiation time 20 seconds, respectively make film thickness 200nm lower membrane. About photoacid generator, crosslinking agent and organic solvent, following substance is used.

Radical polymerization initiator: BASF AG IRGACURE184

Crosslinking agent:

Mitsubishi's gas chemistry diallyl bisphenol type cyanate (DABPA-CN)

Small western chemical industry system diallyl bisphenol (BPA-CA)

Small western chemical industry system benzoxazine (BF-BXZ)

Japanese chemical drug biphenyl aralkyl-type epoxy resin (NC-3000-L)

Organic solvent:

Propylene glycol methyl ether acetate (PGMEA)

The structure of aforementioned crosslinking agent is indicated with following formula.

[evaluation of elching resistant]

It is etched test under conditions of as shown below, evaluates elching resistant.Show the results of the evaluation table 8 and table 9.

(etching test condition)

Etaching device: Samco International Corporation system " RIE-10NR "

Output power: 50W

Pressure: 20Pa

Time: 2 minutes

Etching gas

Ar gas flow: CF₄Gas flow: O₂Gas flow=50:5:5 (sccm)

The evaluation of elching resistant follows the steps below.

Firstly, replacing changing used in embodiment 1-1 using novolaks (group's honor Chemical Co., Ltd. system " PSM4357 ") It closes object (SXBisN-1) and in addition to this under the condition that is similarly to Example 1, makes the lower membrane of novolaks.Then, with The lower membrane of the novolaks carries out above-mentioned etching test as object, measures etch-rate at this time.

Then, using the lower membrane of each Examples and Comparative Examples as object, it is carried out similarly above-mentioned etching test, measures this When etch-rate.

Then, on the basis of the etch-rate of the lower membrane of novolaks, elching resistant is evaluated according to evaluation criteria below.

[evaluation criteria]

A: compared with the lower membrane of novolaks, etch-rate is lower than -10%

B: compared with the lower membrane of novolaks, etch-rate is -10%~+5%

C: compared with the lower membrane of novolaks, etch-rate is more than+5%

[table 8]

[table 9]

* the mass parts of each ingredient are indicated in bracket.

From table 8 and table 9, it is thus identified that use the embodiment of lower layer's forming material of the compound comprising present embodiment In, either solubility and elching resistant face are good.On the other hand, using CR-1 (phenol-modified dimethylnaphthalene formaldehyde tree Rouge) comparative example 1 in, elching resistant is bad.

In addition, as described above, the excellent heat resistance of the compound of embodiment.

[embodiment 45~48]

Then, the lower layer film for lithography comprising SXBisN-1, SE-XBisN-1, SBisF-1 or SE-BisF-1 is formed into material Each solution coating of material is in the SiO of film thickness 300nm₂On substrate, toasted 60 seconds at 240 DEG C, and then toast 120 at 400 DEG C Second, the lower membrane of film thickness 70nm is consequently formed.It is coated with Arf resist solution in the lower membrane, toasts 60 at 130 DEG C Second, the photoresist layer of film thickness 140nm is consequently formed.It should be noted that as Arf resist solution, it is following using being compounded The compound of formula (11): 5 mass parts, nine fluoromethane sulfonate of triphenylsulfonium: 1 mass parts, tri-butylamine: 2 mass parts and PGMEA:92 mass parts and the solution prepared.

The compound of following formula (11) is prepared as follows.Firstly, by 2- methyl -2- methacryloxyadamantane 4.15g, methacryloxy-gamma-butyrolacton 3.00g, methacrylic acid 3- hydroxyl -1- Buddha's warrior attendant alkyl ester 2.08g, azo are double different Butyronitrile 0.38g is dissolved in tetrahydrofuran 80ml and reaction solution is made.For the reaction solution, under nitrogen atmosphere by reaction temperature Be maintained at 63 DEG C make its polymerize 22 hours after, reaction solution is added drop-wise in the n-hexane of 400ml.Make the spanning tree obtained in this way Rouge solidification purifying, the white powder of generation is filtered, dried overnight with 40 DEG C under reduced pressure and obtain.

In previously described formula (11), " 40 ", " 40 ", " 20 " indicate the ratio of each structural unit, rather than indicate block copolymer.

Then, using electron beam lithography system (ELIONIX INC. system；ELS-7500,50kev) to photoresist layer into Row exposure, toasts (PEB) 90 seconds at 115 DEG C, is carried out 60 seconds with 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solutions Development, thus obtains the corrosion-resisting pattern of eurymeric.

