CN112180680A - Radical-cation hybrid photocurable composition and photosensitive dry film resist - Google Patents

Radical-cation hybrid photocurable composition and photosensitive dry film resist Download PDF

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CN112180680A
CN112180680A CN202010976789.XA CN202010976789A CN112180680A CN 112180680 A CN112180680 A CN 112180680A CN 202010976789 A CN202010976789 A CN 202010976789A CN 112180680 A CN112180680 A CN 112180680A
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radical
branched
meth
photocurable composition
acrylate
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邹应全
庞玉莲
辛阳阳
丁艳花
B·斯特雷梅尔
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BAODING LUCKY INNOVATIVE MATERIALS Co.,Ltd.
Sichuan Lekai New Material Co.,Ltd.
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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Abstract

The present invention relates to a radical-cation hybrid photocurable composition comprising (a) at least one alkali-soluble polymer, (b) at least one photopolymerizable compound, (c) at least one infrared absorbing photosensitizer and (d) at least one photopolymerization initiator, wherein the photopolymerizable compound as component (b) contains (b1) at least one radical polymerizable compound and (b2) at least one cationically polymerizable compound selected from the group consisting of alkenyl ether compounds and/or ethylene oxide compounds and/or aziridine compounds and/or oxetane compounds, and the infrared absorbing photosensitizer as component (c) contains at least one polymethine cyanine compound. The radical-cation hybrid photocurable composition of the present invention is suitable for preparing a photosensitive dry film resist.

Description

Radical-cation hybrid photocurable composition and photosensitive dry film resist
Technical Field
The present invention relates to a radical-cation hybrid photocurable composition comprising (a) at least one alkali-soluble polymer, (b) at least one photopolymerizable compound, (c) at least one infrared-absorbing photosensitizer and (d) at least one photopolymerization initiator. The radical-cation hybrid photocurable composition of the present invention is suitable for preparing a photosensitive dry film resist.
Background
Since the advent of Printed Circuit Boards (PCBs), the development and development of materials for PCB pattern transfer has never been stopped. In the PCB fabrication process, pattern transfer is a key process, and dupont company introduced the use of photosensitive dry film resist for PCB pattern transfer in 1968, and has therefore played a leading role in PCB pattern transfer fabrication. With the continuous progress of science and technology, Laser Direct Imaging (LDI) dry films have been produced under the drive of the lightness and density of electronic devices and circuits. The photosensitive dry film resist is a film material for transferring PCB pattern by photopolymerization.
CN103176362A reports a photosensitive resin composition contained in a dry film resist (photoresist), in which photopolymerization is carried out using a single radical photopolymerization system.
The photosensitive system adopting free radical photopolymerization is accompanied with large volume shrinkage and is easily interfered by oxygen inhibition, so that poor adhesion with a base material and poor surface curing are caused.
In addition, various companies at home and abroad have developed various LDI photosensitive dry films for laser direct imaging, and the photosensitive main wavelengths of the LDI photosensitive dry films are ultraviolet laser with the wavelength of 355nm or 405 nm. The maskless direct laser drawing method directly uses the designed required image in the equipment computer, and the laser direct drawing method of irradiation imaging gradually and completely replaces the traditional mercury lamp exposure technology, so that the method is practically applied in the future mainstream. At present, light with a wavelength of 350-410nm, especially i-ray or h-ray, is often used as a light source of the laser direct writing method, and specifically, a multi-mirror multi-beam with a wavelength of 355nm using a YAG laser as a light source, an active light with a wavelength of 390-430nm using a blue-violet semiconductor laser as a light source, and a gallium nitride-based blue laser source with a wavelength of 405nm having a long lifetime and a high output rate are used as a light source. These laser light sources are not good for the health of operators and cannot be operated in the open room from the viewpoints of safety, operability, and the like; from the cost aspect, the equipment price is high. Meanwhile, the penetrating power of ultraviolet light is weak, and some components or pigment substances with conjugated structures in the light curing formula have strong absorption to the ultraviolet light, so that the light intensity is seriously attenuated, the curing is incomplete and the performance of a light curing film is poor; easily produce ozone to pollute the environment, and the like. In addition, ultraviolet light has harm to human body, and the light source has short service life and higher price.
Disclosure of Invention
In view of the problems of the prior art, the present inventors have conducted intensive studies on a radical-cation hybrid photocurable composition suitable for a near-infrared light source. The present inventors have surprisingly found that a specific infrared absorbing photosensitizer-sensitized photopolymerization initiator can initiate a cation-radical hybrid polymerization reaction, which has good photosensitivity, particularly good sensitivity.
The radical-cation hybrid photocurable composition of the present invention, which comprises an alkali-soluble polymer, a specific photopolymerizable compound, an infrared absorbing photosensitizer, and a photopolymerization initiator, makes it possible to achieve cation-radical hybrid polymerization using infrared light instead of ultraviolet light as a light source. The infrared light has long wavelength and good penetrability, and can overcome the difference of imaging of the surface layer and the bottom layer, so that the side wall of the pattern is steeper. In addition, the infrared light has little harm to human bodies, the service life of the light source is longer, and the price is cheaper.
The photosensitive dry film resist containing the free radical-cation hybrid photocurable composition has the characteristics of higher photosensitivity, finer imaging, steeper side wall and the like.
An object of the present disclosure is to provide a radical-cation hybrid photocurable composition for radical-cation hybrid polymerization.
Another object of the present disclosure is to provide a photosensitive dry film resist comprising the radical-cation hybrid photocurable composition of the present invention.
It is still another object of the present disclosure to provide use of the radical-cation hybrid photocurable composition of the present invention for preparing a photosensitive dry film resist.
The technical scheme for achieving the purpose of the invention can be summarized as follows:
1. a radical-cation hybrid photocurable composition comprising the following components:
(a) at least one alkali-soluble polymer, at least one polymer,
(b) at least one kind of a photopolymerizable compound which,
(c) at least one infrared absorbing photosensitizer, and
(d) at least one kind of photopolymerization initiator,
wherein the photopolymerizable compound as the component (b) contains (b1) at least one radical polymerizable compound and (b2) at least one cation polymerizable compound selected from the group consisting of alkenyl ether compounds and/or ethylene oxide compounds and/or aziridine compounds and/or oxetane compounds, and the infrared absorbing photosensitizer as the component (c) contains at least one polymethine cyanine compound.
2. The radical-cation hybrid photocurable composition according to embodiment 1, wherein the alkali-soluble polymer is an alkali-soluble polymer containing a structural unit derived from (meth) acrylic acid and a structural unit derived from a polymerizable compound other than (meth) acrylic acid.
3. The radical-cation hybrid photocurable composition according to embodiment 2, wherein the other polymerizable compound is selected from the group consisting of styrene, α -methylstyrene, (meth) acrylic acid C1-C10Alkyl esters, (meth) acrylic acid C3-C8Cycloalkyl esters, hydroxy C (meth) acrylates1-C6Alkyl esters, benzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, and (meth) acrylic acid(meth) acrylates such as 2,2,3, 3-tetrafluoropropyl ester, dicyclopentenyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, adamantyloxyeethyl (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, and adamantyloxypropyloxyethyl (meth) acrylate; (meth) acrylic acid derivatives such as α -bromoacrylic acid, α -chloroacrylic acid, β -furyl (meth) acrylic acid, and β -styryl (meth) acrylic acid; a polymerizable styrene derivative substituted on the aromatic ring; acrylamides such as diacetone acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; maleic acid; maleic anhydride; maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; unsaturated carboxylic acid derivatives such as fumaric acid, cinnamic acid, α -cyanocinnamic acid, itaconic acid, crotonic acid, and propanoic acid; or a combination thereof, preferably styrene, (meth) acrylic acid C1-C6Alkyl esters, benzyl (meth) acrylate, or combinations thereof, more preferably styrene, methyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, or combinations thereof.
4. The radical-cation hybrid photocurable composition according to embodiment 2 or 3, wherein the amount of the structural unit derived from (meth) acrylic acid is 10 to 40% by weight, preferably 20 to 35% by weight, more preferably 25 to 32% by weight, based on the weight of the alkali-soluble polymer.
5. The radical-cation hybrid photocurable composition according to any one of embodiments 2 to 4, wherein the amount of the structural unit derived from the other polymerizable compound is 60 to 90% by weight, preferably 65 to 80% by weight, more preferably 68 to 75% by weight, based on the weight of the alkali-soluble polymer.
6. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 5, wherein the acid value of the alkali-soluble polymer is from 90 to 250mg KOH/g, preferably 130-230mg KOH/g, more preferably 150-200mg KOH/g.
7. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 6, wherein the weight average molecular weight (Mw) of the alkali-soluble polymer is 10,000-600,000, preferably 20,000-300,000, more preferably 35,000-80,000, as determined by Gel Permeation Chromatography (GPC) as converted by using a standard curve of standard polystyrene.
8. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 7, wherein the polydispersity index (weight average molecular weight/number average molecular weight) of the alkali-soluble polymer is less than or equal to 6.0, preferably less than or equal to 4.0, more preferably from 1.5 to 3.0.
9. The radical-cationic hybrid photocurable composition according to any one of embodiments 1 to 8, wherein the amount of the alkali-soluble polymer is 30 to 68% by weight, preferably 35 to 65% by weight, more preferably 40 to 60% by weight, based on the total weight of the radical-cationic hybrid photocurable composition.
10. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 9, wherein the radical polymerizable compound as the component (b1) is an ethylenically unsaturated group-containing radical polymerizable compound, preferably a monofunctional compound, a difunctional compound, a trifunctional or higher-functional compound, and a mixture thereof.
11. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 10, wherein the radical polymerizable compound as the component (b1) is selected from at least one of radical polymerizable resins, 2-functional or more radical polymerizable monomers, and monofunctional radical polymerizable monomers.
12. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 11, wherein the radical polymerizable compound as the component (b1) is selected from the group consisting of (meth) acrylate compounds, (meth) acryl compounds, vinyl derivatives, styrene compounds, anhydride compounds containing an ethylenically unsaturated double bond, N-vinylpyrrolidone, N-vinylformamide, and mixtures thereof.
13. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 12, wherein the amount of the photopolymerizable compound as the component (b) is 30 to 60% by weight, preferably 35 to 55% by weight, more preferably 40 to 50% by weight, based on the total weight of the radical-cation hybrid photocurable composition.
14. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 13, wherein the weight ratio of component (b1) to component (b2) is from 10:1 to 1:10, preferably from 4:1 to 6:5, more preferably from 3.5:1 to 1: 1.
15. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 14, wherein the cationically polymerizable compound as component (b2) is selected from the group consisting of alkenyl ether compounds and/or oxetane compounds, preferably oxetane compounds.
16. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 15, wherein the polymethine cyanine compound as the component (c) has an absorption maximum at 780nm to 2,000 nm.
17. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 16, wherein the polymethine cyanine compound as the component (c) has a structure represented by formula (I):
Figure BDA0002685496620000051
wherein
Y+Represented are bicyclic, tricyclic or higher heterocyclic rings having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members and carrying a positive charge,
y represents a bicyclic, tricyclic or higher heterocyclic ring having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members,
Y+and said heterocycle in the definition of Y may carry 1 or more substituents selected from halogen, CN, nitro, C1-C12Branched or unbranched alkyl, C1-C12Branched or unbranched alkoxy radical, C1-C12A substituent of a branched or unbranched alkylthio group or a phenylthio group,wherein said C1-C12Branched or unbranched alkyl, said C1-C12Branched or unbranched alkoxy radical, said C1-C12The alkyl groups in a branched or unbranched alkylthio group may be interrupted by 1 or more non-adjacent oxygen atoms;
preferably Y+and/Y is a structural unit shown as follows respectively:
indole salts/indoles
Figure BDA0002685496620000061
Phenyl [ e ]]Indole salts/phenyl [ e ]]Indoles
Figure BDA0002685496620000062
And/or phenyl [ c, d ]]Indole salts/phenyl [ c, d ]]An indole compound having a structure represented by formula (I),
Figure BDA0002685496620000063
wherein said indole salt/indole, phenyl [ e ]]Indole salts/phenyl [ e ]]Indole, and phenyl [ c, d ]]Indole salts/phenyl [ c, d ]]The indole may have 1 or more, preferably 1 or 2, substituents selected from halogen, CN, nitro and C on the benzene ring or naphthalene ring1-C12Branched or unbranched alkyl, C1-C12Branched or unbranched alkoxy radical, C1-C12A substituent of a branched or unbranched alkylthio group or a phenylthio group, wherein said C1-C12Branched or unbranched alkyl, said C1-C12Branched or unbranched alkoxy radical, said C1-C12The alkyl groups in a branched or unbranched alkylthio group may be interrupted by 1 or more non-adjacent oxygen atoms;
wherein R is1Is selected from C1-C12Branched or unbranched alkyl and C1-C12A branched or unbranched alkoxy group, wherein said C1-C12Branched or unbranched alkyl and C1-C12The branched or unbranched alkoxy groups may be interrupted by 1 or more non-adjacent oxygen atoms, e.g. - [ -CH2CHR-O-]nThe polyether shownWherein n is 1-6, R is H or CH3；
Wherein the ring carbon position shown by the arrow is a connecting site with the polymethine chain;
more preferably Y+and/Y is a structural unit shown as follows respectively:
Figure BDA0002685496620000064
and/or
Figure BDA0002685496620000071
Wherein R is1Is selected from C1-C12Branched or unbranched alkyl and C1-C12A branched or unbranched alkoxy group, wherein said C1-C12Branched or unbranched alkyl and C1-C12The branched or unbranched alkoxy groups may be interrupted by 1 or more non-adjacent oxygen atoms, e.g. - [ -CH2CHR-O-]nThe polyether is shown, wherein n is 1-6, R is H or CH3(ii) a And
R2，R3independently of one another, selected from H, halogen, CN, nitro, C1-C12Branched or unbranched alkyl, C1-C12Branched or unbranched alkoxy radical, C1-C12A branched or unbranched alkylthio group or a phenylthio group, wherein said C1-C12Branched or unbranched alkyl, said C1-C12Branched or unbranched alkoxy radical, said C1-C12The alkyl groups in a branched or unbranched alkylthio group may be interrupted by 1 or more non-adjacent oxygen atoms;
wherein the ring carbon position shown by the arrow is a connecting site with the polymethine chain;
n1，n2independently 0, 1 or 2; preferably 0 or 1, more preferably 1;
b and C are independently selected from H, C1-C12Alkyl groups or together with the carbon atoms linking them form a five-or six-membered ring;
a is selected from the structures shown as A-1 to A-13:
Figure BDA0002685496620000072
or C1-C12A branched or unbranched alkoxy group (A-13);
wherein
Denotes the attachment site to the structure of formula (I),
wherein "R2And R2The "radicals, which are identical or different, are each independently selected from hydrogen, halogen, C1-C6Branched or unbranched alkyl, C1-C6Branched or unbranched alkoxy radical, C1-C6A branched or unbranched alkylthio group or a phenylthio group,
preferably the group A is selected from the structures shown as A-4, A-5 or A-7 to A-13;
when the A group is a group A-1 or A-2, n3Is 0, when the A group is a group A3-A13, n3The number of the carbon atoms is1,
and X-Represents a counter ion.
18. The radical-cation hybrid photocurable composition according to embodiment 17, wherein the compound of formula (I) satisfies one or more of the following conditions:
R1is selected from C1-C6Branched or unbranched alkyl and C1-C6A branched or unbranched alkoxy group, wherein said C1-C6Branched or unbranched alkyl and C1-C6The branched or unbranched alkoxy groups may be separated by 1 or 2 non-adjacent oxygen atoms;
R2selected from H, halogen, nitro, C1-C6Branched or unbranched alkyl and C1-C6A branched or unbranched alkoxy group, wherein said C1-C6Branched or unbranched alkyl, said C1-C6The branched or unbranched alkoxy groups may be separated by 1 or 2 non-adjacent oxygen atoms;
R3selected from H, C1-C6Branched or unbranched alkyl and C1-C6A branched or unbranched alkoxy group, wherein said C1-C6Branched or unbranched alkyl and said C1-C6The branched or unbranched alkoxy groups may be separated by 1 or 2 non-adjacent oxygen atoms.
19. The radical-cation hybrid photocurable composition according to embodiment 17 or 18, wherein X-Represents the following counterions: BF (BF) generator4 -、PF6 -、SbF6 -、AsF6 -、[PF3(C2F5)3]-、[Al(OC(CF3)3)4]-、[B(PhF5)4]-、[B(Ph(CF3)2)4]-、[((CF3)2SO2)2N]-、[((CF3)2SO2)3C]-、Cl-、Br-、F-、[Al(O-t-C4F9)4]-、[Al(O-(i-C3F7)CH3)4]-、[C(O-SO2CF3)3]-、[n-C12H25-TsO]-Or [ NTf2]-Among them, BF is preferred4 -、PF6 -、SbF6 -、AsF6 -、[PF3(C2F5)3]-、[Al(OC(CF3)3)4]-、[B(PhF5)4]-、[B(Ph(CF3)2)4]-、[((CF3)2SO2)2N]-、[((CF3)2SO2)3C]-、[Al(O-t-C4F9)4]-、[Al(O-(i-C3F7)CH3)4]-Or [ NTf2]-More preferably, [ PF ]3(C2F5)3]-、[Al(OC(CF3)3)4]-、[B(PhF5)4]-、[B(Ph(CF3)2)4]-、[((CF3)2SO2)2N]-、[((CF3)2SO2)3C]-、[Al(O-t-C4F9)4]-Or [ Al (O- (i-C) ]3F7)CH3)4]-Most preferably, [ Al (O-t-C)4F9)4]-Or [ PF ]3(C2F5)3]-。
20. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 19, wherein the infrared-absorbing photosensitizer as component (c) is selected from one or more of the following compounds S1-S70:
Figure BDA0002685496620000091
Figure BDA0002685496620000092
Figure BDA0002685496620000101
21. the photocurable compound according to any one of embodiments 1-20, wherein the photopolymerization initiator as the component (d) may be a photopolymerization initiator capable of generating radicals and cations in the presence of the component (c).
22. A photocurable compound according to any one of embodiments 1-21, wherein the photopolymerization initiator as component (d) is selected from the group consisting of iodonium salts, sulfonium salts, triazines, and oxime ester-type photopolymerization initiators.
23. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 22, wherein the photopolymerization initiator as component (d) is an iodonium salt, preferably selected from the group consisting of iodonium salts represented by formula II:
Figure BDA0002685496620000111
wherein R is1’-R6' may be the same or different and are independently selected from H, halogen, nitro, C1-C20Branched or unbranched alkyl, C1-C20Branched or unbranched alkoxy and C1-C20A branched or unbranched alkylthio group, and
X’-x in the compounds of formula (I) as in embodiments 17 or 19-The definition of the content of the compound is as follows,
x in the compounds of the formula (I) is preferred-And X 'in the compound of formula (II)'-Are the same.
24. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 23, wherein the photopolymerization initiator as component (d) IS selected from one or more of the following compounds IS1-IS 40:
Figure BDA0002685496620000112
Figure BDA0002685496620000113
Figure BDA0002685496620000121
25. the radical-cationic hybrid photocurable composition according to any one of embodiments 1 to 24, wherein the amount of the infrared absorbing photosensitizer as component (c) is from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight, based on the total weight of the radical-cationic hybrid photocurable composition.
26. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 25, wherein the amount of the photopolymerization initiator as the component (d) is from 1 to 10% by weight, preferably from 2 to 8% by weight, more preferably from 2.5 to 5% by weight, based on the total weight of the radical-cation hybrid photocurable composition.
27. The radical-cation hybrid photocurable composition according to any one of embodiments 1 to 26, wherein the weight ratio of the infrared absorbing photosensitizer as component (c) to the photopolymerization initiator as component (d) is from 10:1 to 1:10, preferably from 8:1 to 1:8, more preferably from 5:1 to 1: 5.
28. A coating liquid comprising the radical-cation hybrid photocurable composition according to any one of embodiments 1 to 27 and at least one organic solvent.
29. A photosensitive dry film resist comprising a support, a photosensitive layer provided on the support, and a protective layer provided on the photosensitive layer, the photosensitive layer comprising the radical-cation hybrid photocurable composition according to any one of embodiments 1 to 27.
30. Use of the radical-cation hybrid photocurable composition according to any one of embodiments 1 to 27 for the preparation of a photosensitive dry film resist.
Detailed Description
Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps) are not essential unless otherwise explicitly stated. The same applies to values and ranges, without limiting the invention.
Herein, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acryl" means acryl or methacryl. The "(poly) ethyleneoxy group" means at least one of an ethyleneoxy group (hereinafter, also referred to as "EO group") and a polyethyleneoxy group in which two or more ethylene groups are linked by an ether bond. The "(poly) propyleneoxy group" means at least one of a propyleneoxy group (hereinafter, also referred to as "PO group") and a polypropyleneoxy group in which two or more propylene groups are linked by an ether bond. "EO-modified" refers to a compound having a (poly) ethyleneoxy group, "PO-modified" refers to a compound having a (poly) propyleneoxy group, and "EO-PO-modified" refers to a compound having both a (poly) ethyleneoxy group and a (poly) propyleneoxy group.
In addition, the numerical ranges used herein represent ranges in which the numerical values recited before and after are respectively the minimum value and the maximum value.
Specific values (including range endpoints) disclosed herein for related features can be combined with each other to form new ranges.
According to the invention, the prefix "Cn-Cm"in each case denotes that the number of carbon atoms contained in the radical is n to m.
