CN104914668B

CN104914668B - Curable resin composition, display element cured film, the forming method of display element cured film and display element

Info

Publication number: CN104914668B
Application number: CN201510105235.1A
Authority: CN
Inventors: 佐藤光央
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2014-03-13
Filing date: 2015-03-10
Publication date: 2019-05-14
Anticipated expiration: 2035-03-10
Also published as: TW201534628A; KR20150107639A; CN104914668A; JP6390125B2; TWI649339B; JP2015175923A; KR102252030B1

Abstract

The purpose of the present invention is to provide a kind of curable resin composition, display element cured film, the forming method of display element cured film and display elements.The present invention is a kind of curable resin composition containing polymer and solvent；The polymer has structural unit and carboxylic structural unit represented by following formula (1).In formula (1), R¹、R²And R³For hydrogen atom or the alkyl of 1 valence.R⁴For the alkyl of (a) (n+1) valence, (b) containing selecting free oxygen atom, sulphur atom ,-SO- and-SO between the carbon-to-carbon of (a) alkyl₂At least one kind of base or (c) (a) alkyl and (b) base made of part or all of at least one kind of substitution of warp in the group being made of halogen atom, cyano, nitro, carboxyl, sulfinic acid base, sulfydryl and alkoxy of hydrogen atom possessed by base in the group of composition.R⁵For singly-bound or-COO-*.

Description

Curable resin composition, display element cured film, display element cured film Forming method and display element

Technical field

The present invention relates to a kind of curable resin composition, radiation-sensitive resin composition, display element cured film, The forming method and display element of the display element cured film.

Background technique

In the display elements such as liquid crystal display element, organic electroluminescent (electroluminescence, EL), it is equipped with Following cured film: to keep the interlayer dielectric of the insulating properties for the wiring closet for being configured to stratiform, to inhibit with touch panel (touch panel) is the protective film of deterioration or the damage of the electronic component of representative, liquid crystal layer etc. is set as fixed film thickness Spacer etc..For such cured film in addition to require it is excellent to the adhesiveness of substrate, transparent conductive film, wiring etc. other than, It is required that the transparency is excellent.

In the formation of the cured film, just to obtain required pattern form the number of steps of it is few and it is available adequately it is flat For the viewpoint of property, curable resin composition is used.As such curable resin composition, so that it may it is hard to obtain high surface For the aspect of degree, study containing the polymer on side chain with ethylene unsaturated bond, and as the polymerization Object it has been known that there is the unsaturated compound made containing epoxy group with carboxyl polymer reacted obtained by, make containing isocyanic acid (reference Japanese Patent Laid-Open obtained by the unsaturated compound of ester group is reacted with the polymer with carboxyl and hydroxyl 11-174464 bulletin and Japanese Patent Laid-Open 2002-20442 bulletin).

Wherein, the requirement recently for the performance of cured film, particularly adhesiveness further increases, the existing hardening Property resin combination is unable to satisfy the requirement.In addition, for the viewpoint of technique (process) stability, to described existing Curable resin composition also require the improvement of storage stability.

[existing technical literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 11-174464 bulletin

[patent document 2] Japanese Patent Laid-Open 2002-20442 bulletin

Summary of the invention

[the problem of invention is to be solved]

The present invention is formed based on case described above, and its purpose is to provide one kind can form adhesiveness and the transparency Excellent cured film, and the curable resin composition of excellent storage stability.

[means solved the problems, such as]

Invention made of in order to solve described problem is a kind of curable resin composition, (below containing polymer Referred to as " [A] polymer ") and solvent (hereinafter also referred to " [B] solvent "), the polymer is with knot represented by following formula (1) Structure unit (hereinafter also referred to " structural unit (I) ") and the structural unit (hereinafter also referred to " structural unit containing acidic groups (II)”)。

[changing 1]

(in formula (1), R¹、R²And R³It is separately hydrogen atom or the alkyl of 1 valence of carbon number 1~20；R¹、R²And R³In 2 or more the carbon atoms that can be mutually bonded and be bonded with them be formed together the ring structure of ring element number 3~20；R⁴For (a) The alkyl of (n+1) valence of carbon number 1~20, (b) between the carbon-to-carbon of (a) alkyl containing select free oxygen atom, sulphur atom ,-SO- and- SO₂At least one kind of base or (c) (a) alkyl and (b) part or all of hydrogen atom possessed by base in the group of composition Through in the group that the alkoxy by halogen atom, cyano, nitro, carboxyl, sulfinic acid base, sulfydryl and carbon number 1~12 forms At least one kind of substitution made of base；The integer that n is 1~6；When n is 2 or more, multiple R¹It may be the same or different, multiple R²It can phase Together can also be different, multiple R³It may be the same or different；R⁵For singly-bound or-COO-*；* expression and R⁴The position of bond；R⁶For hydrogen original Son, methyl or fluorinated methyl)

Another invention made of in order to solve described problem is a kind of as the aobvious of interlayer dielectric, protective film or spacer Show element cured film, is formed by the curable resin composition.

Made of in order to solve described problem and then another invention is a kind of forming method of display element cured film, It include: the step of forming film on substrate；The step of radioactive ray are irradiated at least part of the film；To described through putting The step of film of radiation exposure is developed；And the step of developed film is heated, and by described hard The property changed resin combination forms the film.

Made of in order to solve described problem and then another invention is a kind of display element comprising the display element is used Cured film.

[The effect of invention]

Curable resin composition of the invention can form adhesiveness and transparent excellent cured film, and storage stability It is excellent.Display element of the invention, as described above since adhesiveness and the transparency are excellent, therefore can be used suitably with cured film Make the interlayer dielectric, protective film, spacer etc. of display element.Therefore, these may be suitably used to liquid-crystal apparatus (device) Deng display element manufacturing process.

Specific embodiment

Curable resin composition of the invention contains [A] polymer and [B] solvent.The curable adhensive compositions can contain [C] has polymerizable compound (hereinafter also referred to " [C] polymerizable compound "), [D] radical polymerization of ethylene unsaturated bond Closing initiator, [E] acid producing agent, and/or [F] makes comprising in the group being made of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides It is at least one kind of be copolymerized with the unsaturated compound containing epoxy group monomer made of polymer (hereinafter also referred to " [F] is poly- Close object ") it is used as preferred component, any other ingredient can also be contained in the range of not undermining effect of the invention.

The curable resin composition is available due to (methyl) acryloyl group of the structural unit (I) of [A] polymer It heats and carries out polymerization reaction, therefore can be used as thermosetting resin composition and function.In addition, the hardening resin group Object is closed as described later by the radical polymerization initiator containing radioactivity-sensitive and/or the acid producing agent of radioactivity-sensitive, It can be used as radiation-sensitive resin composition to function.Radioactive ray can for example be enumerated: visible light, ultraviolet light, far ultraviolet, X The electromagnetic waves such as ray；Charged particle beams such as electron beam, alpha ray etc..

Each ingredient is illustrated below.

<[A] polymer>

[A] polymer is the polymer with structural unit (I) Yu structural unit (II).[A] polymer preferably in addition to Other than the structural unit, also has for the structural unit other than structural unit (I) and structural unit (II) and do not contain The structural unit (III) of either one or two of hydroxyl, amino and imino group, can also contain in the range of not undermining effect of the invention Other structures unit other than structural unit (I)~structural unit (III).[A] polymer is containing one kind or two or more each Structural unit.

By containing [A] polymer, the adhesiveness and the transparency of the cured film of the curable resin composition are excellent, and And excellent storage stability.In addition, the radioactive ray sense when the situation of radioactive ray curable resin composition is made as described later It spends excellent.The reasons why obtaining the effect and having the composition about the curable resin composition is not necessarily clear, But such as it can be speculated as follows.That is, there is [A] polymer structural unit (I), which to be used as, contains ethylene insatiable hunger in side chain With the structural unit of key.The structural unit (I) is different from the situation of existing curable resin composition, and does not have and pass through Hydroxyl that carboxyl is generated with reacting for epoxy group reacts the imino group etc. generated by hydroxyl and isocyanate group. Its result thinks: for example, by inhibiting alkaline aqueous solution to the infiltration etc. between pattern in development step, Lai Tigao cured film Adhesiveness.In addition, the structural unit (I) by [A] polymer does not have hydroxyl, imino group etc., and it is considered by these base institutes Rotten when caused heating is inhibited, so that the transparency of cured film improves.And then think, will not cause the hydroxyl, Imino group etc. and the condensation of the carboxyl of structural unit (II) etc. etc., therefore storage stability improves.Radioactive ray hardenability tree is being made When the situation of oil/fat composition, it is believed that because not having hydroxyl, imino group etc. nearby in ethylene unsaturated bond etc., free radical or acid Activity is got higher, as a result, radioactive ray sensitivity further increases.

Each structural unit is illustrated below.

[structural unit (I)]

Structural unit (I) is indicated by following formula (1).

[changing 2]

In the formula (1), R¹、R²And R³It is separately hydrogen atom or the alkyl of 1 valence of carbon number 1~20.R¹、R²And R³ In 2 or more the carbon atoms that can be mutually bonded and be bonded with them be formed together the ring structure of ring element number 3~20.R⁴For (a) alkyl of (n+1) valence of carbon number 1~20, (b) contain between the carbon-to-carbon of (a) alkyl selects free oxygen atom, sulphur atom ,-SO- And-SO₂Composition group at least one kind of base or (c) (a) alkyl and (b) a part of hydrogen atom possessed by base or All through selected from the group being made of the alkoxy of halogen atom, cyano, nitro, carboxyl, sulfinic acid base, sulfydryl and carbon number 1~12 Base made of at least one kind of substitution in group.The integer that n is 1~6.When n is 2 or more, multiple R¹It may be the same or different, multiple R² It may be the same or different, multiple R³It may be the same or different.R⁵For singly-bound or-COO-*.* expression and R⁴The position of bond.R⁶For Hydrogen atom, methyl or fluorinated methyl.

R¹、R²And R³The alkyl of 1 valence of represented carbon number 1~20 can for example be enumerated: the chain hydrocarbon of 1 valence of carbon number 1~20 Base, the alicyclic type hydrocarbon of 1 valence of carbon number 3~20, aromatic hydrocarbyl of 1 valence of carbon number 6~20 etc..

The chain alkyl of 1 valence can for example be enumerated:

The alkyl such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the second butyl, tert-butyl；

The alkenyls such as vinyl, acrylic, cyclobutenyl；

Alkynyls such as acetenyl, propinyl, butynyl etc..

The alicyclic type hydrocarbon of 1 valence can for example be enumerated:

The naphthenic base such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, norborny, adamantyl；

The rings such as cyclopropanyl, cyclobutane base, cyclopentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base, norbornene Alkenyl etc..

The aromatic hydrocarbyl of 1 valence can for example be enumerated:

The aryl such as phenyl, tolyl, xylyl, mesitylene base, naphthalene, anthryl；

Aralkyl such as benzyl, phenethyl, naphthyl methyl, anthrylmethyl etc..

R¹、R²And R³In 2 or more be mutually bonded and ring element number 3 that the carbon atoms that are bonded with them are formed together~ 20 ring structure can for example be enumerated: cyclopropylene structure, cyclobutane structure, cyclopentene structure, cyclohexene, cyclo-octene structure, Cycloalkene structures such as norbornene structure etc..

R¹、R²And R³Preferably the chain alkyl of hydrogen atom, 1 valence, more preferably hydrogen atom, alkyl, and then preferably hydrogen is former Son, methyl, ethyl, particularly preferably hydrogen atom.

R⁴The alkyl of (n+1) valence of represented (a) carbon number 1~20 can for example be enumerated: from as R¹、R²And R³It is represented 1 valence alkyl and base made of n hydrogen atom etc. is removed in the base that illustrates.

R⁴Base of represented (b) between the carbon-to-carbon of (a) alkyl containing oxygen atom can for example be enumerated: from as R¹、R²And R³And base made of (n+1) a hydrogen atom etc. is removed in 2 in the alkyl illustrated and ether made of oxygen atom bond.

R⁴Base of represented (b) between the carbon-to-carbon of (a) alkyl containing sulphur atom can for example be enumerated: from as R¹、R²And R³And base made of (n+1) a hydrogen atom etc. is removed in 2 in the alkyl illustrated and thioether made of sulphur atom bond.

R⁴Base of represented (b) between the carbon-to-carbon of (a) alkyl containing-SO- can for example be enumerated: from as R¹、R²And R³ And removal (n+1) a hydrogen atom forms in sulfoxide compound made of sulphur atom bond of 2 in the alkyl illustrated with-SO- Base etc..

R⁴Represented (b) contains-SO between the carbon-to-carbon of (a) alkyl₂Base can for example enumerate: from as R¹、R²And R³ And 2 in the alkyl illustrated and-SO₂Sulphur atom bond made of remove made of (n+1) a hydrogen atom in sulphones Base etc..

The Alkoxy of carbon number 1~12 can such as be enumerated: methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy.

R⁴The halogen atom of represented (c) base can for example be enumerated: fluorine atom, chlorine atom, bromine atom, iodine atom etc..It is sub- Sulfonic group refers to-SO₂H。

R⁴Preferably (a) alkyl, (b) base, more preferably remove from alkane, cycloalkane, aromatic hydrocarbons and cycloakyl alkyl ethers (n+1) base made of a hydrogen atom, and then preferably from the alkane of carbon number 2~6, the cycloalkane of carbon number 3~15, carbon number 6~18 Aromatic hydrocarbons (arene) and carbon number 5~20 cycloakyl alkyl ethers in remove (n+1) a hydrogen atom made of base, particularly preferably Base made of (n+1) a hydrogen atom is removed from ethyl group, hexamethylene, adamantane, benzene and adamantyl ethylether.

It is provided with for the viewpoint of the synthesis easiness of the monomer of structural unit (I), n is preferably 1~3 integer, more excellent Be selected as 1 or 2, the viewpoint of radioactive ray sensitivity when just further increasing hardenability and radioactive ray curable resin composition is made and Speech, n and then preferably 2.

In R⁴For chain alkyl, alicyclic type hydrocarbon, between the carbon-to-carbon of these bases containing select free oxygen atom, sulphur atom ,- SO- and-SO₂Part or all of warp of hydrogen atom possessed by least one kind of base and the base in the group of composition In the group that the alkoxy by halogen atom, cyano, nitro, carboxyl, sulfinic acid base, sulfydryl and carbon number 1~12 forms When the situation of base made of at least one kind of substitution, R⁵Preferably-COO-*.

R⁶Represented fluorinated methyl can for example be enumerated: methyl fluoride, difluoromethyl, trifluoromethyl etc..It is wherein preferably three Methyl fluoride.

It is provided with for the viewpoint of the copolymerizable of the monomer of structural unit (I), R⁶Preferably methyl.

Structural unit (I) can for example be enumerated: structural unit represented by following formula (1-1)~formula (1-12) is (following to be also referred to as For " structural unit (I-1)~structural unit (I-12) ") etc..