Using Hitachi Co., Ltd's electron microscope (S-4800) observe resulting 55nml/S (1:1) and The shape of the corrosion-resisting pattern of 80nml/S (1:1).About the shape of the corrosion-resisting pattern after development, will there is no pattern collapse, rectangularity The case where good situation is evaluated as " good ", will in addition to this is evaluated as " bad ".In addition, foregoing observations as a result, will not have There is the good the smallest line width of pattern collapse, rectangularity to be set as the index of " resolution ratio " as evaluation.In turn, will describe good The smallest beam energy of good pattern form is set as " sensitivity ", the index as evaluation.It the results are shown in table 10.

[comparative example 2]

Other than the formation without lower membrane, it is carried out similarly with embodiment 45, in SiO₂It is directly formed on substrate Photoresist layer obtains the corrosion-resisting pattern of eurymeric.Show the result in table 10.

[table 10]

As shown in Table 10, it is thus identified that in the embodiment using lower layer's forming material of the compound comprising present embodiment, Corrosion-resisting pattern shape after development is good, does not also observe defect.It confirmed 2 phase of comparative example with the formation that lower membrane is omitted Than resolution ratio and sensitivity are significantly excellent.

Shown as the difference of the corrosion-resisting pattern shape after developing: lower layer film for lithography used in embodiment 45~48 is formed The adaptation of material and anticorrosive additive material is good.

[embodiment 49~52]

By the solution coating of the lower layer film for lithography forming material of embodiment 1-1~2-2 film thickness 300nm SiO₂Substrate On, it is toasted 60 seconds at 240 DEG C, and then toasted 120 seconds at 400 DEG C, the lower membrane of film thickness 80nm is consequently formed.In the lower membrane On, it is coated with siliceous intermediate layer material, is toasted 60 seconds at 200 DEG C, the interlayer film of film thickness 35nm is consequently formed.In turn, at this It is coated with aforementioned Arf resist solution on interlayer film, is toasted 60 seconds at 130 DEG C, the photic anti-of film thickness 150nm is consequently formed Lose layer.It should be noted that as siliceous intermediate layer material, using in Japanese Unexamined Patent Publication 2007-226170 bulletin<synthesis example 1> The polymer containing silicon atom recorded.

Then, using electron beam lithography system ((ELIONIX INC. system；ELS-7500,50kev) to photoresist layer into Row mask exposure, toasts (PEB) 90 seconds at 115 DEG C, is carried out with 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solutions Develop within 60 seconds, thus obtains the corrosion-resisting pattern of the eurymeric of 55nml/S (1:1).

Then, using Samco International Corporation RIE-10NR, using gained corrosion-resisting pattern as Mask carries out the dry ecthing processing of siliceous interlayer film (SOG), then, successively carries out making in the siliceous interlayer film pattern of gained For the dry ecthing processing of the lower membrane of mask, using resulting lower layer's film figure as the SiO of mask₂The dry ecthing of film is processed.

Each etching condition is for example following shown.

(etching condition to interlayer film against corrosion of corrosion-resisting pattern)

Output power: 50W

Pressure: 20Pa

Time: 1 minute

Etching gas

Ar gas flow: CF₄Gas flow: O₂Gas flow=50:8:2 (sccm)

(etching condition to resist lower membrane of film figure among resist)

Output power: 50W

Pressure: 20Pa

Time: 2 minutes

Etching gas

Ar gas flow: CF₄Gas flow: O₂Gas flow=50:5:5 (sccm)

(resist lower layer film figure to SiO₂The etching condition of film)

Output power: 50W

Pressure: 20Pa

Time: 2 minutes

Etching gas

Ar gas flow: C₅F₁₂Gas flow: C₂F₆Gas flow: O₂Gas flow=50:4:3:1 (sccm)

[evaluation]

The patterned section obtained as described above is observed using Hitachi Co., Ltd's electron microscope (S-4800) (the SiO after etching₂The shape of film), as a result confirmed: using present embodiment lower membrane embodiment in multilayer resist The SiO after etching in processing₂The shape of film is rectangle, and defect is also not observed, is good.

[embodiment 53~56]

Using each compound synthesized in aforementioned synthetic example, optical component is prepared according to proportion shown in following table 11 Form composition.It should be noted that the optical component in table 11 is formed in each ingredient of composition, about acid agent, crosslinking Agent, sour dispersion inhibitor and solvent, use following substance.