"halogen" refers to fluorine, chlorine, bromine and iodine. According to the present invention, it is preferred that the halogen comprises F, Cl or a combination thereof. "halo" means substituted by one or more of the same or different halogen atoms.
The term "C" as used herein, alone or in combinationn-CmAlkyl "and" Cn-CmUnbranched or branched alkyl "and means a branched or unbranched saturated hydrocarbon radical having n-m, for example from 1 to 20, preferably from 1 to 12, more preferably from 1 to 8, particularly preferably from 1 to 6, for example from 1 to 5 or from 1 to 4, carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and isomers thereof. C1-C8The alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, and isomers thereof. C1-C6The alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, t-butyl, pentyl, isopentyl, hexyl and isomers thereof. C1-C4The alkyl group may be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, and isomers thereof.
The term "C" as used herein2-CmAlkenyl "means a branched or unbranched unsaturated hydrocarbon group having 2 to m, for example 2 to 20, preferably 2 to 6, more preferably 2 to 4 carbon atoms and having one double bond at any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-4-butenyl, 2-methyl-1-propenyl, 2-methyl-propenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 3-hexenyl, 2-hexenyl, and the like, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl-2-butenyl, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2-dimethyl-3-butenyl, 2, 3-dimethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 3-dimethyl-1-butenyl, 2, 3-dimethyl-3-butenyl, 2, 3-dimethyl-1-butenyl, 1, 2-butenyl, 2, 3-butenyl, 2-dimethyl-3-butenyl, 2, 3-dimethyl, 3, 3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenylAlkenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, and isomers thereof. C2-C6The alkenyl group may be vinyl, propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, neopentynyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, isohexenyl, neohexenyl and isomers thereof. C2-C4The alkenyl group may be vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, and isomers thereof.
The term "C" as used herein3-CmCycloalkyl "means a saturated alicyclic monocyclic group having 3 to m, such as 3 to 20, preferably 3 to 8, more preferably 5 to 6, ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
The term "Cn-CmAlkoxy "and" Cn-CmAlkylthio "means at Cn-CmOpen chain C corresponding to alkyln-CmC having an oxygen or sulfur atom as a linking group bonded to any carbon atom of the alkanen-CmAlkyl radicals, e.g. C1-C20Alkoxy (or thio) radicals, preferably C1-C12Alkoxy (or thio) radicals, more preferably C1-C8Alkoxy (or thio) radicals, particularly preferably C1-C6Alkoxy (or thio) radicals, particularly preferably C1-C4Alkoxy (or thio) group. C1-C8The alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, isooctoxy and isomers thereof. C1-C4The alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and isomers thereof. C1-C8The alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, 2-butylthio, t-butylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, isooctylthio and isomers thereof. C1-C4The alkylthio group can be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio and isomers thereof.
For Y+Y is a bicyclic, tricyclic or higher heterocyclic ring having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members, preferably a bicyclic or tricyclic heterocyclic ring having 8 to 14 ring members and containing 1 nitrogen atom as ring member.
A first aspect of the present disclosure relates to a radical-cation hybrid photocurable composition comprising the following components:
(a) at least one alkali-soluble polymer, at least one polymer,
(b) at least one kind of a photopolymerizable compound which,
(c) at least one infrared-absorbing photosensitizer,
(d) at least one kind of photopolymerization initiator,
wherein the photopolymerizable compound as the component (b) contains (b1) at least one radical polymerizable compound and (b2) at least one cation polymerizable compound selected from the group consisting of alkenyl ether compounds and/or ethylene oxide compounds and/or aziridine compounds and/or oxetane compounds, and the infrared absorbing photosensitizer as the component (c) contains at least one polymethine cyanine compound.
Alkali soluble polymer (a)
According to a preferred embodiment of the present invention, the alkali-soluble polymer is an alkali-soluble polymer containing a structural unit derived from (meth) acrylic acid and a structural unit derived from a polymerizable compound other than (meth) acrylic acid.
The other polymerizable compounds are not particularly limited, and examples thereof include styrene, alpha-methylstyrene, and (meth) acrylic acid C1-C10Alkyl esters, (meth) acrylic acid C3-C8Cycloalkyl esters, hydroxy C (meth) acrylates1-C6Alkyl esters, benzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, adamantyloxyethyl (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, and mixtures thereof, (meth) acrylates such as dicyclopentanyloxypropyloxyethyl (meth) acrylate and adamantyloxypropyloxyethyl (meth) acrylate; (meth) acrylic acid derivatives such as α -bromoacrylic acid, α -chloroacrylic acid, β -furyl (meth) acrylic acid, and β -styryl (meth) acrylic acid; a polymerizable styrene derivative substituted on the aromatic ring; acrylamides such as diacetone acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; maleic acid; maleic anhydride; maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; unsaturated carboxylic acid derivatives such as fumaric acid, cinnamic acid, α -cyanocinnamic acid, itaconic acid, crotonic acid, and propanoic acid; or a combination thereof, preferably styrene, (meth) acrylic acid C1-C6Alkyl esters, benzyl (meth) acrylate, or combinations thereof, more preferably styrene, methyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, or combinations thereof.
The amount of the structural unit derived from (meth) acrylic acid may be 10 to 40% by weight, preferably 20 to 35% by weight, more preferably 25 to 32% by weight, based on the weight of the alkali-soluble polymer.
The amount of the structural unit derived from the other polymerizable compound may be 60 to 90% by weight, preferably 65 to 80% by weight, more preferably 68 to 75% by weight, based on the weight of the alkali-soluble polymer.
The acid value of the alkali-soluble polymer may be 90-250mg KOH/g, preferably 130-230mg KOH/g, more preferably 150-200mg KOH/g.
The weight average molecular weight (Mw) of the alkali-soluble polymer may be 10,000-600,000, preferably 20,000-300,000, more preferably 35,000-80,000 as measured by Gel Permeation Chromatography (GPC) by conversion using a standard curve of standard polystyrene.
The polydispersity index (weight average molecular weight/number average molecular weight) of the alkali-soluble polymer may be less than or equal to 6.0, preferably less than or equal to 4.0, more preferably from 1.5 to 3.0.
According to the present invention, the amount of the alkali-soluble polymer may be 30 to 68% by weight, preferably 35 to 65% by weight, more preferably 40 to 60% by weight, based on the total weight of the radical-cationic hybrid photocurable composition.
The alkali-soluble polymer may be prepared by conventional polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization or emulsion polymerization, preferably solution polymerization.
Radically polymerizable Compound (b1)
According to a preferred embodiment of the present invention, the radical polymerizable compound is a radical polymerizable compound containing an ethylenically unsaturated group. The radical polymerizable compound may be in the form of a monomer or a resin (including oligomers and prepolymers).
The radical polymerizable compound includes a radical polymerizable monofunctional compound, difunctional compound, trifunctional or higher functional compound and a mixture thereof, preferably a monofunctional compound, a mixture of difunctional and trifunctional compounds or a mixture of two or more difunctional compounds.
Free radical polymerizable monofunctional Compound
The radical polymerizable monofunctional compound has a low viscosity, and examples of the photoreactive diluent include (meth) acrylate compounds, (meth) acryl compounds, vinyl derivatives, styrene compounds, acid anhydride compounds (maleic anhydride) containing an ethylenically unsaturated double bond, N-vinylpyrrolidone, and N-vinylformamide.
The following examples may be mentioned as preferred (meth) acrylate compounds:
(meth) acrylic acid C1-C18Alkyl esters, e.g. C (meth) acrylate1-C6Examples of the alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and 2-methacryloyloxyethoxy phthalate;
hydroxy-functional (meth) acrylates, e.g. hydroxy C (meth) acrylate1-C6Alkyl esters, examples being (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycidyl methacrylate, etc.;
(meth) acrylates having a cyclic skeleton such as isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, γ -butyrolactone (meth) acrylate, tricyclodecanol (meth) acrylate; and
alkoxy-modified (e.g. having 1 to 10, such as 2, 4, 6 or 8, preferably 1 to 5 EO and/or PO units) esters of (meth) acrylic acid with EO, PO and the like, for example, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate.
As the (meth) acryloyl group, there may be mentioned acryloylmorpholine and the like, 2-methacryloyloxyethoxysuccinate, N-dimethylacrylamide, N-diethylacrylamide, N-dipropylacrylamide and the like.
As the styrenic compound, chloromethyl styrene and α -methyl styrene can be mentioned.
As the acid anhydride having an ethylenically unsaturated double bond, maleic anhydride and the like can be mentioned.
Mention may be made, as ethylene derivatives, of vinyl esters, preferably C2-C6Vinyl esters of monocarboxylic acids, e.g. vinyl acetate, vinyl propionate, vinyl butyrate, valeric acidVinyl esters, vinyl caproates or mixtures thereof.
The radical polymerizable monofunctional compound may be present in an amount of 5 to 35% by weight, based on the total weight of the radical-cation hybrid photocurable composition of the present invention.
Free radical polymerizable bifunctional compound
The radical polymerizable bifunctional compound has higher reactivity than the monofunctional compound, and can improve the surface curability of the dry film resist. The viscosity of the composition is lower than that of a free radical polymerization trifunctional compound, and the composition can be well used as a diluent of a trifunctional and higher-functional compound by being combined with a monofunctional compound, so that the viscosity of the free radical-cation hybrid photocurable composition and the photosensitive dry film resist is reduced, and the reactivity is improved.
As radically polymerizable difunctional compounds, for example di (meth) acrylates of diols or triols having 2 to 12, such as 2, 4, 6, 8 or 10, carbon atoms, di (meth) acrylates of polyethylene or polypropylene glycols having a number average molecular weight of not more than 1,500, for example not more than 1,200, wherein these compounds are optionally EO or PO modified, such as with 5 to 15 EO and/or PO; as concrete examples, there may be mentioned 2-hydroxy-3-acryloxypropyl (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 2-methyl-1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 3-methyl-1, 5-pentanediol di (meth) acrylate, ethoxylated 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth), Polyethylene glycol #400 di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol #400 di (meth) acrylate, polypropylene glycol #700 di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol #200 di (meth) acrylate, polyethylene glycol #600 di (meth) acrylate, polyethylene glycol #1000 di (meth) acrylate, ethoxylated polypropylene glycol #700 di (meth) acrylate, polypropylene glycol #400 di (meth) acrylate, bisphenol A di (meth) acrylate (which may contain different alkoxy segments such as EO and PO), etc.), Hydrogenated bisphenol A type di (meth) acrylate (which may contain different alkoxy segments such as EO, PO, etc.), dicyclopentadiene, 2-bis (4- (methacryloxypolyethoxy) phenyl) propane (the average number of EO units is 5 to 15 per molecule), etc. 1 or 2 or more of them may be used.