[changing 3]

In the formula (1-1)~formula (1-12), R⁶It is synonymous with the formula (1).

Wherein, preferably structural unit (I-1)~structural unit (I-7).

The method that structural unit (I) is set into [A] polymer is not particularly limited, such as can be listed below method etc.: As shown in following processes, by using the polymerization of monomer represented by following formula (i), synthesis group enters to have following formula (1 ') institute The polymer of the structural unit (I ') of expression, and the polymer is made for example to carry out dehydrohalogenation in the presence of the alkali such as triethylamine Reaction, thus generates ethylene unsaturated double-bond, to form structural unit (I) represented by following formula (1).

[changing 4]

In the process, R¹~R⁶And n is synonymous with the formula (1).X is halogen atom.

For improving the viewpoint of yield of de-hydrogen halide, halogen atom represented by X is preferably chlorine atom, bromine original Son, more preferably chlorine atom.

Monomer represented by the formula (i) can for example be synthesized in the following way: make (methyl) acrylic acid 2- hydroxyl Ethyl ester etc. have the β-such as compound and the 3- chlorpromazine chloride of (methyl) acryloyl group and hydroxyl it is halogenated-acid halide is in alkali such as pyridines In the presence of, dehydrohalogenation condensation reaction is carried out in methylene chloride equal solvent.

The content ratio of the structural unit (I) is with whole monomers used in the synthesis relative to [A] polymer Input ratio meter, preferably 5 moles of %~90 mole %, more preferably 10 moles of %~70 mole %, and then preferably 15 rub You are %~40 mole %.By the way that the content ratio is set as the range, the adhesiveness and thoroughly of cured film can further improve Bright property, storage stability and radioactive ray sensitivity when radioactive ray curable resin composition is made.

[structural unit (II)]

Structural unit (II) is the structural unit containing acidic groups.Acidic groups can enumerate carboxyl, phenolic hydroxyl group, sulfo group, contain There is the base etc. of fluorine alcohol, wherein particularly preferably carboxyl.There is structural unit (II) by [A] polymer, the hardening resin Composition can play alkali-developable, to function as alkali soluble resin.

The monomer for providing the structural unit (II) can for example be enumerated: unsaturated monocarboxylic, unsaturated dicarboxylic, polynary carboxylic List [(methyl) acryloyl group oxygroup alkyl] ester of acid, the acid anhydride of unsaturated dicarboxylic have the poly- of carboxyl and hydroxyl in two ends Close list (methyl) acrylate, the unsaturated polycyclic compound with carboxyl and its acid anhydride etc. of object.

Unsaturated monocarboxylic can for example be enumerated: acrylic acid, methacrylic acid, butenoic acid etc..

Unsaturated dicarboxylic can for example be enumerated: maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc..

List [(methyl) acryloyl group oxygroup alkyl] ester of polybasic carboxylic acid can for example be enumerated: maleic acid list [(methyl) Acryloyl group oxygroup ethyl] ester, succinic acid list [2- (methyl) acryloyl group oxygroup ethyl] ester, phthalic acid list [2- (first Base) acryloyl group oxygroup ethyl] ester etc..

The acid anhydride of unsaturated dicarboxylic can for example be enumerated: the acid anhydride etc. of the compound illustrated as the dicarboxylic acids.

In two ends there is list (methyl) acrylate of the polymer of carboxyl and hydroxyl can for example enumerate: ω-carboxyl is poly- Caprolactone list (methyl) acrylate etc..

Unsaturated polycyclic compound and its acid anhydride with carboxyl can for example be enumerated: bicyclic [2.2.1] the hept- 2- of 5- carboxyl Bicyclic [2.2.1] hept-2-ene" of alkene, 5,6- dicarboxyl, 5- carboxyl -5- methyl bicycle [2.2.1] hept-2-ene", 5- carboxyl -5- ethyl Bicyclic [2.2.1] hept-2-ene", 5- carboxyl -6- methyl bicycle [2.2.1] hept-2-ene", 5- carboxyl -6- ethyl are bicyclic [2.2.1] Bicyclic [2.2.1] hept-2-ene" acid anhydride of hept-2-ene", 5,6- dicarboxyl etc..

Additionally, it is provided chemical combination made of the carboxyl for protecting described carboxylic acid etc. can also be used in the monomer of the structural unit (II) Object.Protected carboxyl in the compound can for example enumerate the hydrogen atom warp-C (R of carboxyl^a)(R^b)(OR^c) made of substitution Base (R^aAnd R^bIt is separately hydrogen atom or the alkyl of 1 valence of carbon number 1~20.R^cFor the alkyl of 1 valence of carbon number 1~20) etc.. R^a、R^bAnd R^cThe alkyl of 1 valence of represented carbon number 1~20 can for example be enumerated and as the R¹、R²And R³And 1 valence illustrated Same base of alkyl etc..Wherein, R^aAnd R^cPreferably alkyl.R^bPreferably hydrogen atom.

Protect compound made of the carboxyl of described carboxylic acid etc. that can for example enumerate: (methyl) acrylic acid 1- butoxyethyl, (methyl) acrylic acid 1- ethoxy ethyl ester, (methyl) acrylic acid 1- Ethoxybutyl etc..

Wherein, the copolymerizable and accessibility and [A] polymer for being provided with the monomer of structural unit (II) are to alkalinity For the deliquescent viewpoint of aqueous solution, preferably unsaturated monocarboxylic, protect unsaturated monocarboxylic carboxyl made of chemical combination Object, more preferably methacrylic acid, methacrylic acid 1- butoxyethyl.

The content ratio of the structural unit (II) is with whole monomers used in the synthesis relative to [A] polymer Input ratio meter, preferably 5 moles of %~50 mole %, more preferably 10 moles of %~40 mole %, and then preferably 15 rub You are %~35 mole %.By the way that the content ratio is set as the range, the alkali of the curable resin composition can be shown Shadow is set as more appropriate property.

[structural unit (III)]

Structural unit (III) be the structural unit other than structural unit (I) and structural unit (II) and be free from hydroxyl, The structural unit of either one or two of amino and imino group.There is structural unit (III) by [A] polymer, can further improve institute State the storage stability of curable resin composition.

The monomer for providing the structural unit (III) can for example enumerate alkyl methacrylate, methacrylic acid cycloalkanes Base ester, alkyl acrylate, acrylate base ester, methacrylic acid aromatic ester, acrylic acid aromatic ester etc., in addition can arrange It lifts for following compound etc. and without either one or two of hydroxyl, amino and imino group etc.: unsaturated dicarboxylic diester, bicyclic insatiable hunger With compound, N- maleimide compounds, unsaturated aromatic compound, conjugated diene, have tetrahydrofuran skeleton, Furans skeleton, the unsaturated compound of oxinane skeleton or pyrans skeleton, other unsaturated compounds etc..

Alkyl methacrylate can for example be enumerated: methyl methacrylate, ethyl methacrylate, methacrylic acid are just Butyl ester, the second butyl ester of methacrylic acid, Tert-butyl Methacrylate, 2-Ethylhexyl Methacrylate, isodecyl The positive Lauryl Ester of ester, methacrylic acid, Tridecyl methacrylate base ester, the positive stearyl of methacrylic acid etc..

Cycloalkyl methacrylate can for example be enumerated: cyclohexyl methacrylate, methacrylic acid 2- methyl cyclohexyl, Methacrylic acid tricyclic [5.2.1.0^2,6] decane -8- base ester, methacrylic acid tricyclic [5.2.1.0^2,6] decane -8- base oxygroup second Ester, isobornyl methacrylate etc..

Alkyl acrylate can for example be enumerated: methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid second The positive Lauryl Ester of butyl ester, tert-butyl acrylate, 2-EHA, isodecyl acrylate, acrylic acid, acrylic acid tridecane Base ester, n-stearyl acrylate etc..

Acrylate base ester can for example be enumerated: cyclohexyl acrylate, acrylic acid -2- methyl cyclohexyl, acrylic acid tricyclic [5.2.1.0^2,6] decane -8- base ester, acrylic acid tricyclic [5.2.1.0^2,6] decane -8- base oxygroup ethyl ester, isobomyl acrylate base Ester etc..

Methacrylic acid aromatic ester can for example be enumerated: the methyl such as phenyl methacrylate, naphthyl Benzyl acrylate；Methacrylic acids aralkyl esters such as benzyl methacrylate, methacrylic acid phenethyl ester etc..

Acrylic acid aromatic ester can for example be enumerated: the benzyl acrylates such as phenyl acrylate, acrylic acid naphthalene ester；Propylene Acrylic acid aralkyl esters such as sour benzyl ester, acrylic acid phenethyl ester etc..

Unsaturated dicarboxylic diester can for example be enumerated: diethyl maleate, diethyl fumarate, itaconic acid two Ethyl ester etc..

Bicyclic unsaturated compound can for example be enumerated: bicyclic [2.2.1] hept-2-ene", 5- methyl bicycle [2.2.1] hept- 2- Bicyclic [2.2.1] hept-2-ene" of alkene, 5- ethyl, bicyclic [2.2.1] hept-2-ene" of 5- methoxyl group, bicyclic [2.2.1] hept- of 5- ethyoxyl Bicyclic [2.2.1] hept-2-ene" of 2- alkene, 5,6- dimethoxy, bicyclic [2.2.1] hept-2-ene" of 5,6- diethoxy, 5- tert-butoxy Bicyclic [2.2.1] hept-2-ene" of carbonyl, bicyclic [2.2.1] hept-2-ene" of 5- cyclohexyl Epoxide carbonyl, 5- phenyloxycarbonyl are bicyclic Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5,6- bis- (tert-butoxycarbonyl), 5,6- bis- (cyclohexyl Epoxide carbonyl) Bicyclic [2.2.1] hept-2-ene" etc..

N- maleimide compounds can for example be enumerated: N- phenylmaleimide, N- cyclohexyl maleic Imidodicarbonic diamide, N- benzylmaleimide, N- (4- hydroxy phenyl) maleimide, N- succinimido -3- Maleimide benzoic ether, N- succinimido -4- maleimide butyrate, N- succinimido - 6- maleimide capronate, N- succinimido -3- maleimide propionic ester, N- (9- acridinyl) are along fourth Alkene imidodicarbonic diamide etc..

Unsaturated aromatic compound can for example be enumerated: styrene, α-methylstyrene, m-methyl styrene, to methyl Styrene, vinyltoluene, to methoxy styrene etc..

Conjugated diene can for example be enumerated: 1,3-butadiene, isoprene, 2,3- dimethyl -1,3-butadiene etc..

Unsaturated compound with tetrahydrofuran skeleton can for example be enumerated: methacrylic acid tetrahydro furfuryl ester, 2- methyl Acryloyl group oxygroup-propionic acid tetrahydro furfuryl ester, 3- (methyl) acryloyl group oxygroup tetrahydrofuran -2- ketone etc..

Unsaturated compound containing furans skeleton can for example be enumerated: 2- methyl -5- (3- furyl) -1- penten-3-one, (methyl) acrylic acid furfuryl group ester, 1- furans -2- butyl -3- alkene -2- ketone, 1- furans -2- butyl -3- methoxyl group -3- alkene -2- ketone, 6- (2- furyl)-2- methyl-1-hexene-3-one, 6- furans-2- base-hex- 1- alkene-3- ketone, acrylic acid 2- furans-2- base-1- Methyl-ethyl ester, 6- (2- furyl)-6- methyl-1-teracrylic acid -one etc..

Unsaturated compound containing oxinane skeleton can for example be enumerated: methacrylic acid oxinane -2- base methyl esters, 2,6- dimethyl -8- (oxinane -2- base oxygroup) octyl- 1- alkene -3- ketone, 2- methacrylic acid oxinane -2- base ester, 1- (oxinane -2- oxygroup) butyl -3- alkene -2- ketone etc..

Unsaturated compound containing pyrans skeleton can for example be enumerated: 4- (Isosorbide-5-Nitrae-dioxa -5- oxo -6- heptenyl) - 6- methyl -2- pyrans, 4- (1,5- dioxa -6- oxo -7- octenyl) -6- methyl -2- pyrans etc..

Other unsaturated compounds can for example be enumerated: acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acryloyl Amine, Methacrylamide, vinyl acetate etc..

Wherein, it is provided with for the viewpoint of the copolymerizable of the monomer of structural unit (III), preferably methacrylate Ester, unsaturated aromatic compound, more preferably methyl methacrylate, styrene.

The content ratio of the structural unit (III) is with whole monomers used in the synthesis relative to [A] polymer Input ratio meter, preferably 0 mole of %~80 mole %, more preferably 20 moles of %~75 mole %, and then preferably 40 rub You are %~70 mole %.By the way that the content ratio is set as the range, the hardening resin combination can further improve The storage stability of object.

[other structures unit]

Other structures unit can for example enumerate the structural unit etc. containing hydroxyl, amino or imino group.Other structures unit Content ratio based on the input ratio of whole monomers used in the synthesis of [A] polymer, preferably 20 moles of % Hereinafter, more preferably 5 moles of % hereinafter, be preferably 0 mole of % in turn.

Relative to the total solid content of the curable resin composition, the amount of [A] polymer is preferably 30 matter Measure % or more, the more preferably 35 mass % of mass %~95, and then preferably 40 mass of mass %~70 %.

[A] polymer can be synthesized in the following way as described, such as use free radical polymerization in a solvent Initiator will provide structure list using de-hydrogen halide after polymerization the monomer as represented by the formula (i) The polymerizations such as the monomer of first (I), the monomer for providing structural unit (II), the monomer for optionally providing structural unit (III), make gained Polymer carry out de-hydrogen halide and form structural unit (I).

Solvent can for example be enumerated: alcohol, chain ether, cyclic ether, glycol ethers, ethylene glycol alkyl ether acetic acid esters, diethylene glycol alkane Base ether, propylene-glycol monoalky lether, propylene-glycol monoalky lether acetic acid esters, propylene-glycol monoalky lether propionic ester, aromatic hydrocarbon, ketone, its His ester etc..

Alcohol can for example be enumerated: methanol, ethyl alcohol, benzylalcohol, 2- phenylethyl alcohol, 3- phenyl-1-propanol etc..

Chain ether can for example be enumerated: diethyl ether, dipropyl ether, butyl oxide, methyl phenyl ethers anisole, diphenyl ether etc..

Cyclic ether can for example be enumerated: tetrahydrofuran, oxinane etc..

Glycol ethers can for example be enumerated: glycol monoethyl ether, ethylene glycol monoethyl ether etc..

Ethylene glycol alkyl ether acetic acid esters can for example be enumerated: methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol Monobutyl ether-acetate, ethylene glycol monoethylether acetate etc..

Diethylene glycol alkyl ether can for example be enumerated: diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diformazan Ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether etc..

Propylene-glycol monoalky lether can for example be enumerated: propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, the third two Alcohol monobutyl ether etc..