Crosslinking agent: SANWA Chemical Co., Ltd. NIKALAC MX270 (NIKALAC)

Organic solvent: propylene glycol methyl ether acetate (PGMEA)

After the optical component of uniform state is formed composition rotary coating on clean Silicon Wafer, in 110 DEG C of baking Prebake conditions (prebake:PB) is carried out in case, 1 μm of thickness of optical component is formed and forms film.Optical component about preparation is formed Film is formed as good situation and is evaluated as " A " by composition, and the case where film existing defects of formation is evaluated as " C ".

Uniform optical component is formed into composition rotary coating after on clean Silicon Wafer, in 110 DEG C of baking oven PB is carried out, 1 μm of thickness of film is formed.For the film, J.A.Woollam multiple angles of incidence light splitting ellipsometer VASE measurement 25 is used Refractive index (λ=589.3nm) at DEG C.About the film of preparation, it is evaluated as " A " in the case where refractive index is 1.65 or more, 1.6 " B " is evaluated as in the case where more than and less than 1.65, less than 1.6 in the case where be evaluated as " C ".In addition, the transparency (λ= It is evaluated as " A " in the case where being 632.8nm) 90% or more, " C " is evaluated as less than 90%.

[table 11]

[embodiment 57~60]

Using each compound synthesized in aforementioned synthesis example and synthetic example, made according to being matched shown in following table 12 Standby anti-corrosion agent composition.It should be noted that in each ingredient of the anti-corrosion agent composition in table 12, about free-radical generating agent, Free radical dispersion inhibitor and solvent use following substance.

Radical polymerization initiator: BASF AG IRGACURE184

Free radical spreads controlling agent: BASF AG IRGACURE1010

Organic solvent: propylene glycol methyl ether acetate (PGMEA)

[evaluation method]

(1) storage stability of anti-corrosion agent composition and film are formed

The storage stability of anti-corrosion agent composition is evaluated as follows: quiet at 23 DEG C, 50%RH after production anti-corrosion agent composition It sets 3 days, visually the presence or absence of observation precipitation, is thus evaluated.In anti-corrosion agent composition after standing 3 days, for homogeneous solution and nothing It is evaluated as A in the case where precipitation, has the case where precipitation to be evaluated as C.In addition, by the anti-corrosion agent composition rotary coating of uniform state After on clean Silicon Wafer, (PB) is toasted before being exposed in 110 DEG C of baking oven, forms the etchant resist of thickness 40nm.It closes In the anti-corrosion agent composition of production, it is evaluated as A in the case where film forms good situation, is commented in the defective situation of film of formation Valence is C.

(2) corrosion-resisting pattern pattern evaluation

By uniform anti-corrosion agent composition rotary coating on clean Silicon Wafer after, exposed in 110 DEG C of baking oven (PB) is toasted before light, forms the etchant resist of thickness 60nm.For gained etchant resist, using electron beam lithography system (ELS-7500, ELIONIX INC. system) irradiation the interval 50nm, 40nm and 30nm 1:1 line and space setting electron beam.It, will after the irradiation Etchant resist heats 90 seconds at an established temperature respectively, is immersed in 60 seconds in PGME and develops.Later, it is cleaned with ultrapure water anti- Erosion film 30 seconds, is dried, forms the corrosion-resisting pattern of minus.For the corrosion-resisting pattern of formation, pass through scanning electron microscope Anti-corrosion agent composition is evaluated in (Hitachi High-Technologies Corporation S-4800) observation line and space Based on electron beam irradiation reactivity.

Sensitivity is indicated with the least energy of per unit area necessary to pattern in order to obtain, is commented according to following Valence.

A: less than 50 μ C/cm²The case where having obtained pattern

C: with 50 μ C/cm²The case where pattern derived above

Pattern is formed, is observed with SEM (scanning electron microscope: Scanning Electron Microscope) Gained pattern form is evaluated according to following.

A: the case where having obtained the pattern of rectangle

B: the case where having obtained substantially rectangular pattern

C: the case where having obtained non-rectangle pattern

[table 12]

As described above, within the scope of its spirit may be used the present invention is not limited to aforementioned embodiments and embodiment Suitably to be changed.

The compound and resin of present embodiment are high to the dissolubility of safety solvent, and heat resistance and elching resistant are good, preceding It states anti-corrosion agent composition and good corrosion-resisting pattern shape is provided.