Di (meth) acrylates of polyethylene glycol having a number average molecular weight of not more than 1,200 (e.g. not more than 800) and 2, 2-bis (4- (methacryloxypolyethoxy) phenyl) propane (with an average number of EO units of 5 to 15 per molecule) and mixtures thereof are preferred.
The radical polymerizable bifunctional compound may be 5 to 40% by weight based on the total weight of the radical-cation hybrid photocurable composition of the present invention.
As the 3-or more functional radical polymerizable compound, there may be mentioned a compound having three or more (meth) acrylate groups. Specific examples include: and polyfunctional acrylates represented by trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, epichlorohydrin-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetra (meth) acrylate, tetramethylolmethane tetraacrylate, ethylene oxide-modified phosphoric triacrylate, propylene oxide-modified phosphoric triacrylate, epichlorohydrin-modified glycerol triacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, or silsesquioxane-modified products thereof, or methacrylate monomers and caprolactone-modified triacryloyloxyethyl isocyanurate corresponding thereto.
The amount of the radical polymerizable trifunctional or higher functional compound may be 5 to 35 wt% based on the total weight of the radical-cation hybrid photocurable composition of the present invention.
In one embodiment of the present invention, the radical polymerizable compound is in the form of a resin (including an oligomer or a prepolymer). As the radical polymerizable resin, there can be mentioned epoxy (meth) acrylate resin, polyester-based (meth) acrylate, urethane (meth) acrylate, ethylenically unsaturated polyester, amino (meth) acrylate resin, photo-imageable alkali-soluble resin, and the like. According to the invention, it is advantageous to use epoxy (meth) acrylate resins, polyester (meth) acrylates, polyurethane (meth) acrylates or combinations thereof.
The epoxy (meth) acrylate resin is preferably bisphenol A epoxy (meth) acrylate, tripropylene glycol di (meth) acrylate diluted bisphenol A epoxy acrylate or a combination thereof, such as bisphenol A epoxy acrylate WSR-U125 from a tin-free resin plant, bisphenol A epoxy acrylate 621A-80 from Taiwan Changxing chemical company diluted with 20% tripropylene glycol diacrylate, modified bisphenol A epoxy acrylate 623-100 from Taiwan Changxing chemical company, and modified bisphenol A epoxy acrylate 6231A-80 from Taiwan Changxing chemical company diluted with 20% tripropylene glycol diacrylate.
The polyester (meth) acrylate is preferably a hyperbranched polyester acrylic resin having a high functionality, in particular a hyperbranched polyester acrylic resin having a functionality of 5 to 30, for example a hyperbranched polyester acrylate prepolymer having a functionality of 6 to 20. As such, for example, there may be mentioned hyperbranched polyester acrylate prepolymer 932-. Polyester-based (meth) acrylates mention may also be made of 20% ethoxylated trimethylolpropane triacrylate diluted polyester polyol acrylic resins.
The urethane (meth) acrylate is preferably an aliphatic urethane acrylate. As such, aliphatic urethane hexaacrylate 6145-100, 6161-100, 15% 1, 6-hexanediol diacrylate (HDDA) diluted aliphatic urethane diacrylate 611B-85, aliphatic urethane diacrylate 6141H-80; aliphatic urethane acrylate CN9013(9 functionality) from sartomer usa, aliphatic urethane acrylate CN966B85(2 functionality) diluted with 15% 1, 6-hexanediol diacrylate (HDDA) from sartomer usa, aliphatic urethane acrylate CN962(2 functionality).
According to the present invention, the amount of the radical polymerizable compound as the component (b1) may be 21 to 45% by weight based on the total weight of the radical-cation hybrid photocurable composition of the present invention.
Cationically polymerizable compound (b2)
According to the present invention, component (b2) is at least one cationically polymerizable compound selected from the group consisting of alkenyl ether-based compounds and/or ethylene oxide-based compounds and/or aziridine-based compounds and/or oxetane-based compounds, which may be in the form of monomers or resins (including oligomers or prepolymers).
According to the invention, the alkenyl ether compound may be C1-C6Alkenyl ether compounds such as vinyl ether, 1-propenyl ether, 1-butenyl ether, 1-pentenyl ether and the like, and vinyl ether compounds are preferred. The alkenyl ether compounds are, for example, alkenyl ethers starting from monohydric alcohols having 1 to 12, preferably 1 to 6, carbon atoms, dihydric alcohols having 2 to 12, preferably 2 to 8, carbon atoms, trihydric or higher alcohols having 3 to 12, preferably 3 to 6, carbon atoms, in particular C1-C6An alkenyl ether. As said alkenyl ether compounds, mention may also be made of polymers containing alkenyl ether, such as vinyl ether, functional groups. Mention may be made, as specific examples, of triethylene glycol divinyl ether, isobutyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, Butyl Vinyl Ether (BVE), hydroxyethyl vinyl ether, diethylene glycol divinyl ether (DEGDVE), triethylene glycol divinyl ether (TEGDVE), vinyl n-octyl ether, divinyl-1, 4-butanediol ether, 2-ethylhexyl vinyl ether, 1, 4-cyclohexyldimethanol divinyl ether, 4-hydroxybutyl vinyl ether (HBVE), triethylene glycol divinyl etherEther (DVE-3), glycerol carbonate vinyl ether, dodecyl vinyl ether, and the like. Further, there can be mentioned compounds having both vinyl ether and alkyl (meth) acrylate structures, and one or more of these compounds may be used simultaneously.
The alkenyl compounds also include carbamates containing 1 or more, e.g., 1 to 3, alkenyl ether structures. The urethane containing an alkenyl ether structure can be obtained by reacting an alkenyl ether having a hydroxyl group with an isocyanate compound (e.g., a polyisocyanate compound). Mention may be made, as examples, of bisvinyloxyalkylcarbamates and trifunctional vinyl ethers prepared from 1, 6-hexamethylene diisocyanate trimer and 4-hydroxyvinyl ether.
According to the present invention, the oxirane compound may be selected, for example, from glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, aliphatic epoxy compounds, alicyclic epoxy compounds, and the like. The oxirane compound may be in the form of a monomer or a resin (e.g., an oligomer or a prepolymer). There may also be mentioned compounds having both an ethylene oxide group and a radical polymerizable group (such as an acrylate group), such as epoxy (meth) acrylate resins. Glycidyl ether type epoxy compounds (particularly aliphatic glycidyl ether type epoxy compounds, bisphenol a type glycidyl ether type epoxy compounds) and aliphatic epoxy resins are preferable. Further, a compound having both an ethylene oxide group (e.g., a cycloaliphatic ethylene oxide group or a glycidyl ether group) and an alkyl (meth) acrylate structure is preferable.
As examples of these oxirane compounds, mention may be made of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate (ERL-4211), bis (3, 4-epoxycyclohexylmethyl) adipate (UVR-6128), trimethylolpropane glycidyl ether (TPEG), 1, 2-epoxy-4-vinylcyclohexane, methyl 3, 4-epoxycyclohexanecarboxylate, diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, bisphenol A diglycidyl ether (E-03 type), 3-oxiranyl 7-oxa-bis (E-03)Cyclo [4,1,0]Heptane, ethylene glycol diglycidyl ether, C12-C14Polyfunctional epoxy compounds such as alkyl glycidyl ethers, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polyether glycol glycidyl ethers, glycidyl methacrylate, trimethylol triglycidyl ether, 1, 4-butanediol diglycidyl ether, and oligomers or copolymers thereof, and also EPIKOTE Resin 862, EPIKOTE Resin 827, EPIKOTE Resin 869, EPIKOTE Resin 320, EPIKOTE Resin 816, EPIKOTE Resin 232, EPIKOTE Resin 144, and the like. These compounds may be used in one or more kinds.
According to the present invention, as the aziridine monomer, trimethylolpropane-tri- β -aziridinylpropionate, tetramethylolmethane-tri- β -aziridinylpropionate, or N, N-hexamethylene-1, 6-bis-1-aziridinecarboxamide, etc. may be mentioned.
As examples of the oxetane compound, according to the present invention, 3' - (oxybismethylene) bis (3-ethyl) oxetane (GR-OXT-03), 3-ethyl-3-oxetanemethanol, bis [ (3-methyl-3-oxetanylmethoxy) methyl ] ether, bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ether, 1, 4-bis [ (3-methyl-3-oxetanylmethoxy) methyl ] benzene, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, 3-methyl-3-oxetanyl) methyl acrylate, 3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, 3-methyl-3-vinylhydroxymethyloxetane, 3-methyl-3-ethylenehydroxypolyethoxylated methyloxetane, 1, 4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1, 6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 1, 3-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] propane Alkyl, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, 3-oxiranyl 7-oxabicyclo [4.1.0] heptane, and 3-ethyl-3-oxetanemethanol (GR-OXT-01), 3-ethyl-3-chloromethyloxetane (GR-OXT-02) produced by solid wetting technology, One or a combination of two or more of 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (GR-OXT-04), 3' - ((((propane-2, 2-diylbis (4, 1-phenylene)) bis (oxy)) bis (methylene)) bis (3-ethyloxetane) (GR-OXT-05), 3-ethyl-3- (phenylmethoxymethyl) oxetane (GR-OXT-06), oxetane methacrylate (GR-OXT-09), bis [ (3-ethyloxetan-3-yl) methyl ] benzene-1, 4-dicarboxylate (GR-OXT-11) and the like, and polyfunctional oxetane compounds such as oligomers or copolymers thereof, and etherates of oxetanol and hydroxyl group-containing resins such as novolak resins, poly (p-hydroxystyrene), Cardo-type bisphenols, calixarenes, and silsesquioxanes. In addition, compounds having both oxetane and alkyl (meth) acrylate structures can be exemplified.
According to the present invention, the amount of the cationically polymerizable compound as the component (b2) may be 9 to 15% by weight based on the total weight of the radical-cationic hybrid photocurable composition.
According to the present invention, the amount of the photopolymerizable compound therein as the component (b) may be 30 to 68% by weight, preferably 35 to 65% by weight, more preferably 40 to 60% by weight, based on the total weight of the curable composition.
According to a preferred embodiment of the present invention, wherein the weight ratio of component (b1) to component (b2) may be from 10:1 to 1:10, preferably from 4:1 to 6:5, more preferably from 3.5:1 to 1: 1.