Propylene-glycol monoalky lether acetic acid esters can for example be enumerated: propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetic acid esters, propylene glycol monobutyl ether acetic acid esters etc..

Propylene-glycol monoalky lether propionic ester can for example be enumerated: propylene glycol monomethyl ether propionate, dihydroxypropane single-ether propionic ester, Propylene glycol monopropyl ether propionic ester, propylene glycol monobutyl ether propionic ester etc..

Aromatic hydrocarbon can for example be enumerated: toluene, dimethylbenzene etc..

Ketone can for example be enumerated: methyl ethyl ketone, cyclohexanone, 4- hydroxy-4-methyl-2-pentanone etc..

Other esters can for example be enumerated: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2- hydroxy-2-methyl methyl propionate, 2- hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, hydroxyl second Acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3- hydroxy methyl propionate, 3- hydroxypropionate, 3- hydroxyl Base propyl propionate, 3- hydracrylic acid butyl ester, 2- hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, methoxyacetic acid second Ester, methoxy propyl acetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid third Ester, ethoxyacetic acid butyl ester, propoxyl group methyl acetate, propoxyl group ethyl acetate, propoxyl group propyl acetate, propoxyl group acetic acid fourth Ester, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2- methoxypropionic acid first Ester, 2- methoxypropionate, 2- methoxy propyl propyl propionate, 2- methoxy propyl acid butyl ester, 2- ethoxypropanoate, 2- ethoxy Base ethyl propionate, 2- ethoxy-c propyl propionate, 2- ethoxy-c acid butyl ester, 2- butoxy methyl propionate, 2- butoxy propionic acid second Ester, 2- butoxy propyl propionate, 2- butoxy butyl propionate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- methoxy Base propyl propionate, 3- methoxy propyl acid butyl ester, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, 3- ethoxy-propionic acid third Ester, 3- ethoxy-c acid butyl ester, 3- propoxyl group methyl propionate, 3- propoxyl group ethyl propionate, 3- propoxyl group propyl propionate, the third oxygen of 3- Base butyl propionate, 3- butoxy methyl propionate, 3- butoxy ethyl propionate, 3- butoxy propyl propionate, 3- butoxy propionic acid fourth Ester etc..

Solvent is preferably other esters, more preferably 3- methoxy methyl propionate.The solvent can be used a kind or 2 kinds with On.

Radical polymerization initiator can for example be enumerated: 2,2 '-azobis isobutyronitriles, 2,2 '-azos are double-(2,4- dimethyl Valeronitrile), 2,2 '-azos it is double-(4- methoxyl group -2,4- methyl pentane nitrile), 4,4 '-azos bis- (4- cyanopentanoic acids), dimethyl -2, 2 '-azos bis- (2 Methylpropionic acid esters), 2,2 '-azos bis- (4- methoxyl group -2,4- methyl pentane nitriles) etc..

It is wherein preferably 2,2 '-azobis isobutyronitriles, 2,2 '-azos pair-(2,4- methyl pentane nitrile).

Relative to total 100 moles of monomer used in polymerization, the usage amount of radical polymerization initiator is preferably 1 to rub You are %~10 mole %, more preferably 2 moles of %~8 mole %.Radical polymerization initiator can be used one kind or two or more.

In the polymerization, molecular weight regulator can be used in order to adjust molecular weight.Molecular weight regulator can for example be enumerated:

The halogenated hydrocarbons such as chloroform, carbon tetrabromide；

The mercaptan such as n-hexyl mercaptan, n octylmercaptan, n-dodecyl mercaptan, tert-dodecylmercaotan, thioglycolic acid Class；

Vulcanize the xanthan acids such as xanthic acid dimethyl ester, diisopropyl xanthate disulfide；

Terpinolene, α-methylstyrenedimer etc..

The usage amount of molecular weight regulator can as expected the molecular weight of [A] polymer and be suitable for selection, but it is opposite The total 100 moles of %, preferably 0.1 mole of %~10 mole %, more preferably 0.5 mole of % of the monomer used in polymerization ~5 moles of %.Molecular weight regulator can be used one kind or two or more.

Polymerization temperature is usually 0 DEG C~150 DEG C, preferably 50 DEG C~120 DEG C.

Polymerization time is usually 10 minutes~20 hours, preferably 30 minutes~6 hours.

Solvent used in de-hydrogen halide after polymerization reaction can be used as workable solvent in the polymerization And the solvent illustrated, preferably directly using solvent used in the polymerization.That is, preferably adding in the polymerization liquid Add alkali, and carries out de-hydrogen halide.

Alkali used in de-hydrogen halide can for example be enumerated:

The amines such as diethylamine, di-n-propylamine, trimethylamine, triethylamine, tripropyl amine (TPA), Pyrrolizidine, piperidines, pyridine, triethanolamine；

The metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide；

The metal carbonates such as sodium carbonate, potassium carbonate, calcium carbonate；

The alkali metal bicarbonate salts such as sodium bicarbonate, saleratus, calcium bicarbonate；

Metal alkoxides such as sodium methoxide, potassium tert-butoxide etc..

Relative to 1 mole of hydrogen halides of disengaging, the amount of alkali used in de-hydrogen halide is preferably 1 mole~10 to rub You, more preferably 1.5 moles~7 moles, and then preferably 2 moles~5 moles.

The temperature of de-hydrogen halide is usually 0 DEG C~150 DEG C, preferably 50 DEG C~100 DEG C.

The time of de-hydrogen halide is usually 10 minutes~20 hours, preferably 30 minutes~6 hours.

The polystyrene converted weight average molecular weight (Mw) of [A] polymer is preferably 2,000~100,000, more preferably It is 3,000~50,000, and then preferably 5,000~20,000.It, can be by the way that the Mw of [A] polymer is set as the range One step improves the adhesiveness of cured film, in addition can further improve radioactive ray sense when radioactive ray curable resin composition is made Degree.

The molecular weight distribution (Mw/Mn) of [A] polymer is preferably 5.0 hereinafter, more preferably 3.0 or less.By the way that [A] is poly- The Mw/Mn for closing object is set as the upper limit hereinafter, the pattern form of cured film can be made further good.

<[B] solvent>

[B] as long as solvent equably dissolves the solvent not reacted containing ingredient and with containing ingredient to use.[B] is molten Agent can for example be enumerated and the same solvent of solvent etc. that illustrates as solvent used in the polymerizeing of synthesis [A] polymer.[B] Solvent can be used one kind or two or more.

For dissolubility, the viewpoints such as the coating of dispersed, the described curable resin composition of solid component, [B] Solvent is preferably propylene glycol monomethyl ether, dihydroxypropane single-ether, acetic acid glycol monoethyl ether ester, propyleneglycolmethyletheracetate monomethyl ether ester, second Acid propylene glycol monoethyl ether ester, acetic acid 3- methoxybutyl, diethylene glycol dimethyl ether, diethylene glycol Methyl ether, cyclohexanone, 2- heptan Ketone, 3- heptanone, 1,3-BDO diacetate esters, 1,6- hexylene glycol diacetate esters, ethyl lactate, 3- methoxy methyl propionate, 3- Methoxypropionate, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, 3- methyl -3- methoxybutyl propionic ester, second Sour N-butyl, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, butyric acid N-butyl, ethyl pyruvate, more preferably 3- methoxy methyl propionate, diethylene glycol Methyl ether, acetic acid 3- methoxybutyl. In addition [B] solvent had preferably also both contained the solvent or had contained high boiling solvent.The high boiling solvent can for example be enumerated: benzyl Base ether, two-n-hexyl ethers, acetonyl acetone, isophorone, caproic acid, octanoic acid, 1- octanol, 1 nonyl alcohol, acetic acid benzyl ester, benzene first Acetoacetic ester, diethyl oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol list Phenyl ether acetate etc..

The amount of [B] solvent is not particularly limited, but is stablized with regard to the screening characteristics of the curable resin composition, preservation For the viewpoints such as property, the preferably 20 mass % of mass %~90, more preferably 40 mass of mass %~80 %.

<[C] polymerizable compound>

[C] polymerizable compound is the polymerizable compound with ethylene unsaturated bond.The hardening resin combination Object can further improve the adhesiveness of cured film when forming negative pattern, in addition exist by also containing [C] polymerizable compound The thermal stability of pattern form can be improved when forming eurymeric pattern.[C] polymerizable compound can also be made to harden by heating, but By can more effectively make its hardening containing aftermentioned [D] radical polymerization initiator.

Base containing ethylene unsaturated bond can for example be enumerated: vinyl, allyl, (methyl) acryloyl group, styrene Base etc..

The number of ethylene unsaturated bond possessed by [C] polymerizable compound also can be multiple for 1.It is hard with regard to improving For the viewpoint for changing the adhesiveness of film, the number of ethylene unsaturated bond is preferably 2 or more, and more preferably 3 or more, it just improves and protects For the viewpoint for depositing stability, the number of ethylene unsaturated bond is preferably 10 hereinafter, more preferably 6 or less.

[C] polymerizable compound can for example be enumerated: monofunctional acrylate, polyfunctional acrylic ester, other polymerisms Close object etc..

Monofunctional acrylate can for example be enumerated: ω-carboxy-polycaprolactone list (methyl) acrylate, ethylene glycol list (first Base) acrylate etc..

Polyfunctional acrylic ester can for example be enumerated: ethylene glycol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) third Olefin(e) acid ester, 1,9- nonanediol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, double phenoxetols Fluorenes two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, methacrylic acid 2- hydroxyl -3- (methyl) Acryloxy propyl ester, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite Four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, three seasons penta Tetrol seven (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, three (2- (methyl) acryloyl-oxyethyl) phosphorus The modified pentaerythritol triacrylate of acid esters, ethylene-oxide-modified dipentaerythritol hexaacrylate, succinic acid, succinic acid are modified Dipentaerythritol Pentaacrylate makes have straight-chain alkyl-sub and ester ring type structure and with 2 or more isocyanate group Compound is with hydroxyl of the intramolecular with 1 or more and the compound with 3~5 (methyl) acryloxies is reacted Obtained by multifunctional (methyl) acrylate compounds such as (methyl) propenoic methyl carbamate etc..

Other polymerizable compounds can for example be enumerated: (methyl) acrylic acid 2- (2 '-vinyloxyethoxy) ethyl ester etc..

The commercially available product of [C] polymerizable compound can for example be enumerated:

Aronix (Aronix) M-400, Aronix (Aronix) M-402, Aronix (Aronix) M-405, Asia Luo Nisi (Aronix) M-450, Aronix (Aronix) M-520, Aronix (Aronix) M-1310, Aronix (Aronix) M-1600, Aronix (Aronix) M-1960, Aronix (Aronix) M-7100, Aronix (Aronix) M-8030, Aronix (Aronix) M-8060, Aronix (Aronix) M-8100, Aronix (Aronix) M-8530, Aronix (Aronix) M-8560, Aronix (Aronix) M-9050, Aronix (Aronix) TO-756, Aronix (Aronix) TO-1450, Aronix (Aronix) TO-1382 (more than, East Asia Synesis Company)；

Block Asia ladd (KAYARAD) DPHA, card Asia ladd (KAYARAD) DPCA-20, card Asia ladd (KAYARAD) DPCA- 30, block Asia ladd (KAYARAD) DPCA-60, card Asia ladd (KAYARAD) DPCA-120, card Asia ladd (KAYARAD) MAX- 3510 (more than, Japanese chemical drug company)；

Than this Carter (Viscoat) 295, than this Carter (Viscoat) 300, than this Carter (Viscoat) 360, than this gram Spy (Viscoat) 802, than this Carter (Viscoat) GPT, than this Carter (Viscoat) 3PA, than this Carter (Viscoat) 400 (more than, Osaka Organic Chemical Industry company)；

New forward position (New Frontier) R-1150 (first industrial pharmaceutical as propenoic methyl carbamate based compound Company)；

Block Asia ladd (KAYARAD) DPHA-40H, card Asia ladd (KAYARAD) DPEA-12, HUX-5000 (more than, it is Japanese Chemical drug company)；

UN-9000H (Gen Shang industrial group)；

Aronix (Aronix) M-5300, Aronix (Aronix) M-5600, Aronix (Aronix) M-5700, Aronix (Aronix) M-210, Aronix (Aronix) M-220, Aronix (Aronix) M-240, Aronix (Aronix) M-270, Aronix (Aronix) M-6200, Aronix (Aronix) M-305, Aronix (Aronix) M- 309, Aronix (Aronix) M-310, Aronix (Aronix) M-315 (more than, East Asia Synesis Company)；

Block Asia ladd (KAYARAD) HDDA, card Asia ladd (KAYARAD) HX-220, card Asia ladd (KAYARAD) HX- 620, it is sub- to block Asia ladd (KAYARAD) R-526, card Asia ladd (KAYARAD) R-167, card Asia ladd (KAYARAD) R-604, card Ladd (KAYARAD) R-684, card Asia ladd (KAYARAD) R-551, card Asia ladd (KAYARAD) R-712, UX-2201, UX- 2301、UX-3204、UX-3301、UX-4101、UX-6101、UX-7101、UX-8101、UX-0937、MU-2100、MU-4001 (more than, Japanese chemical drug company)；

Sub- spy resin (Art Resin) UN-9000PEP, sub- spy resin (Art Resin) UN-9200A, sub- special resin (Art Resin) UN-7600, sub- spy resin (Art Resin) UN-333, sub- spy resin (Art Resin) UN-1003, Ya Te Resin (Art Resin) UN-1255, sub- spy resin (ArtResin) UN-6060PTM, sub- spy resin (Art Resin) UN- 6060P, sub- spy resin (Art Resin) SH-500B (more than, Gen Shang industrial group)；

Than this Carter (Viscoat) 260, than this Carter (Viscoat) 312, than this Carter (Viscoat) 335HP (with On, Osaka Organic Chemical Industry company) etc..

[C] polymerizable compound is preferably polyfunctional acrylic ester, more preferably Dipentaerythritol Pentaacrylate, two seasons Penta tetrol, six acrylate, succinic acid modified pentaerythritol triacrylate, trimethylolpropane trimethacrylate, three Ji Wusi The modified Dipentaerythritol Pentaacrylate of seven acrylate of alcohol, eight acrylate of tripentaerythritol, succinic acid.

Relative to 100 mass parts of [A] polymer, the amount of [C] polymerizable compound be preferably 20 mass parts or more and 200 below the mass, more than more preferably 40 mass parts and 160 below the mass.Pass through containing [C] polymerizable compound Amount is set as the range, and the cured film when curable resin composition can further improve the formation negative pattern glues The thermal stability of pattern form when attached property and formation eurymeric pattern.