Furthermore it is possible to realize can using wet process, in order to be formed under heat resistance and the excellent photoresist of elching resistant Tunic and useful compound, resin and photoetching form composition with film.Moreover, the photoetching forms the heat resistance of composition with film It is high, solvent solubility is also high, using compound or resin with specific structure, therefore, the deterioration quilt of film when high-temperature baking Inhibit, the elching resistant also excellent resist and lower membrane for oxygen plasma etch etc. can be formed.In turn, under formation It is also excellent with the adaptation of resist layer when tunic, therefore, excellent corrosion-resisting pattern can be formed.

In turn, refractive index is high, and coloured by low temperature~high-temperature process it is suppressed, therefore, as various optical sections It is also useful that part, which forms composition,.

Therefore, the present invention is for example electrically with insulating materials, resist resin, semiconductor sealing resin, printing electricity Road plate bonding agent, be equipped on electrical equipment/electronic equipment/industrial equipment etc. it is electrical with laminate, be equipped on electrical equipment/ Matrix resin, lamination laminate sheet material, the fiber-reinforced plastic resin, liquid crystal of the prepreg of electronic equipment/industrial equipment etc. The encapsulation of display panel resin, coating, various smears, bonding agent, the smears of semiconductor, semiconductor resist With in resin, lower membrane formation resin, used with film-form, sheet, in addition to this, in plastic lens (prismatic lens, grating Lens, lenticule, Fresnel lens, viewing angle control lens, contrast improve lens etc.), phase-contrast film, electromagnetic wave shielding use It is film, prism, fiber optics, flexible printed wiring solder resist, resistance plating agent, multilayer board interlayer dielectric, photosensitive It can widely and effectively be utilized in optical components such as property optical waveguide etc..

In particular, the present invention is in photoetching resist, lower layer film for lithography and multilayer resist lower membrane and optical section It can particularly effectively be utilized in the field of part.

Japanese patent application 2016-143622 disclosure filed on July 21st, 2016 is by referring to whole simultaneously by it Enter in this specification.

In addition, whole document, patent application and technical standard documented by specification be by referring to quoting in the application, They are specifically documented in the application by referring to quoting to be equal to by each document, patent application and technical standard respectively Situation.

Claims

1. a kind of following formula (0) compound represented,

In formula (0), R^YFor the aryl of hydrogen atom, the alkyl of carbon number 1~30 or carbon number 6~30,

R^ZFor the group or singly-bound of the N valence of carbon number 1~60,

R^TIt is each independently the alkyl of the optional carbon number 1~30 with substituent group, the carbon number 6~30 optionally with substituent group Aryl, the alkenyl of the optionally carbon number 2~30 with substituent group, the alkoxy of the optionally carbon number 1~30 with substituent group, halogen are former Son, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom base replaced the group containing vinyl phenylmethyl Group, the alkyl, the aryl, the alkenyl, the alkoxy optionally include ehter bond, ketonic bond or ester bond, herein, R^TAt least 1 hydrogen atom group replaced the group containing vinyl phenylmethyl for hydroxyl,

X expression oxygen atom, sulphur atom is no bridge joint,

R is each independently 0~2 integer.

2. compound according to claim 1, wherein formula (0) compound represented is to change shown in following formula (1) Object is closed,

In formula (1), R⁰With the R^YFor identical meanings,

R¹For the group or singly-bound of the n valence of carbon number 1~60,

R²~R⁵Be each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally have the carbon number 6 of substituent group~ 30 aryl, optionally the carbon number 2~30 with substituent group alkenyl, optionally have substituent group carbon number 1~30 alkoxy, halogen Plain atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom replaced the group containing vinyl phenylmethyl Group, the alkyl, the aryl, the alkenyl, the alkoxy optionally include ehter bond, ketonic bond or ester bond, herein, R²~ R⁵At least one be hydroxyl hydrogen atom group replaced the group containing vinyl phenylmethyl,

m²And m³It is each independently 0~8 integer,

m⁴And m⁵It is each independently 0~9 integer,

Wherein, m²、m³、m⁴And m⁵It is not simultaneously 0,

N and the N are identical meanings, and herein, when the integer that n is 2 or more, the structural formula in n [] is optionally identical or different,

p²~p⁵It is identical meanings with the r.