Infrared absorbing photosensitizer (c)
In a preferred embodiment, the polymethine cyanine compound as component (c) is selected from polymethine cyanine compounds having the structure of formula (I):
Figure BDA0002685496620000241
Y+represented are bicyclic, tricyclic or higher heterocyclic rings having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members and carrying a positive charge,
y represents a bicyclic, tricyclic or higher heterocyclic ring having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members,
Y+and the heterocyclic ring in the definition of Y may carry 1 or more groups selected from halogen, CN, nitro, C1-C12Branched or unbranched alkyl, C1-C12Branched or unbranched alkoxy radical, C1-C12A substituent of a branched or unbranched alkylthio group or a phenylthio group, wherein said C1-C12Branched or unbranched alkyl, said C1-C12Branched or unbranched alkoxy radical, said C1-C12The alkyl groups in a branched or unbranched alkylthio group may be interrupted by 1 or more non-adjacent oxygen atoms;
preferably Y+and/Y is a structural unit shown as follows respectively:
indole salts/indoles
Figure BDA0002685496620000242
Phenyl [ e ]]Indole salts/phenyl [ e ]]Indoles
Figure BDA0002685496620000243
And/or phenyl [ c, d ]]Indole salts/phenyl [ c, d ]]An indole compound having a structure represented by formula (I),
Figure BDA0002685496620000244
wherein said indole salt/indole, phenyl [ e ]]Indole salts/phenyl [ e ]]Indole, and phenyl [ c, d ]]Indole salts/phenyl [ c, d ]]The indole may have 1 or more, preferably 1 or 2, substituents selected from halogen, CN, nitro and C on the benzene ring or naphthalene ring1-C12Branched or unbranched alkyl, C1-C12Branched or unbranchedBranched alkoxy radical, C1-C12A substituent of a branched or unbranched alkylthio group or a phenylthio group, wherein said C1-C12Branched or unbranched alkyl, said C1-C12Branched or unbranched alkoxy radical, said C1-C12The alkyl groups in a branched or unbranched alkylthio group may be interrupted by 1 or more non-adjacent oxygen atoms;
wherein R is1Is selected from C1-C12Branched or unbranched alkyl and C1-C12A branched or unbranched alkoxy group, wherein said C1-C12Branched or unbranched alkyl and C1-C12The branched or unbranched alkoxy groups may be interrupted by 1 or more non-adjacent oxygen atoms, e.g. - [ -CH2CHR-O-]nThe polyether is shown, wherein n is 1-6, R is H or CH3；
Wherein the ring carbon position shown by the arrow is a connecting site with the polymethine chain;
more preferably Y+and/Y is a structural unit shown as follows respectively:
Figure BDA0002685496620000251
and/or
Figure BDA0002685496620000252
Wherein R is1Is selected from C1-C12Branched or unbranched alkyl and C1-C12A branched or unbranched alkoxy group, wherein said C1-C12Branched or unbranched alkyl and C1-C12The branched or unbranched alkoxy groups may be interrupted by 1 or more non-adjacent oxygen atoms, e.g. - [ -CH2CHR-O-]nThe polyether is shown, wherein n is 1-6, R is H or CH3(ii) a And
R2，R3independently of one another, selected from H, halogen, CN, nitro, C1-C12Branched or unbranched alkyl, C1-C12Branched or unbranched alkoxy radical, C1-C12A branched or unbranched alkylthio group or a phenylthio group, wherein said C1-C12Branched or unbranched alkyl, said C1-C12Branched or unbranched alkoxy radical, said C1-C12The alkyl groups in a branched or unbranched alkylthio group may be interrupted by 1 or more non-adjacent oxygen atoms;
wherein the ring carbon position shown by the arrow is a connecting site with the polymethine chain;
n1，n2independently 0, 1 or 2; preferably 0 or 1, more preferably 1;
b and C are independently selected from H, C1-C12Alkyl groups or together with the carbon atoms linking them form a five-or six-membered ring;
a is selected from the structures shown as A-1 to A-13:
Figure BDA0002685496620000261
or C1-C12A branched or unbranched alkoxy group (A-13);
wherein
Denotes the attachment site to the structure of formula (I),
wherein "R2And R2The "radicals, which are identical or different, are each independently selected from hydrogen, halogen, C1-C6Branched or unbranched alkyl, C1-C6Branched or unbranched alkoxy radical, C1-C6A branched or unbranched alkylthio group or a phenylthio group,
preferably the group A is selected from the structures shown as A-4, A-5 or A-7 to A-13;
when the A group is a group A-1 or A-2, n3Is 0, when the A group is a group A3-A13, n3The number of the carbon atoms is1,
and X-Represents a counter ion.
In one embodiment, R1Is selected from C1-C6Branched or unbranched alkyl and C1-C6A branched or unbranched alkoxy group, wherein said C1-C6Branched or unbranched alkyl and C1-C6The branched or unbranched alkoxy groups may be separated by 1 or 2 non-adjacent oxygen atoms.
In one embodiment, R2Selected from H, halogen, nitro, C1-C6Branched or unbranched alkyl and C1-C6A branched or unbranched alkoxy group, wherein said C1-C6Branched or unbranched alkyl, said C1-C6The branched or unbranched alkoxy groups may be interrupted by 1 or 2 non-adjacent oxygen atoms, more preferably R2 is selected from H, halogen, nitro and C1-C6A branched or unbranched alkoxy group, wherein said C1-C6The branched or unbranched alkoxy groups may be separated by 1 non-adjacent oxygen atom.
In one embodiment, R3Selected from H, C1-C6Branched or unbranched alkyl and C1-C6A branched or unbranched alkoxy group, wherein said C1-C6Branched or unbranched alkyl and said C1-C6The branched or unbranched alkoxy groups may be interrupted by 1 or 2 non-adjacent oxygen atoms, more preferably R3Selected from H and C1-C6Branched or unbranched alkoxy groups.
In one embodiment, B and C are independently H or together with the carbon atom connecting them form a five or six membered ring. In a preferred embodiment, the five-or six-membered ring carries only one carbon-carbon unsaturated double bond.
In one embodiment, "R" is2And R2The "radicals are identical or different and are each independently selected from hydrogen or C1-C6Branched or unbranched alkyl, preferably hydrogen or C1-C6Branched or unbranched alkyl, more preferably hydrogen.
In one embodiment, X-Represents a counterion selected from one of the following groups: BF (BF) generator4 -、PF6 -、SbF6 -、AsF6 -、[PF3(C2F5)3]-、[Al(OC(CF3)3)4]-、[B(PhF5)4]-、[B(Ph(CF3)2)4]-、[((CF3)2SO2)2N]-、[((CF3)2SO2)3C]-、Cl-、Br-、F-、[Al(O-t-C4F9)4]-、[Al(O-(i-C3F7)CH3)4]-、[C(O-SO2CF3)3]-、[n-C12H25-TsO]-Or [ NTf2]-，
Among them, BF is preferred4 -、PF6 -、SbF6 -、AsF6 -、[PF3(C2F5)3]-、[Al(OC(CF3)3)4]-、[B(PhF5)4]-、[B(Ph(CF3)2)4]-、[((CF3)2SO2)2N]-、[((CF3)2SO2)3C]-、[Al(O-t-C4F9)4]-、[Al(O-(i-C3F7)CH3)4]-Or [ NTf2]-，
More preferably [ PF3(C2F5)3]-、[Al(OC(CF3)3)4]-、[B(PhF5)4]-、[B(Ph(CF3)2)4]-、[((CF3)2SO2)2N]-、[((CF3)2SO2)3C]-、[Al(O-t-C4F9)4]-Or [ Al (O- (i-C) ]3F7)CH3)4]-，
Most preferably [ Al (O-t-C)4F9)4]-Or [ PF ]3(C2F5)3]-。
In the compounds of formula (I), when the A group is A-1 or A-2 and Y is+And R in Y1Is C1-C12Branched or unbranched alkyl or C1-C12When the alkoxy group is branched or unbranched, the moiety of formula (I) is entirely uncharged, X is absent, and when R is2When the group is a group A-3 to A-13, the moiety of formula (I-1) is overall positively charged:
Figure BDA0002685496620000271
wherein Y is+、Y、A、B、C、n1、n2As defined above.
In the compounds of formula (I), when A is selected from A1 or A2, X is absent, i.e. n3Is 0.
When A is selected from A-3 to A-13, the moiety of formula (I-1) bears a positive charge on the whole, X-As defined above, n3Is 1.
According to the invention, the polymethine cyanine compound of formula (I) comprises a moiety of formula (I-1) and, if present, a counterion X-。
Figure BDA0002685496620000281
In the polymethine cyanine compound of the formula (I) of the present invention and the structural moiety of the formula (I-1) contained therein, n1、n2Independently is 0, 1 or 2, n3Independently 0 or 1. B. C independently represents H, C1-C12Alkyl groups either together with the carbon atoms connecting them form a five-or six-membered ring. When n is1、n2Are all 0, the compound of formula (I) is a trimethyl compound, when n is1Is 0, n2Is1, the compound of formula (I) is a pentamethine compound, when n is1，n2When 1, the compound of formula (I) is a heptamethine compound, when n1，n2Is1, and B, C and are linkedWhen the carbon atoms thereof form a five-membered ring or a six-membered ring together, the compound of formula (I) is a heptamethine compound containing the five-membered ring or the six-membered ring at the intermediate position. In a preferred embodiment of the invention, the compound of formula (I) is a trimethyl compound, wherein n is1、n2Are all 0. In another preferred embodiment of the invention, the compound of formula (I) is a pentamethine compound, wherein n is1Is 0, n2Is 1. In a further preferred embodiment of the invention, the compound of formula (I) is B, C heptamethine compounds forming a five-membered ring together with the carbon atom to which they are attached, wherein n1，n2Is 1.
In the polymethine cyanine compound of the formula (I) of the present invention, (X)-)n3If present, it represents a counterion to the structural moiety of formula (I-1), which, depending on the type of A group, is either not present at all or is anionic.
When the structural moiety of the formula (I-1) is entirely uncharged, n3Is 0, i.e. the compound of formula (I) is free of any counter ion.
In one embodiment of the present invention, in the polymethine cyanine compound of the formula (I) of the present invention and the structural moiety of the formula (I-1) comprised therein, Y is+And Y each comprise a nitrogen-containing heterocycle, Y+The difference from the structure of Y is that Y+The nitrogen containing ring atoms have a positive charge and Y does not exhibit any charge.
Advantageously, the A group is A-4, A-5 or A-7 to A-13, more preferably A-4, A-5, A-7, A-8, A-11, A-12 or A-13.
Preferred cyanine dyes can be classified into four groups: the following S-1, S-2, S-3 and S-4:
Figure BDA0002685496620000291
a, R therein1、R2，R3M and X-As defined above.
In an advantageous embodiment of the present invention, the polymethine cyanine compound as component (c) is one or more selected from the group consisting of compounds S1-S70 below. These compounds are sometimes also referred to as infrared absorbing photosensitizers S1-S70.
Figure BDA0002685496620000292
Figure BDA0002685496620000301
Figure BDA0002685496620000311
The compounds of formula (I) of the present invention are known per se, for example, from jp 2010-209191 a, or can be prepared by conventional methods in the art.
According to the present invention, the amount of the infrared absorbing photosensitizer as component (c) may be 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the total weight of the radical-cation hybrid photocurable composition.