<[D] radical polymerization initiator>

[D] radical polymerization initiator is the ingredient for generating following reactive species, and the reactive species, which can cause, has polymerism Compound free radical polymerization.The curable resin composition, which passes through, contains [D] radical polymerization initiator, can be further Improve the adhesiveness of cured film.[D] radical polymerization initiator can for example enumerate: being decomposed and generated free radicals by heating [D1] thermonasty radical polymerization initiator, [D2] the radioactivity-sensitive free radical generated free radicals by the irradiation of radioactive ray Polymerization initiator etc..[D] radical polymerization initiator in the curable resin composition containing form can for it is aftermentioned that The form of the low molecular compound of sample, as [A] polymer etc. a part and the form, the described two forms that are entered by group. One kind or two or more [D] radical polymerization initiator can be contained.

[[D1] thermonasty radical polymerization initiator]

[D1] thermonasty radical polymerization initiator is the compound for decomposing and generating free radicals by heating.It is described hard If the property changed resin combination contains [D1] thermonasty radical polymerization initiator, thermosetting resin composition performance can be used as Function.

[D1] thermonasty radical polymerization initiator can for example be enumerated: azobis isobutyronitrile (azobisisobutyronitrile, AIBN), 2,2 '-azos bis- (4- methoxyl group -2,4- methyl pentane nitriles), 2,2 '-azos The azos such as bis- (2- cyclopropyl propionitrile), 2,2 '-azos bis- (2,4- methyl pentane nitriles), 2,2 '-azobisisobutylonitrile acid esters of dimethyl It is radical initiator；The peroxide such as benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide system is certainly By base initiator etc..

[[D2] radioactivity-sensitive radical polymerization initiator]

[D2] radioactivity-sensitive radical polymerization initiator is the compound generated free radicals by the irradiation of radioactive ray. If the curable resin composition contains [D2] radioactivity-sensitive radical polymerization initiator, radioactive ray hardenability can be used as Resin combination functions, and [A] polymer, [C] polymerizable compound etc. are polymerize using the free radical of generation, thus Play negative radiation-sensitive characteristic.The curable resin composition containing [D2] radioactivity-sensitive free radical polymerization by drawing Agent is sent out, can further improve radioactive ray sensitivity.

[D2] radioactivity-sensitive radical polymerization initiator can for example enumerate O- acyl group oxime compound, acetophenone compound, United imidazole, thioxanthone compound etc..

O- acyl group oxime compound can for example be enumerated: 1- [4- (thiophenyl) -2- (O- benzoyl oximes)], 1,2- acetyl caproyl 1- [4- (thiophenyl) -2- (O- benzoyl oximes)], ethyl ketone -1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- Base] -1- (O- acetyl group oxime), 1- [9- ethyl -6- benzoyl -9.H.- carbazole -3- base]-octane -1- ketoxime-O- acetic acid esters, 1- [9- ethyl -6- (2- methyl benzoyl) -9.H.- carbazole -3- base]-ethane -1- ketoxime-O- benzoic ether, 1- [the positive fourth of 9- Base -6- (2- ethylamino benzonitrile acyl group) -9.H.- carbazole -3- base]-ethane -1- ketoxime-O- benzoic ether, ethyl ketone -1- [9- ethyl - 6- (2- methyl -4- tetrahydrofuran base benzoyl) -9.H.- carbazole -3- base] -1- (O- acetyl group oxime), ethyl ketone -1- [9- second Base -6- (2- methyl -4- THP trtrahydropyranyl benzoyl) -9.H.- carbazole -3- base] -1- (O- acetyl group oxime), ethyl ketone -1- [9- Ethyl -6- (2- methyl -5- tetrahydrofuran base benzoyl) -9.H.- carbazole -3- base] -1- (O- acetyl group oxime), ethyl ketone -1- [9- ethyl -6- { 2- methyl -4- (2,2- dimethyl -1,3- dioxolyl) methoxybenzoyl base } -9.H.- carbazole -3- Base] -1- (O- acetyl group oxime) etc..

Acetophenone compound can for example be enumerated: α-aminoketone compound, alpha-hydroxyacetone compounds etc..

α-aminoketone compound can for example be enumerated: 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl)-butane -1- Ketone, 2- dimethylamino-2- (4- methylbenzyl)-1- (4- morpholine-4- base-phenyl)-butane-1- ketone, 2- methyl-1-(4- first Sulfenyl phenyl) -2- morpholinopropane -1- ketone etc..

Alpha-hydroxyacetone compounds can for example be enumerated: 1- phenyl -2- hydroxy-2-methyl propane -1- ketone, 1- (4- cumene Base) -2- hydroxy-2-methyl propane -1- ketone, 4- (2- hydroxyl-oxethyl) phenyl-(2- hydroxyl -2- propyl) ketone, 1- hydroxy cyclohexylphenyl Base phenyl ketone.

United imidazole can for example be enumerated: 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-connection miaows Azoles, 2,2 '-bis- (2,4- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines, 2,2 '-bis- (2,4,6- trichloro-benzenes Base) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines etc., preferably 2,2 '-bis- (2,4- dichlorophenyls) -4,4 ', 5,5 '-four benzene 1,2 '-bisglyoxaline of base-.

Thioxanthone compound can for example be enumerated: thioxanthone, 2,4- diethyl thioxanthone, 2- isopropyl thioxanthone anthracene Ketone, 2,4- diisopropyl thioxanthone, 2- chlorothiaxanthenone etc..

Wherein, preferably O- acyl group oxime compound, acetophenone compound, thioxanthone compound, more preferably O- acyl group Oxime compound, α-aminoketone compound, thioxanthone compound, and then preferably ethyl ketone -1- [9- ethyl -6- (2- methylbenzene first Acyl group)-9H- carbazole-3- base]-1- (O- acetyl group oxime), 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinopropane-1- ketone, 2,4- diethyl thioxanthones.

Relative to 100 mass parts of [A] polymer, the amount of [D] radical polymerization initiator is preferably 1 mass parts or more And 40 below the mass, more than more preferably 5 mass parts and 30 below the mass.By by [D] radical polymerization initiator Amount is set as the range, and the curable resin composition can further improve the adhesiveness of cured film, in addition to put When the situation of ray hardened property resin combination, radioactive ray sensitivity can be improved in turn.

<[E] acid producing agent>

[E] acid producing agent is the compound for generating acid.The acid of the generation is such as can enumerate carboxylic acid, sulfonic acid.It is described hard The property changed resin combination, which passes through, contains [E] acid producing agent, and the characteristics such as heat resistance, the hardness of cured film can be improved.[E] acid producing agent It such as can enumerate: [E1] the thermonasty acid producing agent of acid being generated by heating, acid is generated by the irradiation of radioactive ray [E2] radioactivity-sensitive acid producing agent etc..[E] acid producing agent in the curable resin composition can be containing form after State such low molecular compound form, as [A] polymer etc. a part and the form, the described two shapes that are entered by group State.The curable resin composition contains one kind or two or more [E] acid producing agent.

[[E1] thermonasty acid producing agent]

[E1] thermonasty acid producing agent is the compound that acid is generated by heating.If the curable resin composition contains There is [E1] thermonasty acid producing agent, then can be used as thermosetting resin composition and function.

[E1] thermonasty acid producing agent can for example be enumerated: salt such as sulfonium salt, benzothiazolium salt, ammonium salt, phosphonium salt etc..[E1] The concrete example of thermonasty acid producing agent compound can be enumerated and as recorded in Japanese Patent Laid-Open 2010-134442 bulletin [E] ingredient and the same compound of compound that illustrates.

[[E2] radioactivity-sensitive acid producing agent]

[E2] radioactivity-sensitive acid producing agent is the compound that acid is generated by the irradiation of radioactive ray.The hardenability tree If oil/fat composition contains [E2] radioactivity-sensitive acid producing agent, it can be used as radioactive ray curable resin composition and function. The curable resin composition, which passes through, contains [E2] radioactivity-sensitive acid producing agent, can further improve radioactive ray sensitivity.

[E2] acid producing agent can for example be enumerated: quinone di-azido compound, oxime sulfonate compounds, salt, sulfimide Close object, halogen-containing compound, diazomethane compound, sulphones, sulfonate compound, carboxylate compound etc..

Quinone di-azido compound generates carboxylic acid by the irradiation of radioactive ray.The curable resin composition is by containing Quinone di-azido compound is used as [E2] acid producing agent, then the carboxylic acid generated improves radioactive ray irradiation part in alkaline-based developer Thus dissolubility can play eurymeric radiation characteristic.

Phenoloid or alcohol compound (hereinafter also referred to " parent nucleus ") and 1 for example can be used in quinone di-azido compound, The condensation product of two nitrine sulfonic acid halide of 2- naphthoquinones.

Parent nucleus can for example be enumerated: trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxy two Benzophenone, (polyhydroxy phenyl) alkane, other parent nucleus etc..

Trihydroxybenzophenone can for example be enumerated: 2,3,4- trihydroxybenzophenones, 2,4,6- trihydroxybenzophenones etc..

Tetrahydroxybenzophenone can for example be enumerated: 2,2 ', 4,4 '-tetrahydroxybenzophenones, 2,3,4,3 '-tetrahydroxy hexichol Ketone, 2,3,4,4 '-tetrahydroxybenzophenones, 2,3,4,2 '-tetrahydroxys -4 '-methyl benzophenone, 2,3,4,4 '-tetrahydroxys - 3 '-methoxy benzophenones etc..

Pentahydroxybenzophenone can for example be enumerated: 2,3,4,2 ', 6 '-pentahydroxybenzophenones etc..

Hexahydroxy benzophenone can for example be enumerated: 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone, 3, and 4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone etc..

(polyhydroxy phenyl) alkane can for example be enumerated: bis- (2,4- dihydroxy phenyl) methane, bis- (p-hydroxybenzene) methane, Three (p-hydroxybenzene) methane, 1,1,1- tri- (p-hydroxybenzene) ethane, bis- (2,3,4- trihydroxy phenyl) methane, 2,2- are bis- (2,3,4- trihydroxy phenyl) propane, 1,1,3- tri- (2,5- dimethyl -4- hydroxy phenyl) -3- phenyl-propane, 4,4 '-[1- [4- [1- [4- hydroxy phenyl] -1- Methylethyl] phenyl] ethylidene] bis-phenol, bis- (2,5- dimethyl -4- hydroxy phenyl) -2- hydroxyls Phenylmethane, 3,3,3 ', 3 '-tetramethyl -1,1 '-spirobindene -5,6,7,5 ', 6 ', 7 '-hexanols, 2,2,4- trimethyl -7,2 ', 4 '-trihydroxy flavane etc..

Other parent nucleus can for example be enumerated: 2- methyl -2- (2,4- dihydroxy phenyl) -4- (4- hydroxy phenyl) -7- hydroxyl color Full, 1- [1- { 3- (1- [4- hydroxy phenyl] -1- Methylethyl) -4,6- dihydroxy phenyl } -1- Methylethyl] -3- (1- { 3- (1- [4- hydroxy phenyl] -1- Methylethyl) -4,6- dihydroxy phenyl } -1- Methylethyl) benzene, bis- { 1- (the 4- hydroxy benzenes of 4,6- Base) -1- Methylethyl } -1,3- dihydroxy benzenes etc..

In the parent nucleus be preferably 2,3,4,4 '-tetrahydroxybenzophenones, 1,1,1- tri- (p-hydroxybenzene) ethane, 4, 4 '-[1- [4- [1- [4- hydroxy phenyl] -1- Methylethyl] phenyl] ethylidene] bis-phenols.

1,2- naphthoquinones, two nitrine sulfonic acid halide is preferably 1,2- naphthoquinones, two nitrine sulfonic acid chloride.1,2- naphthoquinones, two nitrine sulfonic acid chloride example It can such as enumerate: 1,2- naphthoquinones, two nitrine -4- sulfonic acid chloride, 1,2- naphthoquinones, two nitrine -5- sulfonic acid chloride etc..It is wherein preferably 1,2- naphthoquinones Two nitrine -5- sulfonic acid chlorides.

The synthesis of quinone di-azido compound can be carried out by well known condensation reaction.In the condensation reaction, relative to OH radix in phenoloid or alcohol compound, can be used be equivalent to preferably 30 moles of %~85 mole %, more preferably For 1,2- naphthoquinones, the two nitrine sulfonic acid halide of 50 moles of %~70 mole %.

In addition, quinone di-azido compound, which can also be properly used, is changed to amido bond for the ester bond of parent nucleus illustrated by just now Made of 1,2- naphthoquinones, two nitrine sulfonamides, such as 2,3,4- triamido benzophenone-1, two nitrine -4- sulfonamide of 2- naphthoquinones Deng.

It is other than quinone di-azido compound, such as oxime sulfonate compounds, salt, sulfimide in [E2] acid producing agent The feelings of compound, halogen-containing compound, diazomethane compound, sulphones, sulfonate compound, carboxylate compound etc. When shape, about the curable resin composition, reacted simultaneously by aftermentioned [F] polymer of effect etc. of the acid of generation Hardening, thus can usually play negative radiation-sensitive characteristic.

Oxime sulfonate compounds can for example be enumerated: (5- sulfonyl propyl base oxygroup imino group -5H- thiophene -2- subunit)-(2- Aminomethyl phenyl) acetonitrile, (5- octyl sulfonyl oxygroup imino group -5H- thiophene -2- subunit)-(2- aminomethyl phenyl) acetonitrile, (camphor Sulfonyl oxygroup imino group -5H- thiophene -2- subunit)-(2- aminomethyl phenyl) acetonitrile, (5- p-toluenesulfonyl oxygroup imino group - 5H- thiophene -2- subunit)-(2- aminomethyl phenyl) acetonitrile, (5- octyl sulfonyl oxygroup imino group)-(4- methoxyphenyl) acetonitrile Deng.

Salt compound can for example enumerate: Iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, pyridiniujm.The tool of preferred salt Body example can be enumerated: Er Ben Ji Iodonium fluoroform sulphonate, Er Ben Ji Iodonium tosilate, Er Ben Ji Iodonium hexafluoro antimonate, hexichol Ji Iodonium hexafluorophosphate, Er Ben Ji Iodonium tetrafluoroborate, triphenylsulfonium triflate sulfonate, triphenylsulfonium tosilate, Triphenylsulfonium hexafluoro antimonate, 4- tert-butyl-phenyl diphenyl sulfonium fluoroform sulphonate, 4- tert-butyl-phenyl diphenyl sulfonium Tosilate, 4,7-, bis--n-butoxy naphthalene thiophane fluoroform sulphonate, 4- (thiophenyl) phenyl diphenyl sulfonium Three (pentafluoroethyl group) three fluorophosphates, two benzene base Phosphonium hexafluorophosphate of 4- (thiophenyl) phenyl.

N- sulfonyl oxygroup imide compound can for example be enumerated: N- (trifluoromethyl sulfonyl oxygroup) succinimide, N- (trifluoromethyl sulfonyl oxygroup) phthalimide, N- (trifluoromethyl sulfonyl oxygroup) diphenyl maleoyl- are sub- Amine, bicyclic [2.2.1] hept- 5- alkene -2, the 3- dicarboximide of N- (trifluoromethyl sulfonyl oxygroup), N- (trimethyl fluoride sulfonyl Base oxygroup) naphthalene acid imide.