3. compound according to claim 1, wherein formula (0) compound represented is to change shown in following formula (2) Object is closed,

In formula (2), R^0AWith the R^YFor identical meanings,

R^1AFor the n of carbon number 1~60^AThe group or singly-bound of valence,

R^2AIt is each independently the alkyl of the optional carbon number 1~30 with substituent group, the carbon number 6~30 optionally with substituent group Aryl, the alkenyl of the optionally carbon number 2~30 with substituent group, the alkoxy of the optionally carbon number 1~30 with substituent group, halogen are former Son, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom base replaced the group containing vinyl phenylmethyl Group, the alkyl, the aryl, the alkenyl, the alkoxy optionally include ehter bond, ketonic bond or ester bond, herein, R^2AAt least 1 hydrogen atom group replaced the group containing vinyl phenylmethyl for hydroxyl,

n^AIt is identical meanings, herein, n with the N^AFor 2 or more integer when, n^AStructural formula in a [] is optionally identical or different,

X^AIt is identical meanings with the X,

q^AIt is each independently 0 or 1.

4. compound according to claim 2, wherein formula (1) compound represented is shown in following formula (1-1) Compound,

In formula (1-1), R⁰、R¹、R⁴、R⁵、n、p²~p⁵、m⁴And m⁵With it is aforementioned be identical meanings,

R⁶~R⁷Be each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally have the carbon number 6 of substituent group~ Alkenyl, halogen atom, nitro, amino, carboxylic acid group, the sulfydryl of 30 aryl, the optionally carbon number 2~30 with substituent group,

Herein, R¹⁰~R¹¹At least one be the group containing vinyl phenylmethyl,

m⁶And m⁷It is each independently 0~7 integer,

Wherein, m⁴、m⁵、m⁶And m⁷It is not simultaneously 0.

5. compound according to claim 4, wherein formula (1-1) compound represented is shown in following formula (1-2) Compound,

In formula (1-2), R⁰、R¹、R⁶、R⁷、R¹⁰、R¹¹、n、p²~p⁵、m⁶And m⁷With it is aforementioned be identical meanings,

R⁸~R⁹With the R⁶~R⁷For identical meanings,

R¹²~R¹³With the R¹⁰~R¹¹For identical meanings,

m⁸And m⁹It is each independently 0~8 integer,

Wherein, m⁶、m⁷、m⁸And m⁹It is not simultaneously 0.

6. compound according to claim 3, wherein formula (2) compound represented is shown in following formula (2-1) Compound,

In formula (2-1), R^0A、R^1A、n^A、q^AAnd X^AIt is identical meanings with explanation in the formula (2),

R^3AIt is each independently the alkyl of the optional carbon number 1~30 with substituent group, the carbon number 6~30 optionally with substituent group Alkenyl, halogen atom, nitro, amino, carboxylic acid group, the sulfydryl of aryl, the optionally carbon number 2~30 with substituent group,

Herein, R^4AAt least one be the group containing vinyl phenylmethyl,

m^6AIt is each independently 0~5 integer.

7. a kind of resin is using compound described in claim 1 as obtained from monomer.

8. resin according to claim 7, with structure shown in following formula (3),

In formula (3), L is the alkylidene of the optional carbon number 1~30 with substituent group, the carbon number 6~30 optionally with substituent group The alkylene oxide group or singly-bound of arlydene, the optionally carbon number 1~30 with substituent group, the alkylidene, the arlydene, the Asia Alkoxy optionally includes ehter bond, ketonic bond or ester bond,

R⁰With the R^YFor identical meanings,

R¹For the group or singly-bound of the n valence of carbon number 1~60,

R²~R⁵Be each independently the alkyl of the optional carbon number 1~30 with substituent group, optionally have the carbon number 6 of substituent group~ 30 aryl, optionally the carbon number 2~30 with substituent group alkenyl, optionally have substituent group carbon number 1~30 alkoxy, halogen Plain atom, nitro, amino, carboxylic acid group, sulfydryl, hydroxyl or hydroxyl hydrogen atom replaced the group containing vinyl phenylmethyl Group, the alkyl, the aryl, the alkenyl, the alkoxy optionally include ehter bond, ketonic bond or ester bond,

m²And m³It is each independently 0~8 integer,

m⁴And m⁵It is each independently 0~9 integer,

Wherein, m²、m³、m⁴And m⁵It is not simultaneously 0, R²~R⁵At least one be hydroxyl hydrogen atom by contain vinyl phenylmethyl Group replaced group,

p²~p⁵It is identical meanings with the r.