Photopolymerization initiator (d)
According to an embodiment of the present invention, the photopolymerization initiator as the component (d) may be a photopolymerization initiator capable of generating radicals and cations in the presence of the component (c). Preferably, the photopolymerization initiator as the component (d) is selected from the group consisting of a photopolymerization initiator of an iodonium salt compound, a sulfonium salt compound, a triazine compound and an oxime ester compound, and is preferably an iodonium salt compound.
As the iodonium salt compound suitable for the present invention, an iodonium salt compound of the formula (II) is preferably included
Figure BDA0002685496620000312
Wherein R is1’-R6' may be the same or different and are independently selected from H, halogen, nitro, C1-C20Branched or unbranched alkyl, C1-C20Branched or unbranched alkoxy and C1-C20A branched or unbranched alkylthio group, and X'-As above for X in the compound of formula (I)-As defined. In one embodiment, R1’-R6' may be the same or different and are independently selected from H, C1-C12Branched or unbranched alkyl, C1-C12Branched or unbranched alkoxy and C1-C12Branched or unbranched alkylthio. In a preferred embodiment, X in the compound of formula (I)-And X 'in the compound of formula (II)'-Are the same.
The iodonium salts of formula (II) of the present invention are known per se and can be prepared by conventional methods in the art.
In an advantageous embodiment of the invention, the iodonium salt initiator of formula (II) IS one or more selected from the following compounds IS1-IS 40:
Figure BDA0002685496620000313
Figure BDA0002685496620000321
wherein the amount of the photopolymerization initiator as component (d) may be 1 to 10% by weight, preferably 2 to 8% by weight, more preferably 2.5 to 5% by weight, based on the total weight of the radical-cationic hybrid photocurable composition.
In the initiator system used according to the invention, the weight ratio of the infrared-absorbing photosensitizer as component (c) to the photopolymerization initiator as component (d) may be from 10:1 to 1:10, preferably from 8:1 to 1:8, more preferably from 5:1 to 1: 5.
The present invention also relates to a coating liquid comprising the radical-cation hybrid photocurable composition of the present invention and at least one organic solvent. Examples of the organic solvent include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; aprotic polar solvents such as N, N-dimethylformamide and the like. These organic solvents may be used alone or in combination of two or more. The total amount of the organic solvent in the coating liquid may be appropriately selected depending on the purpose, etc., and is, for example, 10 to 40% by weight, preferably 15 to 30% by weight, based on the radical-cation hybrid photocurable composition.
The coating liquid is applied to the surface of a support and dried to form a photosensitive layer as a coating film of the radical-cation hybrid photocurable composition, and a protective layer is coated on the surface of the photosensitive layer to obtain a photosensitive dry film resist. As the support, a polymer film having heat resistance and solvent resistance, such as polyester, e.g., polyethylene terephthalate, polypropylene, and polyethylene, can be used. Examples of the protective layer include polymer films such as polyethylene and polypropylene. The thickness of the photosensitive layer to be formed is not particularly limited and may be appropriately selected depending on the use. For example, it may be 1 to 100 μm in thickness after drying.
According to one aspect of the present invention, there is provided a photosensitive dry film resist comprising a support, a photosensitive layer provided on the support, and a protective layer provided on the photosensitive layer, the photosensitive layer comprising the radical-cation hybrid photocurable composition of the present invention.
The photosensitive dry film resist may contain other components such as an amine compound, a plasticizer, a pigment, a filler, a defoaming agent, a flame retardant, a stabilizer, an adhesion imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an image forming agent, and a thermal crosslinking agent, if necessary. These other components may be used alone or in combination of two or more.
In the case where the above-mentioned dry film photosensitive resist contains these other components, the amount thereof is usually 0.01 to 20 parts by weight relative to 100 parts by weight of the nonvolatile components of the dry film photosensitive resist.
The present invention also relates to the use of the radical-cation hybrid photocurable composition of the invention for the preparation of a dry film photosensitive resist.
Examples
The present invention will be specifically described with reference to the following examples, but the present invention is not limited to these examples. In the following, unless otherwise specified, "part" means part by weight.
(A) Alkali soluble polymer
Synthetic examples
Preparation example 1: polymer A1
In a 500mL flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen inlet tube, 100g of methyl ethyl ketone was added as a solvent, then 30g of polymerizable monomers methacrylic acid, 30g of styrene and 40g of butyl methacrylate were added as shown in table 1, 0.8g of azobisisobutyronitrile as an initiator was slowly added under stirring at 80 ℃ under a nitrogen atmosphere, and the mixture was kept warm for 10 hours while stirring at 80 ℃ and cooled to obtain an alkali-soluble polymer solution as the component (a) having a nonvolatile component concentration (solid component concentration) of 50% by weight.
Preparation examples 2 to 4: polymers A2, A3 and A4
In the same manner as in the case of obtaining the alkali-soluble polymer a1 except for following the weight ratios shown in table 1 and using the materials shown in table 1 as polymerizable monomers, alkali-soluble polymers a2, A3 and a4 were obtained.
The polymer obtained in the preparation example was subjected to physical property measurement by the following method, and the results thereof are shown in table 1.
(1) Acid value measurement
1g of the alkali-soluble polymer was dissolved in 50ml of a mixed solvent (methanol 20%, acetone 80%), 2 drops of 1% phenolphthalein indicator were added dropwise, and then titration was performed with 0.1mol/L KOH standard solution, thereby determining the acid value.
(2) Molecular weight and PDI determination
The weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene were measured by gel permeation chromatography (Waters: Waters 707). The alkali-soluble polymer prepared in the above preparation example was dissolved in tetrahydrofuran to a concentration of 4000ppm, and then 100. mu.l was injected into GPC. The mobile phase of GPC was flowed in at a flow rate of 1.0ml/min using tetrahydrofuran, and analysis was performed at 35 ℃. Four of Waters HR-05, 1,2 and 4E were connected in series as a chromatography column. The assay was performed using an RI and PAD Detector Detector at 35 ℃. At this time, PDI (polydispersity index) was calculated by dividing the measured weight average molecular weight by the number average molecular weight.
TABLE 1
Figure BDA0002685496620000351
Details of each component shown in tables 2 to 9 below are as follows.
(B) Photopolymerizable compound
B1: 2, 2-bis (4- (methacryloxypolyethoxy) phenyl) propane (EO group: 10mol (average)) (New Zhongcun chemical industry Co., Ltd. "BPE-500")
B2: polyethylene glycol #400 dimethacrylate (9G, product of Xinzhongcun chemical industry Co., Ltd.)
B3: 3,3' - (oxybis-methylene) bis (3-ethyl) oxetane (OXT-3, Hubei Gurun science and technology Co., Ltd.)
(C) Infrared absorbing photosensitizers
The infrared absorbing photosensitizer as component (C) is one or more selected from the compounds S1-S70, numbered supra. These compounds are known from japanese patent application laid-open No. 2010-209191, or can be prepared by a conventional method in the art.
(D) Photopolymerization initiator
(D) The component comprises an iodonium salt compound of formula (II) above, which as photopolymerization initiator may be selected from one or more of the compounds IS1-IS40, numbered supra. These compounds can be prepared by conventional methods in the art.
In comparative examples, the photopolymerization initiator included EMK (tetraethyl mikrone, available from guzhi science co., ltd., northhubei), HABI-101(2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbisimidazol [2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer, available from changzhou tough new material ltd.), NPG (N-phenylglycine, available from changzhou tough new material ltd.).
Other components:
LCV: colorless crystal violet, available from Changzhou powerful new materials, Inc.
Preparation of photosensitive dry film resist
The alkali-soluble polymers, radical polymerizable compounds, cation polymerizable compounds, infrared absorbing photosensitizers, and photopolymerization initiators of preparation examples 1 to 4 were added to a solvent according to the following tables 2 to 9, stirred at room temperature for 4 hours, and impurities were removed with a 200 mesh filter to obtain photocurable composition solutions, i.e., coating solutions, of examples 1 to 77 and comparative examples 1 to 3. In addition, examples 1-77 used an infrared laser scanning exposure device with a wavelength of 808nm for evaluation of dry film properties. In contrast, comparative examples 1 to 3 each employed an ultraviolet exposure apparatus having a wavelength of 365nm, and comparative example 1 was a photocurable composition solution of an ultraviolet radical polymerization system, the photopolymerizable compound being only a radical polymerizable monomer; comparative example 2 is a photocurable composition solution of an ultraviolet cationic polymerization system, and the photopolymerizable compound is only a cationic polymerization monomer; comparative example 3 is a photocurable composition solution of an ultraviolet radical-cation hybrid system, and photopolymerizable compounds are radical polymerizable monomers and cation polymerizable monomers. In addition, the amounts of the (a) components shown in tables 2 to 9 are the weights of the nonvolatile components (solid component amounts).
The photocurable composition solutions of examples 1-77 and comparative examples 1-3 obtained above were uniformly coated on a PET support film layer having a thickness of 20 μm, dried with a hot air convection dryer at 100 ℃ for 5min, and then heat-laminated with a PE film having a thickness of 18 μm using a rubber roller, thereby obtaining a photosensitive dry resist film. The thickness of the photocurable composition layer after drying was 40 μm. The photosensitive dry film resist compositions are shown in tables 2 to 9.
TABLE 2
Figure BDA0002685496620000361
Figure BDA0002685496620000371
TABLE 3
Figure BDA0002685496620000372
Figure BDA0002685496620000381
TABLE 4
Figure BDA0002685496620000382
Figure BDA0002685496620000391
TABLE 5
Figure BDA0002685496620000392
Figure BDA0002685496620000401
TABLE 6
Figure BDA0002685496620000402
Figure BDA0002685496620000411
TABLE 7
Figure BDA0002685496620000412
Figure BDA0002685496620000421
TABLE 8
Figure BDA0002685496620000422
Figure BDA0002685496620000431
TABLE 9
Figure BDA0002685496620000432
Figure BDA0002685496620000441
The following process was performed on a photosensitive dry film resist obtained using the photocurable composition obtained according to the above composition.
Lamination of
By hot pressing, the substrate was preheated at 120 deg.C, laminated at 110 deg.C, and pressed at 4.0kgf/cm2And a test substrate was obtained by laminating the photocurable composition layer on the copper surface of the substrate to be treated using a heating roll while peeling off the protective PE film at a roll speed of 1.5 m/min.
Evaluation of sensitivity
After 41 grids of stepped exposure scales (exposure scale density range 0.00-2.00, density step 0.05, exposure table plate (rectangle) size 20mm × 187mm, and grid (rectangle) size 3mm × 12mm) were placed on the photocurable composition layer of the above test substrate, examples 1-77 were exposed by using an infrared laser scanning exposure apparatus having a wavelength of 808nm, while comparative examples 1-3 were exposed by using an ultraviolet exposure apparatus having a wavelength of 365nm at three different exposure energies. Is connected withAfter the PET film was peeled off, it was developed with a 1.0% sodium carbonate aqueous solution in parts by weight at 30 ℃ to remove the unexposed portion, and the number of residual squares of the exposure scale of the photocurable film formed on the copper-clad substrate was measured by observation to evaluate the sensitivity of the photocurable composition. The sensitivity was determined by the exposure energy (unit: mJ/cm) of 20 residual steps2) In this case, the lower the value, the better the sensitivity. The results are set forth in Table 10.