Halogen-containing compound can for example be enumerated: the hetero ring type chemical combination of the hydrocarbon compound of haloalkyl containing, haloalkyl containing Object.The concrete example of preferred halogen-containing compound can be enumerated: 1,10- bis- bromo- n-decane, 1,1- bis- (4- chlorphenyls) -2,2, Bis- (the trichloromethyl)-s-triazine of 2- trichloroethanes, phenyl-, 4- methoxyphenyl-bis- (trichloromethyl)-s-triazine, styrene The Striazine derivatives such as bis- (the trichloromethyl)-s-triazine of base-, bis- (the trichloromethyl)-s-triazine of naphthalene-.

Diazomethane compound can for example be enumerated: bis- (trifluoromethyl sulfonyl) diazomethanes, bis- (cyclohexylsulfonyls) Diazomethane, bis- (phenyl sulfonyl) diazomethanes.

Sulphones can for example be enumerated: the α-two of β -one sulphones, 'Beta '-sulfonyl sulphones and these compounds is even Nitrogen compound.The concrete example of preferred sulphones can be enumerated: 4- tri-benzoyl methyl sulfone, mesitylene base phenacyl Sulfone, bis- (phenacyl sulfonyl) methane etc..

Sulfonate compound can for example be enumerated: alkyl sulfonates, haloalkyl sulfonate class, aryl sulfonates, Asia Sulfamic acid esters.The concrete example of preferred sulfonate compound can be enumerated: styrax tosylate, pyrogallol three (three Fluorine methanesulfonates), adjacent nitro benzyl triflate, adjacent nitro benzyl p-methyl benzenesulfonic acid ester.

Carboxylate compound can for example be enumerated: carboxylic acid adjacent nitro benzyl ester etc..

Relative to 100 mass parts of [A] polymer, the amount of [E] acid producing agent is preferably 5 mass parts or more and 100 matter Part is measured hereinafter, more than more preferably 10 mass parts and 50 below the mass.By the way that the amount of [E] acid producing agent is set as described Range, the curable resin composition can further improve the adhesiveness of cured film, in addition for radioactive ray hardening resin When the situation of composition, radioactive ray sensitivity can be improved in turn.

<[F] polymer>

[F] polymer is following polymer: being made containing selected from the group being made of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides At least one kind of (hereinafter also referred to " (F1) compound ") in group and the unsaturated compound containing epoxy group are (hereinafter also referred to " (F2) compound ") monomer be copolymerized.The curable resin composition, which passes through, contains [F] polymer, can be into one Step improves the adhesiveness of cured film, and solvent resistance and hardness can be improved.[F] polymer can also be made to harden by heating, but logical It crosses containing [D] radical polymerization initiator and/or [E] acid producing agent, can more effectively make its hardening.

In the synthesis of [F] polymer, the unsaturated compound other than (F1) compound and (F2) compound can be made (following Also referred to as " (F3) compound ") copolymerization.These compounds can be used one kind or two or more.

Each compound is illustrated below.

[(F1) compound]

(F1) compound is at least one kind of in the group being made of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides.(F1) Compound can be enumerated: unsaturated monocarboxylic, unsaturated dicarboxylic, the acid anhydride of unsaturated dicarboxylic, polybasic carboxylic acid list [(methyl) third Enoyl- oxygroup alkyl] ester, in list (methyl) acrylate of polymer of two ends with carboxyl and hydroxyl, with carboxyl Unsaturated polycyclic compound and its acid anhydride etc..These compounds can be enumerated and the structural unit (II) as offer [A] polymer Monomer and the same compound of compound etc. that illustrates.

Wherein, with regard to copolyreaction and accessibility and [F] polymer to the deliquescent viewpoint of alkaline aqueous solution For, the preferably acid anhydride of monocarboxylic acid, dicarboxylic acids, more preferably acrylic acid, methacrylic acid, maleic anhydride, and then preferably For methacrylic acid.

The content ratio of structural unit from (F1) compound is used in the synthesis relative to [F] polymer The input ratio meter of whole monomers, the preferably 1 mass % of mass %~40, the more preferably 2 mass % of mass %~30, and then preferably For 3 mass of mass %~20 %.By the way that the content ratio is set as the range, [F] polymer can be made to alkaline aqueous solution Dissolubility optimization, can further improve the developability of the curable resin composition.

[(F2) compound]

(F2) compound is the unsaturated compound containing epoxy group.(F2) compound have it is free-radical polymerised and usually both Also there is ethylene unsaturated bond with epoxy group.The epoxy group can be enumerated: oxiranyl (1,2- epoxy construction), oxa- Cyclobutyl (1,3- epoxy construction).

Unsaturated compound with oxiranyl can for example be enumerated: glycidyl acrylate, methacrylic acid contracting Water glyceride, α-ethylacrylate ethylene oxidic ester, α-n-propyl glycidyl acrylate, α-n-butyl shrink sweet Grease, acrylic acid -3,4- epoxy group butyl ester, methacrylic acid -3,4- epoxy group butyl ester, acrylic acid -6,7- epoxy group heptyl ester, first Base acrylic acid -6,7- epoxy group heptyl ester, α-ethylacrylate -6,7- epoxy group heptyl ester, adjacent vinylbenzyl glycidyl ether, Vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, methacrylic acid 3,4- epoxycyclohexyethylSiOi ester etc..

Unsaturated compound with oxetanylmethoxy can for example be enumerated: 3- (acryloyl group oxygroup methyl) oxa- ring fourth Alkane, 3- (acryloyl group oxygroup methyl) -2- methy oxetane, 3- (acryloyl group oxygroup methyl) -3- ethyl oxa- ring fourth Alkane, 3- (acryloyl group oxygroup methyl) -2- trifluoromethyl oxetanes, 3- (acryloyl group oxygroup methyl) -2- pentafluoroethyl group Oxetanes, 3- (acryloyl group oxygroup methyl) -2- phenyl oxetanes, 3- (acryloyl group oxygroup methyl) -2,2- bis- Fluorine oxetanes, -2,2,4- trifluoro oxetanes of 3- (acryloyl group oxygroup methyl), 3- (acryloyl group oxygroup methyl) - 2,2,4,4- tetrafluoro oxetanes, 3- (2- acryloyl group oxygroup ethyl) oxetanes, 3- (2- acryloyl group oxygroup second Base) -2- Ethyloxetane, 3- (2- acryloyl group oxygroup ethyl) -3- Ethyloxetane, 3- (2- acryloyl group oxygen Base ethyl) -2- trifluoromethyl oxetanes, 3- (2- acryloyl group oxygroup ethyl) -2- pentafluoroethyl group oxetanes, 3- (2- acryloyl group oxygroup ethyl) -2- phenyl oxetanes, 3- (2- acryloyl group oxygroup ethyl) -2,2- difluoro oxa- ring fourth Alkane, 3- (2- acryloyl group oxygroup ethyl) -2,2,4- trifluoro oxetanes, 3- (2- acryloyl group oxygroup ethyl) -2,2,4, The acrylate of 4- tetrafluoro oxetanes etc.；

3- (methylacryloyl oxygroup methyl) oxetanes, 3- (methylacryloyl oxygroup methyl) -2- methyl oxygen Azetidine, 3- (methylacryloyl oxygroup methyl) -3- Ethyloxetane, 3- (methylacryloyl oxygroup methyl) - 2- trifluoromethyl oxetanes, 3- (methylacryloyl oxygroup methyl) -2- pentafluoroethyl group oxetanes, 3- (methyl-prop Alkenoyloxymethyl) -2- phenyl oxetanes, 3- (methylacryloyl oxygroup methyl) -2,2- difluoro oxetanes, - 2,2,4- trifluoro oxetanes of 3- (methylacryloyl oxygroup methyl), 3- (methylacryloyl oxygroup methyl) -2,2,4, 4- tetrafluoro oxetanes, 3- (2- methylacryloyl oxygroup ethyl) oxetanes, 3- (2- methylacryloyl oxygroup second Base) -2- Ethyloxetane, 3- (2- methylacryloyl oxygroup ethyl) -3- Ethyloxetane, 3- (2- methyl-prop Enoyl- oxygroup ethyl) -2- trifluoromethyl oxetanes, 3- (2- methylacryloyl oxygroup ethyl) -2- pentafluoroethyl group oxygen Azetidine, 3- (2- methylacryloyl oxygroup ethyl) -2- phenyl oxetanes, 3- (2- methylacryloyl oxygroup second Base) -2,2- difluoro oxetanes, 3- (2- methylacryloyl oxygroup ethyl) -2,2,4- trifluoro oxetanes, 3- (2- Methylacryloyl oxygroup ethyl) -2,2,4,4- tetrafluoro oxetanes etc. methacrylate etc..

Wherein, for the viewpoint of copolyreaction and the indurative raising of the curable resin composition, preferably For glycidyl methacrylate, methacrylic acid -6,7- epoxy group heptyl ester, adjacent vinylbenzyl glycidyl ether, second Alkenyl benzyl glycidyl ether, to vinylbenzyl glycidyl ether, methacrylic acid 3,4- epoxycyclohexyethylSiOi ester, more preferably Glycidyl methacrylate, methacrylic acid 3,4- epoxycyclohexyethylSiOi ester.

The content ratio of structural unit from (F2) compound is used in the synthesis relative to [F] polymer The input ratio meter of whole monomers, the preferably 5 mass % of mass %~70, more preferably 10 mass of mass %~60 %, Jin Eryou It is selected as 15 mass of mass %~50 %.By the way that the content ratio is set as the range, the resistance to of cured film can further improve Solvent borne and hardness.

[(F3) compound]

(F3) compound is the unsaturated compound other than (F1) compound and (F2) compound.(F3) as long as compound It is then not particularly limited with free-radical polymerised unsaturated compound.(F3) compound can for example be enumerated: methacrylic acid Arrcostab, cycloalkyl methacrylate, the methacrylate with hydroxyl, alkyl acrylate, acrylate base ester, Acrylate, methacrylic acid aromatic ester, acrylic acid aromatic ester, unsaturated dicarboxylic diester with hydroxyl, it is bicyclic not Saturated compounds, unsaturated aromatic compound, conjugated diene, has tetrahydrofuran bone at N- maleimide compounds The unsaturated compound of skeleton represented by frame, furans skeleton, oxinane skeleton, pyrans skeleton or following formula (2), following formula (3) unsaturated compound containing phenolic hydroxyl group represented by, the unsaturated compound with hydrolysable silanes base, other unsaturations Compound etc..

[changing 5]

In the formula (2), R⁷For hydrogen atom or methyl.The integer that m is 1 or more.

[changing 6]

In the formula (3), R⁸For hydrogen atom or the alkyl of carbon number 1~4.R⁹~R¹³It is separately hydrogen atom, hydroxyl Or the alkyl of carbon number 1~4.Y is singly-bound ,-COO- or-CONH-.The integer that p is 0~3.Wherein, R⁹~R¹³At least one be hydroxyl Base.

Alkyl methacrylate, cycloalkyl methacrylate, alkyl acrylate, acrylate base ester, methyl Acrylic acid aromatic ester, acrylic acid aromatic ester, unsaturated dicarboxylic diester, bicyclic unsaturated compound, N- maleoyl- Group with imine moiety, conjugated diene, has tetrahydrofuran skeleton, furans skeleton, oxinane skeleton at unsaturated aromatic compound Or unsaturated compound, other compounds of pyrans skeleton can for example be enumerated and the structural unit as offer [A] polymer (III) compound and the same compound of compound etc. illustrated.

Methacrylate with hydroxyl can for example be enumerated: methacrylic acid hydroxyl methyl esters, methacrylic acid 2- hydroxyl Ethyl ester, methacrylic acid 3- hydroxy propyl ester, methacrylic acid 4- hydroxybutyl, diethylene glycol monomethyl acrylate, methyl-prop Olefin(e) acid 2,3- dihydroxy propyl ester, 2- methacryloxyethyl glucoside, methacrylic acid 4- hydroxy benzenes base ester etc..

Acrylate with hydroxyl can for example be enumerated: dihydroxypropyl methyl esters, acrylic acid 2- hydroxy methacrylate, acrylic acid 3- Hydroxy propyl ester, acrylic acid 4- hydroxybutyl, diethylene glycol monoacrylate, acrylic acid 2,3- dihydroxy propyl ester, 2- acryloyl-oxy Base ethyl cyclophosphadenosine glycoside, acrylic acid 4- hydroxy benzenes base ester etc..

Unsaturated compound containing skeleton represented by the formula (2) can for example be enumerated: polyethylene glycol (n=2~10) Single (methyl) acrylate of single (methyl) acrylate, polypropylene glycol (n=2~10) etc..

Unsaturated compound containing phenolic hydroxyl group represented by the formula (3) can be enumerated: according to the definition of Y and p under State the compound etc. that formula (4)~formula (8) indicates.

[changing 7]

In the formula (4), q be 1~3 integer.R⁸~R¹³It is synonymous with the formula (3).

[changing 8]

In the formula (5), R⁸~R¹³It is synonymous with the formula (3).

[changing 9]

In the formula (6), r be 1~3 integer.R⁸~R¹³It is synonymous with the formula (3).

[changing 10]

In the formula (7), R⁸~R¹³It is synonymous with the formula (3).

[changing 11]

In the formula (8), R⁸~R¹³It is synonymous with the formula (3).

Unsaturated compound with hydrolysable silanes base can for example be enumerated: 2- methacryloxyethyl trimethoxy Silane, 2- methacryloxyethyl triethoxysilane, 3- methacryloxypropyl trimethoxy silane, 3- methyl Acryloxypropyl triethoxysilane, 3- methacryloxypropyl tripropyl silane, 3- methacryloxy third Base trichlorosilane, 4- methacryloxy butyl trimethoxy silane, 4- methacryloxy butyl triethoxysilane, 2- acryloyl-oxyethyl trimethoxy silane, 2- acryloyl-oxyethyl triethoxysilane, 3- acryloxypropyl three Methoxy silane, 3- acryloxypropyl triethoxysilane, 3- acryloxypropyl tripropyl silane, 3- acryloyl-oxy Base propyltrichlorosilan, 4- acryloxy butyl trimethoxy silane, 4- acryloxy butyl triethoxysilane etc..