9. resin according to claim 7, with structure shown in following formula (4),

In formula (4), L is the alkylidene of the optional carbon number 1~30 with substituent group, the carbon number 6~30 optionally with substituent group The alkylene oxide group or singly-bound of arlydene, the optionally carbon number 1~30 with substituent group, the alkylidene, the arlydene, the Asia Alkoxy optionally includes ehter bond, ketonic bond or ester bond,

R^0AWith the R^YFor identical meanings,

R^1AFor the n of carbon number 1~30^AThe group or singly-bound of valence,

X^AIt is identical meanings with the X,

q^AIt is each independently 0 or 1.

10. a kind of composition, contains: selected from by compound according to any one of claims 1 to 6 and claim 7~9 Any one of described in resin composition one or more of group.

11. composition according to claim 10, also contains solvent.

12. composition described in 0 or 11 according to claim 1, also contains acid agent.

13. composition described in any one of 0~12 according to claim 1, also contains crosslinking agent.

14. composition according to claim 13, wherein the crosslinking agent be selected from by phenolic compounds, epoxide, Cyanate esters, amino-compound, benzoxazine compound, melamine compound, guanamines compound, glycoluril compounds, It is at least one kind of in the group of carbamide compound, isocyanate compound and azido compound composition.

15. composition described in 3 or 14 according to claim 1, wherein the crosslinking agent has at least one allyl.

16. composition described in any one of 3~15 according to claim 1, wherein relative to containing selected from by claim 1 One or more of the group of the composition of resin described in any one of compound and claim 7~9 described in any one of~6 100 mass parts of total quality of composition, the content of the crosslinking agent are 0.1~100 mass parts.

17. composition described in any one of 3~16 according to claim 1, also contains crosslinking accelerator.

18. composition according to claim 17, wherein the crosslinking accelerator is selected from by amine, imidazoles, organic It is at least one kind of in phosphine and the group of lewis acid composition.

19. composition described in 7 or 18 according to claim 1, wherein relative to containing selected from by any in claim 1~6 The conjunction of the composition of one or more of group of resin composition described in any one of compound and claim 7~9 described in 100 mass parts of quality are counted, the content of the crosslinking accelerator is 0.1~5 mass parts.

20. composition described in any one of 0~19 according to claim 1, also contains radical polymerization initiator.

21. composition described in any one of 0~20 according to claim 1, wherein the radical polymerization initiator be selected from In the group be made of ketone system Photoepolymerizationinitiater initiater, organic peroxide system polymerization initiator and azo system polymerization initiator at least 1 kind.

22. composition described in any one of 0~21 according to claim 1, wherein relative to containing selected from by claim 1 One or more of the group of the composition of resin described in any one of compound and claim 7~9 described in any one of~6 100 mass parts of total quality of composition, the content of the radical polymerization initiator are 0.05~25 mass parts.

23. composition described in any one of 0~22 according to claim 1 is used for photoetching and is formed with film.

24. composition described in any one of 0~22 according to claim 1 is used for permanent film against corrosion and is formed.

25. composition described in any one of 0~22 according to claim 1 is used for optical component and is formed.

26. a kind of corrosion-resisting pattern forming method comprising following process: using the composition described in claim 23 on substrate After forming photoresist layer, predetermined region illumination radiation line to the photoresist layer simultaneously develops.

27. a kind of corrosion-resisting pattern forming method comprising following process: using the composition described in claim 23 on substrate Lower membrane is formed, after forming at least 1 layer of photoresist layer in the lower membrane, to the predetermined region of the photoresist layer Illumination radiation line simultaneously develops.

28. a kind of circuit pattern forming method comprising following process: using the composition described in claim 23 on substrate Lower membrane is formed, forms interlayer film in the lower membrane using interlayer film material against corrosion, the shape on the interlayer film After at least 1 layer of photoresist layer, predetermined region illumination radiation line to the photoresist layer simultaneously develops, thus shape At corrosion-resisting pattern, later, the interlayer film is etched using the corrosion-resisting pattern as mask, by gained interlayer film figure Case is etched the lower membrane as etching mask, loses using gained lower layer film figure as etching mask to substrate It carves, thus forms pattern in substrate.

29. a kind of following formula (5) compound represented,

In formula (5), R^5AFor the N of carbon number 1~60^BThe group or singly-bound of valence,

m¹⁰It is each independently 1~3 integer,

N^BFor 1~4 integer, N^BFor 2 or more integer when, N^BStructural formula in a [] is optionally identical or different.