Evaluation of resolution
The photocurable composition layer of the laminated substrate was exposed to light using a drawing pattern having a line width (L)/space (S) (hereinafter, referred to as "L/S") of 10/10 to 60/60 (unit: μm) and exposure energy at which the number of remaining cells was 20 after development at an exposure scale of 41 cells on the photocurable composition layer of the laminated test substrate (examples 1 to 77 used an infrared laser scanning exposure apparatus having a wavelength of 808nm, and comparative examples 1 to 3 used an ultraviolet exposure apparatus having a wavelength of 365 nm). After the development treatment was performed under the same conditions as the evaluation of the sensitivity, the resist pattern was observed using an optical microscope, and the minimum value of the interval width between line widths generated by no meandering or chipping of lines was defined as the resolution. Among them, the smaller the numerical value, the better the analysis, and the results are shown in table 10.
Evaluation of adhesion
The photocurable composition layer of the laminated test substrate was exposed with exposure energy of 20 remaining cells after development with an exposure scale of 41 cells using drawing patterns of equal Line pitch and different Line widths with Line/Space of n/400 μm (n ranges from 5 to 51, and is increased by 3 each time) (examples 1 to 77 used an infrared laser scanning exposure apparatus having a wavelength of 808nm, and comparative examples 1 to 3 used an ultraviolet exposure apparatus having a wavelength of 365 nm). After the development treatment was performed under the same conditions as the evaluation of the sensitivity, the resist pattern was observed with an optical microscope, and the adhesion (μm) was evaluated by the minimum line width value which remained without peeling and wrinkling. A smaller value indicates better adhesion. The results are set forth in Table 10.
Evaluation of resist shape
On the photocurable composition layer of the test substrates laminated as described above, exposure was carried out with an exposure amount of 20 residual steps after development of a Hitachi 41-grid exposure scale using a drawing pattern having a line width (L)/space (S) (hereinafter, referred to as "L/S") of 5/5 to 60/60 (unit: μm) (examples 1 to 77 used an infrared laser scanning exposure apparatus having a wavelength of 808nm, and comparative examples 1 to 3 used an ultraviolet exposure apparatus having a wavelength of 365 nm). After the development treatment was performed under the same conditions as the evaluation of the sensitivity, the appearance of the resist pattern after the development was observed by using a scanning electron microscope S8100 of hitachi, japan. It is very important that the resist shape is excellent. Since a short circuit or an open circuit may occur in a circuit formed by a subsequent etching treatment or plating treatment if the sectional shape of the resist is a trapezoid or an inverted trapezoid or the bottom of the resist is smeared, it is preferable that the sectional shape of the resist pattern after development is a rectangular shape without the bottom smear. The case where bottom smear was observed in the resist pattern was referred to as "bottom smear", and the case where development residue was observed was referred to as "development residue". Here, "bottom tailing" means that, in the case of observing the sectional shape of the resist pattern, the developed resist pattern formed on the surface of the substrate copper foil is not rectangular but is tailing at the bottom of the gap portion (unexposed portion). The term "development residue" means that, when the cross-sectional shape of the resist pattern is observed, the developed resist pattern is not rectangular but has a pronounced bottom smear, and the development residue remains in the gap portion and fills the lines. The results are set forth in Table 10.
Evaluation of peeling Properties
On the photocurable composition layer of the test substrates stacked as described above, exposure was carried out with an exposure amount of 20 frames of the residual number after development with a Hitachi 41-frame exposure scale using a drawing pattern of 60mm × 45mm (in examples 1 to 77, an infrared laser scanning exposure apparatus having a wavelength of 808nm was used, and in comparative examples 1 to 3, an ultraviolet exposure apparatus having a wavelength of 365nm was used). After the development treatment was performed under the same conditions as those for the evaluation of the sensitivity, the resultant was immersed in a 3% aqueous solution of sodium hydroxide (stripping solution) in parts by weight at 50 ℃. The peeling characteristics were evaluated by the time (peeling time) from the start of stirring until the cured film was completely peeled off and removed from the substrate. For the evaluation of the peeling property, the shorter the peeling time, the better. The results are set forth in Table 10.
Watch 10
Figure BDA0002685496620000471
Figure BDA0002685496620000481
Figure BDA0002685496620000491
Figure BDA0002685496620000501
And (4) conclusion: from the evaluation results in table 10 above, it is clear that the photocurable compositions of examples 1-77 are excellent in all of sensitivity, resolution, adhesion, resist shape and peeling characteristics after curing. On the other hand, in comparative example 1 in which only the radical polymerization system was used for the photocurable composition and comparative example 2 in which only the cationic polymerization system was used for the photocurable composition, when both dry film properties were evaluated, the sensitivity, resolution, adhesion and resist shape were inferior to those of the examples after replacing the exposure system with the infrared exposure apparatus. On the other hand, as is clear from table 10, in comparative example 3 in which the radical-cation hybrid system was used as the photocurable composition, and in the evaluation of the dry film properties, the exposure system was changed from the infrared exposure apparatus to the ultraviolet exposure apparatus, and the sensitivity, resolution, adhesion, and resist shape were inferior to those of the examples. The photosensitive film obtained by using the infrared light sensitive free radical-cation hybrid system photo-curing composition has the characteristics of higher sensitivity, finer imaging, steeper side wall and the like compared with a single free radical polymerization system or cation polymerization system.

Claims (30)

1. A radical-cation hybrid photocurable composition comprising the following components:
(a) at least one alkali-soluble polymer, at least one polymer,
(b) at least one kind of a photopolymerizable compound which,
(c) at least one infrared absorbing photosensitizer, and
(d) at least one kind of photopolymerization initiator,
wherein the photopolymerizable compound as the component (b) contains (b1) at least one radical polymerizable compound and (b2) at least one cation polymerizable compound selected from the group consisting of alkenyl ether compounds and/or ethylene oxide compounds and/or aziridine compounds and/or oxetane compounds, and the infrared absorbing photosensitizer as the component (c) contains at least one polymethine cyanine compound.
2. The radical-cation hybrid photocurable composition according to claim 1, wherein the alkali-soluble polymer is an alkali-soluble polymer containing a structural unit derived from (meth) acrylic acid and a structural unit derived from a polymerizable compound other than (meth) acrylic acid.
3. The radical-cation hybrid photocurable composition according to claim 2, wherein the other polymerizable compound is selected from the group consisting of styrene, α -methylstyrene, (meth) acrylic acid C1-C10Alkyl esters, (meth) acrylic acid C3-C8Cycloalkyl esters, hydroxy C (meth) acrylates1-C6Alkyl esters, benzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, and (meth) acrylic acid(meth) acrylates such as acid dicyclopentenyloxyethyl ester, dicyclopentenyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, adamantyloxyethyl (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, and adamantyloxypropyloxyethyl (meth) acrylate; (meth) acrylic acid derivatives such as α -bromoacrylic acid, α -chloroacrylic acid, β -furyl (meth) acrylic acid, and β -styryl (meth) acrylic acid; a polymerizable styrene derivative substituted on the aromatic ring; acrylamides such as diacetone acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; maleic acid; maleic anhydride; maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; unsaturated carboxylic acid derivatives such as fumaric acid, cinnamic acid, α -cyanocinnamic acid, itaconic acid, crotonic acid, and propanoic acid; or a combination thereof, preferably styrene, (meth) acrylic acid C1-C6Alkyl esters, benzyl (meth) acrylate, or combinations thereof, more preferably styrene, methyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, or combinations thereof.
4. The radical-cation hybrid photocurable composition according to claim 2 or 3, wherein the amount of the structural unit derived from (meth) acrylic acid is 10 to 40% by weight, preferably 20 to 35% by weight, more preferably 25 to 32% by weight, based on the weight of the alkali-soluble polymer.
5. The radical-cationic hybrid photocurable composition according to any one of claims 2 to 4, wherein the amount of the structural units derived from other polymerizable compounds is 60 to 90% by weight, preferably 65 to 80% by weight, more preferably 68 to 75% by weight, based on the weight of the alkali-soluble polymer.
6. The radical-cation hybrid photocurable composition according to any one of claims 1 to 5, wherein the acid value of the alkali-soluble polymer is from 90 to 250mg KOH/g, preferably 130 to 230mg KOH/g, more preferably 150 to 200mg KOH/g.
7. The radical-cation hybrid photocurable composition according to any one of claims 1 to 6, wherein the weight average molecular weight (Mw) of the alkali-soluble polymer, as determined by Gel Permeation Chromatography (GPC) (converted by using a standard curve of standard polystyrene), is 10,000-600,000, preferably 20,000-300,000, more preferably 35,000-80,000.
8. The radical-cation hybrid photocurable composition according to any one of claims 1 to 7, wherein the polydispersity index (weight average molecular weight/number average molecular weight) of the alkali-soluble polymer is less than or equal to 6.0, preferably less than or equal to 4.0, more preferably from 1.5 to 3.0.
9. The radical-cationic hybrid photocurable composition according to any one of claims 1 to 8, wherein the amount of the alkali-soluble polymer is from 30 to 68% by weight, preferably from 35 to 65% by weight, more preferably from 40 to 60% by weight, based on the total weight of the radical-cationic hybrid photocurable composition.
10. The radical-cation hybrid photocurable composition according to any one of claims 1 to 9, wherein the radical polymerizable compound as component (b1) is an ethylenically unsaturated group-containing radical polymerizable compound, preferably a monofunctional compound, a difunctional compound, a trifunctional or higher functional compound and mixtures thereof.
11. The radical-cation hybrid photocurable composition according to any one of claims 1 to 10, wherein the radical polymerizable compound as the component (b1) is selected from at least one of radical polymerizable resins, 2-functional or more radical polymerizable monomers, and monofunctional radical polymerizable monomers.
12. The radical-cation hybrid photocurable composition according to any one of claims 1 to 11, wherein the radical polymerizable compound as component (b1) is selected from the group consisting of (meth) acrylate compounds, (meth) acryl compounds, vinyl derivatives, styrene compounds, anhydride compounds containing an ethylenically unsaturated double bond, N-vinylpyrrolidone, N-vinylformamide and mixtures thereof.
13. The radical-cationic hybrid photocurable composition according to any one of claims 1 to 12, wherein the amount of the photopolymerizable compound as component (b) is from 30 to 60% by weight, preferably from 35 to 55% by weight, more preferably from 40 to 50% by weight, based on the total weight of the radical-cationic hybrid photocurable composition.