Wherein, preferably alkyl methacrylate, cycloalkyl methacrylate, N- maleimide chemical combination Object has tetrahydrofuran skeleton, furans skeleton, oxinane skeleton, skeleton represented by pyrans skeleton or the formula (2) not Unsaturated compound, unsaturated aromatic compound, propylene represented by saturated compounds, the formula (3) containing phenolic hydroxyl group Sour cycloalkyl ester, the unsaturated compound with hydrolysable silanes base.Wherein, with regard to copolyreaction and [F] polymer to alkalinity For the deliquescent aspect of aqueous solution be more preferably styrene, Tert-butyl Methacrylate, the positive Lauryl Ester of methacrylic acid, Methacrylic acid tricyclic [5.2.1.0^2,6] decane -8- base ester, to methoxy styrene, acrylic acid 2- methyl cyclohexyl, N- phenyl Maleimide, N- cyclohexylmaleimide, (methyl) tetrahydrofurfuryl acrylate, polyethylene glycol (n=2~ 10) single (methyl) acrylate, 3- (methyl) acryloyl group oxygroup tetrahydrofuran -2- ketone, (methyl) acrylic acid 4- hydroxybenzyl Ester, (methyl) acrylic acid 4- hydroxy benzenes base ester, o-hydroxystyrene, 4-Vinyl phenol, Alpha-Methyl -4-Vinyl phenol, into And preferably Alpha-Methyl -4-Vinyl phenol, styrene, methacrylic acid tetrahydro furfuryl ester, N- cyclohexyl maleoyl- are sub- The positive Lauryl Ester of amine, methacrylic acid, methacrylic acid tricyclic [5.2.1.0^2,6] decane -8- base ester, 3- methacryloxy Propyl-triethoxysilicane.

The content ratio of structural unit from (F3) compound is used in the synthesis relative to [F] polymer The input ratio meter of whole monomers, the preferably 10 mass % of mass %~90, more preferably 30 mass of mass %~80 %, Jin Eryou It is selected as 40 mass of mass %~65 %.By the way that the content ratio is set as the range, the hardenability can further improve The developability of resin combination and the solvent resistance of cured film.

[F] polymer can be synthesized in the following way: in the same manner as the polymerization of described synthesis [A] polymer, molten Make (F1) compound and (F2) compound and (F3) compound optionally etc. using radical polymerization initiator in agent It is polymerize.

The Mw of [F] polymer is preferably 2,000~100,000, more preferably 3,000~50,000, and then preferably 5, 000~20,000.By the way that the Mw of [F] polymer is set as the range, the curable resin composition be can further improve Developability can further improve radioactive ray sensitivity in addition when the situation of radioactive ray curable resin composition is made.

Relative to 100 mass parts of [A] polymer, the amount of [F] polymer is preferably 10 mass parts or more and 3,000 matter Part is measured hereinafter, 500 below the mass more than more preferably 50 mass parts and 1, and then more than preferably 150 mass parts and 800 matter Measure part or less.By the way that the amount of [F] polymer is set as the range, the curable resin composition be can further improve The hardness of cured film.

Any other ingredient can for example be enumerated: epoxide, adhesion aid, metal oxide particle, surfactant, Curing agent etc..The curable resin composition contains one kind or two or more any other ingredient, can also contain a kind Or respective ingredient of more than two kinds.

[epoxide]

Epoxide is the compound (wherein, being equivalent to except the compound of described [F] polymer) with epoxy group. The curable resin composition by containing epoxide, can further improve the heat resistance of cured film, surface hardness and Film thickness uniformity.

Epoxy group can for example enumerate oxiranyl, oxetanylmethoxy etc..Epoxide can have 1 or 2 or more Epoxy group.

Compound with 1 epoxy group can for example be enumerated: (methyl) glycidyl acrylate, α-ethylacrylate contracting Water glyceride, α-n-propyl glycidyl acrylate, α-n-butyl acryloyloxy ethyl acid glycidyl ester, (methyl) acrylic acid 3,4- ring Oxygroup butyl ester, α-ethylacrylate 3,4- epoxy group butyl ester, (methyl) acrylic acid 6,7- epoxy group heptyl ester, α-ethylacrylate 6, 7- epoxy group heptyl ester, adjacent vinylbenzyl glycidyl ether, vinylbenzyl glycidyl ether, shrink to vinyl benzyl it is sweet Oily ether, 3- methyl -3- (methyl) acryloyloxymethyl oxetanes, 3- ethyl -3- (methyl) acryloyloxymethyl oxygen Azetidine, phenyl glycidyl ether, γ-glycidoxypropyltrimewasxysilane, β-(3,4- expoxycyclohexyl) Ethyl trimethoxy silane, γ-glycidoxypropyl diethoxy silane etc..

Compound with 2 or more epoxy groups can for example be enumerated:

3,4- epoxycyclohexylmethyls -3 ', 4 '-epoxycyclohexane carboxylates, 2- (3,4- expoxycyclohexyl -5, 5- spiral shell -3,4- epoxy group) hexamethylene-dioxanes, bis- (3,4- epoxycyclohexylmethyl) adipate esters, bis- (3,4- epoxies Base -6- methylcyclohexylmethyl) adipate ester, 3,4- epoxy group -6- methylcyclohexyl -3 ', 4 '--6 '-methyl cyclohexanes of epoxy group Alkane carboxylate, di-2-ethylhexylphosphine oxide (3,4- epoxy-cyclohexane), bicyclopentadiene dicyclic oxide, ethylene glycol two (3,4- epoxies Butylcyclohexyl methyl) ether, ethylenebis (3,4- epoxycyclohexane carboxylate)；

Bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol-S diglycidyl ether, hydrogenated bisphenol A two shrink The bisphenol types 2-glycidyl ethers such as glycerin ether, A Hydrogenated Bisphenol A F diglycidyl ether, hydrogenated bisphenol A D diglycidyl ether；

1,4-butanediol diglycidyl ether, 1,6- hexanediol diglycidyl ether, glycerin triglycidyl ether, three hydroxyls The bunching of the polyalcohols such as methylpropane triglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether Water glycerol ethers；

And the one kind or two or more alkylene oxide of the addition on the aliphatic polyols such as ethylene glycol, propylene glycol, glycerine The poly epihydric alcohol ethers of the polyether polyol of acquisition；

Phenol novolak type epoxy resin；

Cresol novolak type epoxy resin；

More phenol-type epoxy resins；

The 2-glycidyl esters of aliphatic long-chain binary acid；

The glycidol esters of higher fatty acids；

Aliphatic polyglycidyl ethers；

Epoxidised soybean oil, epoxidized linseed etc..

The commercially available product of compound with 2 or more epoxy groups can for example be enumerated:

Ai Pikaote (Epikote) 1001, Ai Pikaote (Epikote) as phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin 1002, Ai Pikaote (Epikote) 1003, Ai Pikaote (Epikote) 1004, Ai Pikaote (Epikote) 1007, Ai Pikao Spy (Epikote) 1009, Ai Pikaote (Epikote) 1010, Ai Pikaote (Epikote) 828 (more than, Japanese epoxy resin (Japan Epoxy Resins) company) etc.；

Ai Pikaote (Epikote) 807 (more than, Japanese epoxy resin company) etc. as bisphenol f type epoxy resin；

Ai Pikaote (Epikote) 152, Ai Pikaote (Epikote) as phenol novolak type epoxy resin 154, Ai Pikaote (Epikote) 157S65 (more than, Japanese epoxy resin company), EPPN201, EPPN202 (more than, Japan Chemical drug company) etc.；

As EOCN102, EOCN103S of cresol novolak type epoxy resin, EOCN104S, 1020,1025,1027 (more than, Japanese chemical drug company), Ai Pikaote (Epikote) 180S75 (Japanese epoxy resin company) etc.；

Ai Pikaote (Epikote) 1032H60, Ai Pikaote (Epikote) XY-4000 as more phenol-type epoxy resins (more than, Japanese epoxy resin company) etc.；

As cyclic aliphatic epoxy resin CY-175, CY-177, CY-179, Ai Laoda (Araldite) CY-182, Ai Laoda (Araldite) 192,184 (more than, Ciba (Ciba specialty chemicals) manufacture), ERL- 4234,4299,4221,4206 (more than, U.C.C company), clear dyne (Shodain) 509 (Showa electrician company), Chinese mugwort clone (Epiclon) 200, Chinese mugwort clone (Epiclon) 400 (more than, DIC (DIC) company), Ai Pikaote (Epikote) 871, Ai Pikaote (Epikote) 872 (more than, Japanese epoxy resin company), ED-5661, ED-5662 (more than, Celanese coating (Celanese Coating) company) etc.；

As Ai Bolaite (Epolight) 100MF (chemical company, common prosperity society) of aliphatic polyglycidyl ether, skin is liked Oulu (Epiol) TMP (Nof Corp.) etc..

Relative to 100 mass parts of [A] polymer, the amount of epoxide is preferably 100 below the mass, more preferably Below the mass for 75, and then preferably 50 below the mass.By the way that the amount of epoxide is set as the range, institute The heat resistance, surface hardness and film thickness uniformity of cured film can be improved in turn by stating curable resin composition.

[adhesion aid]

Adhesion aid to improve the adherency by the resulting cured film of the curable resin composition and substrate etc. in turn Property.Such adhesion aid is preferably functional silanes coupling agent.Functional silanes coupling agent can for example be enumerated: have carboxyl, first Base acryloyl group, isocyanate group, coupling agent of epoxy group isoreactivity base etc..Such functional silanes coupling agent can for example arrange It lifts: trimethoxy silane yl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyl triacetoxy silicon Alkane, vinyltrimethoxysilane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyl trimethoxy Base silane, β-(3,4- expoxycyclohexyl) ethyl trimethoxy silane etc..

Relative to 100 mass parts of [A] polymer, the amount of adhesion aid is preferably 20 below the mass, more preferably 10 below the mass.By the way that the amount of adhesion aid is set as 20 below the mass, the development that can inhibit in development step is residual The generation stayed.

[metal oxide particle]

Metal oxide particle can remain described exhausted when forming the situation of insulating film by the curable resin composition The electrical insulating property of velum and the rising that can inhibit relative dielectric constant.The metal oxide particle can also wait for this purpose To use, that is, the control of the refractive index of insulating film, insulating film the transparency control, because being split caused by mitigating curing shrinkage The inhibition of line, the raising of insulating film surface hardness.

Metal oxide particle is, for example, the oxide particle of silicon, aluminium, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium, hafnium. Metal oxide particle can be that single oxide particle is also composite oxide particle.

Single oxide can be enumerated: silica, aluminium oxide, zirconium oxide, titanium dioxide, cerium oxide etc..

Composite oxides can for example be enumerated: barium titanate, strontium titanates, antimony tin (antimony-tin oxide, ATO), Tin indium oxide (indium-tin oxide, ITO), indium zinc oxide (indium-zinc oxide, IZO) etc..

Wherein, the preferably oxide particle of silicon, zirconium, titanium, zinc, barium, more preferably silicon dioxide granule, zirconium oxide grain Son, TiO 2 particles, barium titanate (BaTiO₃).Uncommon love chemical conversion for example can be used in the commercially available product of metal oxide particle (C.I.Kasei) " nano reaches gram (Nanotec) (registered trademark) " etc. of company.

The shape of metal oxide particle is not particularly limited, can for it is spherical be also indefinite shape, in addition can also be Empty particle, Porous particle, core shell partical etc..

In terms of the value found out using dynamic light scattering method, the volume average particle size of metal oxide particle be preferably 5nm~ 200nm, more preferably 5nm~100nm, and then preferably 10nm~80nm.If the volume average particle size of metal oxide particle Less than 5nm, then there is the worry reduced using the hardness of insulating film obtained by curable resin composition and can not show and sought Relative dielectric constant worry.On the other hand, if volume average particle size is more than 200nm, have the mist degree of insulating film get higher and The worry that the flatness of worry and insulating film that transmitance reduces deteriorates.

Relative to 100 mass parts of [A] polymer, the amount of metal oxide particle be preferably 0.01 mass parts or more and 20 below the mass, more than more preferably 1 mass parts and 10 below the mass.If the amount of metal oxide particle is less than 0.01 mass parts then have the worry that can not be controlled in the relative dielectric constant of insulating film in required range.On the other hand, if it is golden The blending amount for belonging to oxide particle is more than 20 mass parts, then has the mist degree of the reduction of the hardenability of coating or film and insulating film to become High worry.

[surfactant]

Surfactant is the compound for improving the coating of the curable resin composition.The surfactant is excellent It is selected as fluorine system surfactant, silicone-based surfactant, nonionic surfactants.

Fluorine system surfactant can for example be enumerated: 1,1,2,2- tetrafluoro octyl (1,1,2,2- tetra- fluoropropyl) ether, 1, and 1,2, 2- tetrafluoro octyl hexyl ether, eight ethylene glycol two (1,1,2,2- tetrafluoro butyl) ethers, six ethylene glycol (1,1,2,2,3,3- hexafluoro penta Base) ether, eight propylene glycol two (1,1,2,2- tetrafluoro butyl) ethers, six propylene glycol two (1,1,2,2,3,3- hexafluoro amyl) ethers, perfluor Dodecyl sodium sulfate, 1,1,2,2,8,8,9,9,10,10- ten fluorine dodecane, 1,1,2,2,3,3- hexafluoro decane etc., additionally It can enumerate: fluoroalkyl benzene sodium sulfonate；Fluoroalkyl oxygroup ethyleneether；Fluoroalkyl ammonium iodide, fluothane ethyl polyethylene-oxide ether, perfluor Alkyl polyoxygenated ethyl alcohol；Perfluoroalkyl alcoxylates；Fluorine system Arrcostab etc..

The commercially available product of fluorine system surfactant can for example be enumerated: " BM-1000 ", " BM-1100 " (more than, green footpath between fields chemistry (BM Chemie) company), " Mei Jiafa (Megafac) F142D ", " Mei Jiafa (Megafac) F172 ", " Mei Jiafa (Megafac) F173 ", " Mei Jiafa (Megafac) F183 ", " Mei Jiafa (Megafac) F178 ", " Mei Jiafa (Megafac) F191 ", " Mei Jia Method (Megafac) F471 " (more than, big Japanese ink chemical industrial company), " Fu Luode (Fluorad) FC-170C ", " Fu Luo Moral (Fluorad) FC-171 ", " Fu Luode (Fluorad) FC-430 ", " Fu Luode (Fluorad) FC-431 " (more than, Sumitomo 3M company), " Sha Fulong (Surflon) S-112 ", " Sha Fulong (Surflon) S-113 ", " Sha Fulong (Surflon) S-131 ", " Sha Fulong (Surflon) S-141 ", " Sha Fulong (Surflon) S-145 ", " Sha Fulong (Surflon) S-382 ", " Sha Fulong (Surflon) SC-101 ", " Sha Fulong (Surflon) SC-102 ", " Sha Fulong (Surflon) SC-103 ", " Sha Fulong (Surflon) SC-104 ", " Sha Fulong (Surflon) SC-105 ", " Sha Fulong (Surflon) SC-106 " (more than, Asahi Glass Company), " Ai Futuo (Eftop) EF301 ", " Ai Futuo (Eftop) EF303 ", " Ai Futuo (Eftop) EF352 " (more than, newly Autumn fields is melted into company) etc..