14. The radical-cationic hybrid photocurable composition according to any one of claims 1 to 13, wherein the weight ratio of component (b1) to component (b2) is from 10:1 to 1:10, preferably from 4:1 to 6:5, more preferably from 3.5:1 to 1: 1.
15. The radical-cation hybrid photocurable composition according to any one of claims 1 to 14, wherein the cationically polymerizable compound as component (b2) is selected from the group consisting of alkenyl ether compounds and/or oxetane compounds, preferably oxetane compounds.
16. The radical-cation hybrid photocurable composition according to any one of claims 1 to 15, wherein the polymethine cyanine compound as component (c) has an absorption maximum in the range of 780nm to 2,000 nm.
17. The radical-cation hybrid photocurable composition according to any one of claims 1 to 16, wherein the polymethine cyanine compound as component (c) has a structure represented by formula (I):
Figure FDA0002685496610000031
wherein
Y+Represented are bicyclic, tricyclic or higher heterocyclic rings having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members and carrying a positive charge,
y represents a bicyclic, tricyclic or higher heterocyclic ring having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members,
Y+and said heterocycle in the definition of Y may carry 1 or more substituents selected from halogen, CN, nitro, C1-C12Branched or unbranched alkyl, C1-C12Branched or unbranched alkoxy radical, C1-C12A substituent of a branched or unbranched alkylthio group or a phenylthio group, wherein said C1-C12Branched or unbranched alkyl, said C1-C12Branched or unbranched alkoxy radical, said C1-C12The alkyl groups in a branched or unbranched alkylthio group may be interrupted by 1 or more non-adjacent oxygen atoms;
preferably Y+and/Y is a structural unit shown as follows respectively:
indole salts/indoles
Figure FDA0002685496610000041
Phenyl [ e ]]Indole salts/phenyl [ e ]]Indoles
Figure FDA0002685496610000042
And/or phenyl [ c, d ]]Indole salts/phenyl [ c, d ]]An indole compound having a structure represented by formula (I),
Figure FDA0002685496610000043
wherein said indole salt/indole, phenyl [ e ]]Indole salts/phenyl [ e ]]Indole, and phenyl [ c, d ]]Indole salts/phenyl [ c, d ]]The indole may have 1 or more, preferably 1 or 2, substituents selected from halogen, CN, nitro and C on the benzene ring or naphthalene ring1-C12Branched or unbranched alkyl, C1-C12Branched or unbranched alkoxy radical, C1-C12A substituent of a branched or unbranched alkylthio group or a phenylthio group, wherein said C1-C12Branched or unbranched alkyl, said C1-C12Branched or unbranched alkoxy radical, said C1-C12The alkyl groups in a branched or unbranched alkylthio group may be interrupted by 1 or more non-adjacent oxygen atoms;
wherein R is1Is selected from C1-C12Branched or unbranched alkyl and C1-C12A branched or unbranched alkoxy group, wherein said C1-C12Branched or unbranched alkyl and C1-C12The branched or unbranched alkoxy groups may be interrupted by 1 or more non-adjacent oxygen atoms, e.g. - [ -CH2CHR-O-]nThe polyether is shown, wherein n is 1-6, R is H or CH3；
Wherein the ring carbon position shown by the arrow is a connecting site with the polymethine chain;
more preferably Y+and/Y is a structural unit shown as follows respectively:
Figure FDA0002685496610000051
and/or
Figure FDA0002685496610000052
Wherein R is1Is selected from C1-C12Branched or unbranched alkyl and C1-C12A branched or unbranched alkoxy group, wherein said C1-C12Branched or unbranched alkyl and C1-C12The branched or unbranched alkoxy groups may be interrupted by 1 or more non-adjacent oxygen atoms, e.g. - [ -CH2CHR-O-]nThe polyether is shown, wherein n is 1-6, R is H or CH3(ii) a And
R2，R3independently of one another, selected from H, halogen, CN, nitro, C1-C12Branched or unbranched alkyl, C1-C12Branched or unbranched alkoxy radical, C1-C12A branched or unbranched alkylthio group or a phenylthio group, wherein said C1-C12Branched or unbranched alkyl, said C1-C12Branched or unbranched alkoxy radical, said C1-C12The alkyl groups in a branched or unbranched alkylthio group may be interrupted by 1 or more non-adjacent oxygen atoms;
wherein the ring carbon position shown by the arrow is a connecting site with the polymethine chain;
n1，n2independently 0, 1 or 2; preferably 0 or 1, more preferably 1;
b and C are independently selected from H, C1-C12Alkyl groups or together with the carbon atoms linking them form a five-or six-membered ring;
a is selected from the structures shown as A-1 to A-13:
Figure FDA0002685496610000053
or C1-C12A branched or unbranched alkoxy group (A-13);
wherein
It represents the site of attachment to the structure of formula (I),
wherein "R2And R2The "radicals, which are identical or different, are each independently selected from hydrogen, halogen, C1-C6Branched or unbranched alkyl, C1-C6Branched or unbranched alkoxy radical, C1-C6A branched or unbranched alkylthio group or a phenylthio group,
preferably the group A is selected from the structures shown as A-4, A-5 or A-7 to A-13;
when the A group is a group A-1 or A-2, n3Is 0, when the A group is a group A3-A13, n3The number of the carbon atoms is1,
and X-Represents a counter ion.
18. The radical-cation hybrid photocurable composition according to claim 17, wherein the compound of formula (I) satisfies one or more of the following conditions:
R1is selected from C1-C6Branched or unbranched alkyl and C1-C6A branched or unbranched alkoxy group, wherein said C1-C6Branched or unbranched alkyl and C1-C6The branched or unbranched alkoxy groups may be separated by 1 or 2 non-adjacent oxygen atoms;
R2selected from H, halogen, nitro, C1-C6Branched or unbranched alkyl and C1-C6A branched or unbranched alkoxy group, wherein said C1-C6Branched or unbranched alkyl, said C1-C6The branched or unbranched alkoxy groups may be separated by 1 or 2 non-adjacent oxygen atoms;
R3selected from H, C1-C6Branched or unbranched alkyl and C1-C6A branched or unbranched alkoxy group, wherein said C1-C6Branched or unbranched alkyl and said C1-C6The branched or unbranched alkoxy groups may be separated by 1 or 2 non-adjacent oxygen atoms.
19. The radical-cation hybrid photocurable composition according to claim 17 or 18, wherein X is-Represents the following counterions: BF (BF) generator4 -、PF6 -、SbF6 -、AsF6 -、[PF3(C2F5)3]-、[Al(OC(CF3)3)4]-、[B(PhF5)4]-、[B(Ph(CF3)2)4]-、[((CF3)2SO2)2N]-、[((CF3)2SO2)3C]-、Cl-、Br-、F-、[Al(O-t-C4F9)4]-、[Al(O-(i-C3F7)CH3)4]-、[C(O-SO2CF3)3]-、[n-C12H25-TsO]-Or [ NTf2]-Among them, BF is preferred4 -、PF6 -、SbF6 -、AsF6 -、[PF3(C2F5)3]-、[Al(OC(CF3)3)4]-、[B(PhF5)4]-、[B(Ph(CF3)2)4]-、[((CF3)2SO2)2N]-、[((CF3)2SO2)3C]-、[Al(O-t-C4F9)4]-、[Al(O-(i-C3F7)CH3)4]-Or [ NTf2]-More preferably, [ PF ]3(C2F5)3]-、[Al(OC(CF3)3)4]-、[B(PhF5)4]-、[B(Ph(CF3)2)4]-、[((CF3)2SO2)2N]-、[((CF3)2SO2)3C]-、[Al(O-t-C4F9)4]-Or [ Al (O- (i-C) ]3F7)CH3)4]-Most preferably, [ Al (O-t-C)4F9)4]-Or [ PF ]3(C2F5)3]-。
20. The radical-cation hybrid photocurable composition according to any one of claims 1 to 19, wherein the infrared-absorbing photosensitizer as component (c) is selected from one or more of the following compounds S1-S70:
Figure FDA0002685496610000071
Figure FDA0002685496610000072
Figure FDA0002685496610000081
21. the photocurable compound according to any one of claims 1 to 20, wherein the photopolymerization initiator as the component (d) may be a photopolymerization initiator capable of generating radicals and cations in the presence of the component (c).
22. The photocurable compound according to any one of claims 1-21, wherein the photopolymerization initiator as component (d) is selected from the group consisting of iodonium salt, sulfonium salt, triazine, and oxime ester type photopolymerization initiators.
23. The radical-cation hybrid photocurable composition according to any one of claims 1 to 22, wherein the photopolymerization initiator as component (d) is an iodonium salt, preferably selected from the group consisting of iodonium salts represented by formula II:
Figure FDA0002685496610000091
wherein R is1’-R6' may be the same or different and are independently selected from H, halogen, nitro, C1-C20Branched or unbranched alkyl, C1-C20Branched or unbranched alkoxy and C1-C20A branched or unbranched alkylthio group, and
X'-as claimed in claim 17 or 19 for X in the compound of formula (I)-The definition of the content of the compound is as follows,
x in the compounds of the formula (I) is preferred-And X 'in the compound of formula (II)'-Are the same.
24. The radical-cation hybrid photocurable composition according to any one of claims 1 to 23, wherein the photopolymerization initiator as component (d) IS selected from one or more of the following compounds IS1-IS 40:
Figure FDA0002685496610000092
Figure FDA0002685496610000093
Figure FDA0002685496610000101
25. the radical-cationic hybrid photocurable composition according to any one of claims 1 to 24, wherein the amount of the infrared absorbing photosensitizer as component (c) is from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight, based on the total weight of the radical-cationic hybrid photocurable composition.
26. The radical-cation hybrid photocurable composition according to any one of claims 1 to 25, wherein the amount of the photopolymerization initiator as component (d) is from 1 to 10% by weight, preferably from 2 to 8% by weight, more preferably from 2.5 to 5% by weight, based on the total weight of the radical-cation hybrid photocurable composition.
27. The radical-cation hybrid photocurable composition according to any one of claims 1 to 26, wherein the weight ratio of the infrared-absorbing photosensitizer as component (c) to the photopolymerization initiator as component (d) is from 10:1 to 1:10, preferably from 8:1 to 1:8, more preferably from 5:1 to 1: 5.
28. A coating liquid comprising the radical-cation hybrid photocurable composition according to any one of claims 1 to 27 and at least one organic solvent.
29. A photosensitive dry film resist comprising a support, a photosensitive layer provided on the support, and a protective layer provided on the photosensitive layer, the photosensitive layer comprising the radical-cation hybrid photocurable composition according to any one of claims 1 to 27.
30. Use of the radical-cation hybrid photocurable composition according to any one of claims 1 to 27 for the preparation of a photosensitive dry film resist.
CN202010976789.XA 2020-09-16 2020-09-16 Radical-cation hybrid photocurable composition and photosensitive dry film resist Pending CN112180680A (en)

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