The commercially available product of silicone-based surfactant can for example be enumerated: " DC3PA ", " DC7PA ", " FS-1265 ", " SF- 8428”、“SHl 1PA”、“SH21PA”、“SH28PA”、“SH29PA”、“SH30PA”、“SH-190”、“SH-193”、“SZ- 6032 " (more than, beautiful DOW CORNING silicone (the toray dowcoming silicone) company in east), " TSF-4440 ", " TSF- 4300 ", " TSF-4445 ", " TSF-4446 ", " TSF-4460 ", " TSF-4452 " (more than, silicone company, GE Toshiba) etc..

Nonionic surfactants can for example be enumerated:

The polyethylene glycol oxides such as polyoxyethylene lauryl ether, polyoxyethylene stearylether, polyethylene glycol oxide oleyl ether Alkyl ether；

The polyoxyethylene aryl ethers class such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylplenyl ether；

The polyethylene glycol oxides dialkyl esters such as polyethylene glycol oxide dilaurate, polyethylene glycol oxide distearate；

(methyl) acrylic acid series copolymer class etc..

The commercially available product of nonionic surfactants can be enumerated: " wave power not Lip river (Polyflow) No.57 ", " wave power not Lip river (Polyflow) No.95 " (more than, chemical company, common prosperity society) etc..

Relative to 100 mass parts of [A] polymer, the amount of surfactant is preferably 10 below the mass, more preferably Below the mass for 5, and then preferably 3 below the mass.By the way that the amount of surfactant is set as 10 below the mass, It can further improve the coating of the curable resin composition.

[curing agent]

Documented curing agent in Japanese Patent Laid-Open 2012-88459 bulletin for example can be used in curing agent.

The curable resin composition can be prepared as follows: by [A] polymer and [B] solvent, optionally [C] polymerizable compound, [D] radical polymerization initiator, [E] acid producing agent, [F] polymer and other any ingredients are equably Mixing, is preferably filtered using 0.2 μm or so of membrane filter.Preferably the curable resin composition is dissolved In solvent appropriate and with solution shape come using.

The curable resin composition can form adhesiveness and transparent excellent cured film, therefore may be suitably used to Such as the formation of the display element cured film as interlayer dielectric, protective film or spacer.

Display element of the invention is formed with cured film by the curable resin composition.Because the display element is with firmly Change film to be formed by the curable resin composition, therefore adhesiveness and the transparency are excellent, such as may be suitably used to display element Interlayer dielectric, protective film, spacer etc..The forming method of display element cured film is not particularly limited, but excellent It is selected as the forming method using display element cured film as described below.

The forming method of display element of the invention cured film includes

In the step of forming film on substrate (hereinafter also referred to " film forming step "), at least part of film is shone The step of penetrating radioactive ray (hereinafter also referred to " irradiating step "), the step of developing to the film irradiated through radioactive ray, are (following Also referred to as " development step "), and the step of developed film is heated (hereinafter also referred to " heating stepses ").The shape The film is formed by the curable resin composition in method.The curable resin composition is preferably by containing Radioactive ray obtained by [D2] the radioactivity-sensitive radical polymerization initiator and/or [E2] radioactivity-sensitive acid producing agent etc. are hard The property changed resin combination.

[film forming step]

In this step, it is coated with the curable resin composition in substrate surface, and preferably by progress prebake conditions (prebake) film is formed to remove solvent.Substrate used in this step can for example be enumerated: glass substrate, silicon wafer, Plastic base and the substrate of various metals is formed on the surface of these substrates.Plastic base can for example be enumerated with poly- to benzene two Formic acid second diester (Polyethylene Terephthalate, PET), polybutylene terephthalate, polyether sulfone, poly- carbonic acid The plastics such as ester, polyimides are the substrate etc. of principal component.

Spray-on process, rolling method, method of spin coating (spin coating for example can be used in the coating method of the curable resin composition (spincoat) method), the suitable method of slit mold coating method, stick rubbing method, ink-jet method etc..It is preferably revolved in the coating method Coating, stick rubbing method, slit mold coating method.Prebake conditions are according to the kind containing ingredient of the curable resin composition Class, amount etc. and it is different, but can for example be set as carrying out 30 seconds~10 minutes or so at 60 DEG C~120 DEG C.The film Film thickness is in terms of the value after prebake conditions, and preferably 0.1 μm~8 μm, more preferably 0.1 μm~6 μm, and then preferably 0.1 μm~4 μ m。

[irradiating step]

In this step, it is situated between to the film formed in the film forming step and is put every the mask irradiation with predetermined pattern Ray.Radioactive ray at this time can for example be enumerated: ultraviolet light, far ultraviolet, X-ray, charged particle beam etc..

Ultraviolet light can for example enumerate g ray (wavelength 436nm), i ray (wavelength 365nm) etc..Far ultraviolet can for example arrange Lift KrF excimer laser etc..X-ray can for example enumerate synchrotron radioactive ray etc..Charged particle beam can for example enumerate electronics Beam etc..It is preferably ultraviolet light in these radioactive ray, particularly preferably includes the radioactive ray of g ray and/or i ray in ultraviolet light.It exposes Light quantity is preferably 30J/m²~1,500J/m²。

[development step]

In this step, it can develop to the film for having irradiated radioactive ray in the irradiating step, it is desired to be formed Pattern.Alkaline aqueous solution can be used in developer solution used in development treatment.Alkali can for example be enumerated: sodium hydroxide, hydroxide Potassium, sodium carbonate, sodium metasilicate, sodium metasilicate, ammonia, ethamine, n-propylamine, diethylamine, DEAE diethylaminoethanol, two-n-propyl amine, three Ethamine, methyl-diethyl-amine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, pyrroles, piperazine Pyridine, 1,8- diazabicyclo [5.4.0] -7- hendecene, 1,5- diazabicyclo [4.3.0] -5- nonane etc..In addition, developer solution It may be used in the alkaline aqueous solution and adds made of the water-miscible organic solvents such as suitable methanol, ethyl alcohol or surfactant Aqueous solution or in order to dissolve by film that the curable resin composition is formed and containing the aobvious of a small amount of various organic solvents Shadow liquid.In turn, developing method is for example using the methods of covering liquid method, dipping (dipping) method, shake infusion process, spray process.It is aobvious The shadow time is different according to the composition of curable resin composition, but can for example be set as 30 seconds~120 seconds.

After developing, it is preferably handled as follows: patterned film being carried out to utilize flowing water cleaning Elution processing then comprehensively irradiates the radioactive ray that (post-exposure) is originated from high-pressure mercury-vapor lamp etc., thus [D2] remaining in film Radioactivity-sensitive radical polymerization initiator, [E2] radioactivity-sensitive acid producing agent etc. decompose.Light exposure when post-exposure is preferred For 2,000J/m²~5,000J/m²Left and right.

[heating stepses]

In this step, added using heating plate, the baking oven etc. calcined to developed film in the development step Thermal is heated (rear baking processing) to the film, thus carries out the hardening of film.In addition, heating temperature is preferably 100 DEG C~300 DEG C, more preferably 120 DEG C~280 DEG C, and then preferably 150 DEG C~250 DEG C.Heating time is according to heating equipment Type and it is different, preferably 5 minutes~300 minutes, more preferably 10 minutes~180 minutes, and then preferably 20 minutes~ 120 minutes.

It is that the curable resin composition utilizes radiation according to the forming method of the display element cured film Property and by exposure, development and heating come the method that forms pattern, therefore can easily form adhesiveness and the transparency is excellent Harden film figure.

Display element of the invention has the display element cured film.The display element can enumerate liquid crystal display member Part, organic EL element etc..Such display element has cured film and is used as such as interlayer dielectric, protective film, spacer.

[embodiment]

Hereinafter, be based on embodiment and specifically describe the present invention, but the present invention and it is not limited to the examples restriction.

[Mw and Mn]

In synthesis example below, pass through the gel permeation chromatography (Gel using following measurement devices and determination condition Permeation Chromatography, GPC) measure the Mw and Mw/Mn of [A] polymer.

Measurement device: " GPC-101 " of Showa electrician company

Determination condition:

GPC tubing string: connection uses " GPC-KF-801 ", " GPC-KF-802 ", " GPC-KF-803 " of Showa electrician company And " GPC-KF-804 ".

Mobile phase: tetrahydrofuran

[synthesis example 1] (synthesis of compound (HC-1))

In the 5L reactor for being provided with blender and addition funnel, 2-hydroxyethyl methacrylate 65.1g is put into (0.5mol), pyridine 59.3g (0.75mol) and methylene chloride 500mL will be cooled to 0 DEG C on one side under a nitrogen in reactor, 3- chlorpromazine chloride 76.18g (0.6mol) is added dropwise from addition funnel on one side, is then reacted 2 hours under 0 DEG C, stirring.To resulting Reaction solution is concentrated under reduced pressure after successively being cleaned using sodium bicarbonate aqueous solution and saturated salt solution, utilizes silica gel tubing string color Spectrometry is purified, thus to obtain compound 83.4g (yield 76%) represented by following formula (HC-1).

[changing 12]

[synthesis example 2] (synthesis of compound (HC-2))

In the 5L reactor for being provided with blender and addition funnel, 4- hydroxy-alpha-methyl styrene 67.1g is put into (0.5mol), pyridine 59.3g (0.75mol) and methylene chloride 500mL will be cooled to 0 DEG C on one side under a nitrogen in reactor, 3- chlorpromazine chloride 76.18g (0.6mol) is added dropwise from addition funnel on one side, is then reacted 2 hours under 0 DEG C, stirring.To resulting Reaction solution is concentrated under reduced pressure after successively being cleaned using sodium bicarbonate aqueous solution and saturated salt solution, utilizes silica gel tubing string color Spectrometry is purified, thus to obtain compound 80.0g (yield 71%) represented by following formula (HC-2).

[changing 13]

[synthesis example 3] (synthesis of compound (HC-3))

In the 5L reactor for being provided with blender and addition funnel, methacrylic acid 2,3- dihydroxy propyl ester are put into 80.1g (0.5mol), pyridine 118.7g (1.5mol) and methylene chloride 500mL will be cooled in reactor on one side under a nitrogen 0 DEG C, 3- chlorpromazine chloride 152.4g (1.2mol) is added dropwise from addition funnel on one side, is then reacted 2 hours under 0 DEG C, stirring.To institute The reaction solution obtained is concentrated under reduced pressure after successively being cleaned using sodium bicarbonate aqueous solution and saturated salt solution, utilizes silicone tube Column chromatography is purified, thus to obtain compound 106.3g (yield 62%) represented by following formula (HC-3).

[changing 14]

[synthesis example 4] (synthesis of compound (HC-4))

In the 5L reactor for being provided with blender and addition funnel, put into methacrylic acid (3,4- dihydroxy butylcyclohexyl) Methyl esters 107.2g (0.5mol), pyridine 118.7g (1.5mol) and methylene chloride 500mL under a nitrogen on one side will be in reactors It is cooled to 0 DEG C, 3- chlorpromazine chloride 152.4g (1.2mol) is added dropwise from addition funnel on one side, then reaction 2 is small under 0 DEG C, stirring When.It is concentrated under reduced pressure after successively being cleaned using sodium bicarbonate aqueous solution and saturated salt solution to resulting reaction solution, benefit Purified with silica gel column chromatography, thus to obtain compound 125.5g (yield 64%) represented by following formula (HC-4).

[changing 15]

[synthesis example 5] (synthesis of compound (HC-5))

In the 5L reactor for being provided with blender and addition funnel, methacrylic acid 3- hydroxyl -1- adamantyl is put into Ester 118.2g (0.5mol), pyridine 59.3g (0.75mol) and methylene chloride 500mL under a nitrogen on one side will be cold in reactor But to 0 DEG C, 3- chlorpromazine chloride 76.18g (0.6mol) is added dropwise from addition funnel on one side, is then reacted 2 hours under 0 DEG C, stirring. It is concentrated under reduced pressure after successively being cleaned using sodium bicarbonate aqueous solution and saturated salt solution to resulting reaction solution, utilizes silicon Sebific duct column chromatography is purified, thus to obtain compound 117.2g (yield 72%) represented by following formula (HC-5).

[changing 16]

[synthesis example 6] (synthesis of compound (HC-6))

In the 5L reactor for being provided with blender and addition funnel, put into methacrylic acid 3- (2- hydroxyl-oxethyl)- Adamantane esters 140.2g (0.5mol), pyridine 59.3g (0.75mol) and methylene chloride 500mL under a nitrogen on one side will be anti- It answers and is cooled to 0 DEG C in device, 3- chlorpromazine chloride 76.18g (0.6mol) is added dropwise from addition funnel on one side, it is then anti-under 0 DEG C, stirring It answers 2 hours.It carries out depressurizing after successively cleaning resulting reaction solution using sodium bicarbonate aqueous solution and saturated salt solution dense Contracting, is purified using silica gel column chromatography, thus to obtain compound 128.5g (yield represented by following formula (HC-6) 69%).

[changing 17]

[synthesis example 7] (synthesis of compound (HC-7))

In the 5L reactor for being provided with blender and addition funnel, methacrylic acid 4- hydroxy benzenes base ester 89.1g is put into (0.5mol), pyridine 59.3g (0.75mol) and methylene chloride 500mL will be cooled to 0 DEG C on one side under a nitrogen in reactor, 3- chlorpromazine chloride 76.18g (0.6mol) is added dropwise from addition funnel on one side, is then reacted 2 hours under 0 DEG C, stirring.To resulting Reaction solution is concentrated under reduced pressure after successively being cleaned using sodium bicarbonate aqueous solution and saturated salt solution, utilizes silica gel tubing string color Spectrometry is purified, thus to obtain compound 105.1g (yield 78%) represented by following formula (HC-7).

[changing 18]

[synthesis example 8] (synthesis of polymer (A-1))

By compound (HC-1) 36.6g (20 moles of %), methacrylic acid 17.8g (25 moles of %) and first of the synthesis Base methyl acrylate 45.6g (55 moles of %) is dissolved in the 3- methoxy methyl propionate of 140g, addition 2,2 '-azos it is bis- (2, 4- methyl pentane nitrile) 14.4g prepares monomer solution.Then, have the 500mL's of the 3- methoxy methyl propionate of 60g to addition After three-necked flask carries out nitrogen flushing in 30 minutes, it is heated to 70 DEG C while stirring, spends 2 hours dropwise addition institutes using addition funnel State the monomer solution of preparation.Dropwise addition is started at the beginning of being set as polymerization reaction, 4 hours polymerization reactions are implemented.Thereafter, will gather The temperature for closing reaction solution is set as 90 DEG C, stirs 30 minutes.And then thereafter, the temperature of polymerization liquid is set as 70 DEG C, addition three Ethamine 77.9mL keeps 70 DEG C of temperature to stir 3 hours.After being cooled to room temperature, 12N hydrochloric acid water 55.9mL is added, stirs 30 points Ethyl acetate is added after clock and carries out liquid separation.Benefit after organic phase, be concentrated to the organic phase of recycling and sharp wash with distilled water 3- methoxy methyl propionate (as (B-1) of [B] solvent) is used to be diluted, thus to obtain 40 mass % polymer (A- are contained 1) polymer solution.The Mw of polymer (A-1) is 7,000.

[9~synthesis example of synthesis example 19]

Other than using the monomer of type and usage amount shown in following table 1, it is carried out similarly operation with synthesis example 8, Synthesize each polymer.The Mw and Mw/Mn of synthesized each polymer are shown in Table 1 together.In addition, "-" is indicated and is not used Qualified monomer.In synthesis example 16 and synthesis example 19, the methacrylic acid 1- butoxy second made of using protection carboxyl Ester as provide structural unit (II) compound situation when, in resulting [A] polymer, carboxylic is generated through deprotection Base.

[table 1]

[synthesis example 20] (synthesis of polymer (a-1))

In the flask for having cooling tube and blender, put into 2,2 '-azos bis- (2,4- methyl pentane nitriles) 7 mass parts and 3- methoxy methyl propionate ((B-1) as [B] solvent) 200 mass parts.Then, 40 mass parts of methacrylic acid and first are put into 60 mass parts of base methyl acrylate and after carrying out nitrogen displacement, start slowly to stir.The temperature of polymerization liquid is warming up to 70 DEG C, after the temperature is kept for 5 hours, add 30 mass parts of glycidyl methacrylate and 3 matter of tetrabutylammonium bromide Part is measured, and then reacts it 10 hours at 90 DEG C, obtains the polymer solution for containing 40 mass % polymer (a-1).Polymerization The Mw of object (a-1) is 10,000.

[synthesis example 21] (synthesis of polymer (F-1))

In the flask for having cooling tube and blender, put into 2,2 '-azos bis- (2,4- methyl pentane nitriles) 8 mass parts and Diethylene glycol Methyl ether ((B-2) as [B] solvent) 220 mass parts, and then add 13 mass parts of methacrylic acid, methyl 40 mass parts of glycidyl acrylate, 10 mass parts of Alpha-Methyl -4-Vinyl phenol, 10 mass parts of styrene, metering system Sour 12 mass parts of tetrahydro furfuryl ester, 15 mass parts of N- cyclohexylmaleimide and positive 10 matter of Lauryl Ester of methacrylic acid Measure part, carry out nitrogen displacement after, slowly stir and the temperature of solution is risen to 70 DEG C, by the temperature keep 5 hours simultaneously It is polymerize, thus to obtain the solution for containing polymer (F-1).The solid component concentration of the solution is 31.9 mass %.It is poly- The Mw for closing object (F-1) is 8,000, and molecular weight distribution (Mw/Mn) is 2.3.

[synthesis example 22] (synthesis of polymer (F-2))

In the flask for having cooling tube and blender, 2,2 '-azobis isobutyronitrile, 5 mass parts and acetic acid 3- methoxy are put into Base butyl ester ((B-3) as [B] solvent) 250 mass parts, and then add 7 mass parts of methacrylic acid, methacrylic acid tricyclic [5.2.1.0^2,6] 18 mass parts of decane -8- base ester, 15 mass parts of styrene, 3- methacryloxypropyl triethoxysilicane 20 mass parts of 40 mass parts of alkane and glycidyl methacrylate, after carrying out nitrogen displacement, slowly stirring and by solution Temperature rises to 80 DEG C, and the temperature is kept for 5 hours and polymerize, thus to obtain the solution for containing polymer (F-2).Institute The solid component concentration for stating solution is 28.8 mass %.The Mw of the polymer (F-2) is 12,000, molecular weight distribution (Mw/ It Mn) is 2.2.

[synthesis example 23] (synthesis of polymer (F-3))

In the flask for having cooling tube and blender, 2,2 '-azobis isobutyronitrile, 5 mass parts and acetic acid 3- methoxy are put into 250 mass parts of base butyl ester, and then add 7 mass parts of methacrylic acid, methacrylic acid tricyclic [5.2.1.0^2,6] decane -8- base 40 mass parts of 28 mass parts of ester, 25 mass parts of styrene and glycidyl methacrylate, after carrying out nitrogen displacement, slowly It stirs and the temperature of solution is risen to 80 DEG C, the temperature is kept for 5 hours and polymerize, thus to obtain polymer is contained (F-3) solution.The solid component concentration of the solution is 28.8 mass %.The Mw of the polymer (F-3) is 10,000, point Son amount distribution (Mw/Mn) is 2.2.

[synthesis example 24] (synthesis of polymer (F-4))

In the flask for having cooling tube and blender, 2,2 '-azobis isobutyronitrile, 5 mass parts and acetic acid 3- methoxy are put into 250 mass parts of base butyl ester, and then add 7 mass parts of methacrylic acid, methacrylic acid tricyclic [5.2.1.0^2,6] decane -8- base 28 mass parts of ester, 25 mass parts of styrene and methacrylic acid 3,40 mass parts of 4- expoxycyclohexyl methyl esters carry out nitrogen and set It after changing, slowly stirs and the temperature of solution is risen to 80 DEG C, the temperature is kept for 5 hours and polymerize, is thus obtained Obtain the solution containing polymer (F-4).The solid component concentration of the solution is 28.8 mass %.The polymer (F-4) Mw is 11,000, and molecular weight distribution (Mw/Mn) is 2.1.

[B] solvent, [C] polymerizable compound used in preparation by curable resin composition, [D] free radical polymerization Initiator and [E] acid producing agent are shown in following.

[[B] solvent]

B-1:3- methoxy methyl propionate

B-2: diethylene glycol Methyl ether

B-3: acetic acid 3- methoxybutyl

[[C] polymerizable compound]

C-1: the mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol hexaacrylate be (Japanese chemical drug company " card Asia ladd (KAYARAD) DPHA ")

C-2: modified pentaerythritol triacrylate (" Aronix (Aronix) TO- of East Asia Synesis Company of succinic acid 756”)

C-3: trimethylolpropane trimethacrylate

C-4: mixture (Osaka organic chemistry work of eight acrylate of tripentaerythritol and seven acrylate of tripentaerythritol " than this Carter (Viscoat) 802 " of industry company)

C-5: modified Dipentaerythritol Pentaacrylate (" Aronix (Aronix) M- of East Asia Synesis Company of succinic acid 520”)

[[D] radical polymerization initiator]

D-1:2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinopropane-1- ketone (BASF (BASF) company it is " gorgeous good (Gu Irgacure) 907 ")

D-2: ethyl ketone -1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -1- (O- acetyl group oxime) (bar " gorgeous good solid (Irgacure) OXE02 " of Si Fu company)

D-3:2,4- diethyl thioxanthone

[[E] acid producing agent]

E-1:4,4 '-[1- [4- [1- [4- hydroxy phenyl] -1- Methylethyl] phenyl] ethylidene] bis-phenol -1,2- naphthoquinones two Nitrine -5- sulphonic acid ester

[embodiment 1]

(A-1) 100 mass parts synthesized in the synthesis example 8 as [A] polymer will be contained and as [B] solvent (B-1) solution of 150 mass parts, as (B-1) 200 mass parts of [B] solvent, as (C-1) 50 of [C] polymerizable compound Mass parts and as [D] radical polymerization initiator (D-1) 10 mass parts mix, utilize 0.2 μm of the membrane filter in aperture It is filtered, thus prepares curable resin composition (J-1).

[2~embodiment of embodiment 25 and 1~comparative example of comparative example 3]

In addition to mixed in a manner of each ingredient containing type shown in following table 2 and table 3 and amount each raw material with Outside, it is operable to prepare curable resin composition (J-2)~curable resin composition (J-25) similarly to Example 1 And curable resin composition (CJ-1)~curable resin composition (CJ-3)."-" expression in table 3 is not used eligible Ingredient.

For the curable resin composition of the preparation, according to the adhesiveness of following methods evaluation cured film and transparent Property and storage stability and radioactive ray sensitivity.

[adhesiveness of cured film]

The adhesiveness of cured film is evaluated after exposure delay hardening film figure.Specifically, firstly, using rotation Apply after device is coated with curable resin composition on the glass substrate, at 90 DEG C on hot plate prebake conditions 2 minutes and form film Thick 3.0 μm of film.Then, using exposure machine (" MPA-600FA (mixing of ghi ray) " of Canon (Canon) company), be situated between every 10 μm of line and space (1: 1) pattern, which is formed, uses mask, with 700 (J/m²) light exposure be exposed.Thereafter, using 0.5 matter The tetramethylammonium hydroxide aqueous solution for measuring % utilizes the development of covering liquid method progress 80 seconds at 25 DEG C.Then, using ultrapure water into Row flowing water cleaning in 1 minute, it is followed by dry, to form pattern on the glass substrate.Developed using optical microphotograph sem observation Substrate afterwards, the presence or absence of confirmation pattern removing.According to the adhesiveness of following judgement benchmark evaluation pattern.

The situation of pattern removing: "○" is not almost found

Slightly find the situation of pattern removing: " △ "

Pattern is peeling-off, the almost situation of non-residual pattern on substrate: "×"

[transparency of cured film]

On a silicon substrate, the film with a thickness of 3.0 μm is formed using curable resin composition.In cleaning oven with 220 DEG C are heated the silicon substrate 1 hour and form cured film.To the cured film, spectrophotometer (Hitachi is used " 150-20 type dual-beam ") measurement wavelength 400nm when transmitance.The value of the transmitance (%) is shown in table 2 and table 3 In.About the transparency, it is good for can be evaluated in the situation that the transmitance is 90% or more, can in the situation less than 90% It is evaluated as bad.

[evaluation of storage stability]

Curable resin composition is placed 1 week in 40 DEG C of baking oven.The viscosity (1) at measurement initial stage and after placing 1 week Viscosity (2), according to | viscosity (2)-viscosity (1) | × 100/ viscosity (1) calculates rate of change in viscosity (%).| viscosity (2)-is viscous Degree (1) | refer to the absolute value of the difference of viscosity (2) Yu viscosity (1).The value of the rate of change in viscosity (%) is shown in table 2 and table 3 In.About storage stability, it is good for can be evaluated when rate of change in viscosity is 5% situation below, when being more than 5% situation It is bad for can be evaluated.

[radioactive ray sensitivity]

After being coated with curable resin composition on the glass substrate using spinner, the prebake conditions on hot plate at 90 DEG C 2 minutes and form 3.0 μm of film thickness of film.Then, using exposure machine (Canon Inc. " (ghi ray is mixed by MPA-600FA Close) "), it is situated between every the mask of line and space (1: 1) pattern with 10 μm, and light exposure is set as variable and film irradiation is put Ray.Thereafter, using the tetramethylammonium hydroxide aqueous solution of 0.5 mass %, 80 seconds aobvious is carried out using covering liquid method at 25 DEG C Shadow.Then, 1 minute flowing water is carried out using ultrapure water to clean, it is followed by dry, pattern is thus formed on the glass substrate.This When, the space pattern of 10 μm of investigation is completely dissolved required light exposure.By the light exposure (J/m²) value be shown in table 2 and In table 3.It is 500 (J/m in the light exposure about radioactive ray sensitivity²) situation below when to can be evaluated be good.

[table 2]

[table 3]

It is defined according to the result of table 2 and table 3: about the curable resin composition of embodiment, the adhesiveness of cured film And the transparency, storage stability and radioactive ray sensitivity when radioactive ray curable resin composition is made are excellent.Relative to This, the performance that the curable resin composition of comparative example is whole about these does not obtain good result.

[industrial availability]

Curable resin composition of the invention can form adhesiveness and transparent excellent cured film, and storage stability It is excellent.Display element cured film of the invention can suitably be used as display element since adhesiveness and the transparency are excellent Interlayer dielectric, protective film, spacer etc..Therefore, these manufacturing process that may be suitably used to the display elements such as liquid-crystal apparatus In.

Claims

1. a kind of curable resin composition, it is characterised in that contain: polymer and solvent, the polymer have following formula (1) structural unit represented by and the structural unit containing acidic groups,

In formula (1), R¹、R²And R³It is separately hydrogen atom or the alkyl of 1 valence of carbon number 1~20；R¹、R²And R³In 2 It can mutually be bonded above and the carbon atom that is bonded with them is formed together the ring structure of ring element number 3~20；R⁴For (a) carbon number 1 The alkyl, (b) of~20 (n+1) valence contain between the carbon-to-carbon of (a) alkyl selects free oxygen atom, sulphur atom ,-SO- and-SO₂- At least one kind of base in the group of composition or (c) (a) alkyl and (b) part or all of hydrogen atom possessed by base are through selecting Free halogen atom, cyano, nitro, carboxyl, sulfinic acid base, sulfydryl and carbon number 1~12 alkoxy composition group in extremely Base made of few a kind of substitution；The integer that n is 1~6；When n is 2 or more, multiple R¹It may be the same or different, multiple R²It can be identical Can be different, multiple R³It may be the same or different；R⁵For-COO-*；* expression and R⁴The position of bond；R⁶For hydrogen atom, methyl or fluorine Change methyl；Wherein, when n is 1, R⁴It is the cyclic hydrocarbon group of (n+1) valence of (d) carbon number 1~20, (e) in (d) cyclic hydrocarbon group Contain between carbon-to-carbon and selects free oxygen atom, sulphur atom ,-SO- and-SO₂At least one kind of base, (f) in the group of composition is in carbon number Containing selected from by sulphur atom ,-SO- and-SO between the carbon-to-carbon of the chain alkyl of 1~20 (n+1) valence₂In the group of composition extremely Few a kind of base or (g) (d) cyclic hydrocarbon group, (e) base and (f) part or all of hydrogen atom possessed by base through selected from by halogen Plain atom, cyano, nitro, carboxyl, sulfinic acid base, sulfydryl and carbon number 1~12 alkoxy composition group at least one kind of take Base made of generation.

2. curable resin composition according to claim 1, it is characterised in that also contain: having ethylene unsaturated bond Polymerizable compound.

3. curable resin composition according to claim 1 or 2, it is characterised in that also contain:

It is at least one kind of in the group being made of radical polymerization initiator and acid producing agent.

4. curable resin composition according to claim 3, it is characterised in that contain the radical polymerization initiator.

5. curable resin composition according to claim 4, which is characterized in that the radical polymerization initiator is sense Radiation is linear.

6. curable resin composition according to claim 3, it is characterised in that contain the acid producing agent.

7. curable resin composition according to claim 6, which is characterized in that the acid producing agent is radiation Property.

8. curable resin composition according to claim 1 or 2, it is characterised in that:

Its formation for being used for the display element cured film as interlayer dielectric, protective film or spacer.

9. a kind of display element cured film, it is characterised in that: it is as interlayer dielectric, protective film or spacer, and it is It is formed by curable resin composition as claimed in claim 8.

10. a kind of forming method of display element cured film, characterized by comprising:

In the step of forming film on substrate；

The step of radioactive ray are irradiated at least part of the film；

The step of developing to the film irradiated through the radioactive ray；And

The step of film through the development is heated；

And the film is formed by curable resin composition as described in claim 5 or 7.

11. a kind of display element, characterized by comprising: display element cured film according to claim 9.