CN107325237B - Free radical-cation hybrid photocuring system and application thereof - Google Patents

Free radical-cation hybrid photocuring system and application thereof Download PDF

Info

Publication number
CN107325237B
CN107325237B CN201610238062.5A CN201610238062A CN107325237B CN 107325237 B CN107325237 B CN 107325237B CN 201610238062 A CN201610238062 A CN 201610238062A CN 107325237 B CN107325237 B CN 107325237B
Authority
CN
China
Prior art keywords
acrylate
compound
meth
group
ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610238062.5A
Other languages
Chinese (zh)
Other versions
CN107325237A (en
Inventor
钱晓春
胡春青
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
Original Assignee
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changzhou Tronly New Electronic Materials Co Ltd, Changzhou Tronly Advanced Electronic Materials Co Ltd filed Critical Changzhou Tronly New Electronic Materials Co Ltd
Priority to CN201610238062.5A priority Critical patent/CN107325237B/en
Priority to PCT/CN2017/077367 priority patent/WO2017177795A1/en
Publication of CN107325237A publication Critical patent/CN107325237A/en
Application granted granted Critical
Publication of CN107325237B publication Critical patent/CN107325237B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention discloses a free radical-cation hybrid type photo-curing composition, which comprises the following components in percentage by weight: the anthracene ester sensitizer is selected from a compound with a structure shown in a formula (I) and/or a macromolecular compound taking the compound shown in the formula (I) as a main structure; a cation-reactive type compound and a radical-reactive type compound including at least one unsaturated double bond-containing compound and at least one epoxy group-containing compound; a cationic photoinitiator; optionally, a free radical photoinitiator. The composition can combine the advantages of two photocuring systems of free radicals and cations by optimizing the components, has excellent response to a light source within the wavelength range of 200-500nm, and has the advantages of high curing speed, small shrinkage, good developing property and pattern integrity, high hardness of a cured film and strong adhesive force on a base material.

Description

Free radical-cation hybrid photocuring system and application thereof
Technical Field
The invention belongs to the field of organic photocuring, and particularly relates to a free radical-cation hybrid photocuring composition and application thereof in the field of photocuring.
Background
The ultraviolet curing technology has very wide application in the fields of electronic material preparation and the like, and can be divided into two categories of free radical type and cationic type according to different initiation polymerization mechanisms. The two have advantages and disadvantages, the source of free radical type polymerization raw materials is wide, the formula adjustability is high, but the curing shrinkage rate is large, and oxygen inhibition is easily caused; cationic polymerization does not have the problems of shrinkage and oxygen inhibition, but has slow curing speed and higher cost. Radical-cation hybrid photocuring systems are considered to be an effective way to possibly combine the advantages of both. However, the conventional mixing method cannot achieve the expected effect, and the situation that the application effect of the mixing is poor due to poor compatibility of the components occurs sometimes. Therefore, the optimized preparation of the components and the improvement of the compatibility of the components are a key for the development of the hybrid photocuring system.
On the other hand, the initiation light source of the current photo-curing system mainly comprises a high-pressure mercury lamp (with a wavelength range of 200-. LED light sources (wavelength range is usually 320-500nm) have small damage, high energy and low consumption, and are considered to be good substitutes for conventional light sources in photocuring systems by replacing mercury lamps. However, most of the existing light curing systems have poor absorption capacity to the LED light source, and often cannot be cured or are not cured completely, and few applicable systems have more limitations on the types of components and are expensive.
In view of the above, in line with the current technical development trend and practical application requirements, it is significant to develop a hybrid photo-curing system having excellent photo-curing performance in the wavelength range of 200-.
Summary of The Invention
Aiming at the defects of the prior art, the invention aims to provide a free radical-cation hybrid photocuring composition, which can combine the advantages of two photocuring systems of a free radical and a cation through component optimization, has excellent response to a light source in the wavelength range of 200-500nm, and has the advantages of high curing speed, small shrinkage, good developability and pattern integrity, high hardness of a cured film and strong adhesive force on a base material.
Specifically, the radical-cation hybrid photocurable composition of the present invention comprises the following components:
(A) the anthracene ester sensitizer is selected from a compound with a structure shown in a formula (I) and/or a macromolecular compound taking the compound shown in the formula (I) as a main structure:
Figure BDA0000966921830000021
R1and R2Each independently represents hydrogen, nitro, cyano, halogen, C1-C40Straight or branched alkyl of (2), C1-C40Alkoxy of (a), or a-O-CO-R group, and R1And R2At least one of which is an-O-CO-R group, R represents C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C40Containing an ester group, C2-C40Containing epoxy groups, halogens, C3-C20Alkyl substituted by halogen of (1);
R3、R4、R5、R6、R7、R8、R9、R10each independently represents hydrogen, nitro, cyano, halogen, C1-C40Straight or branched alkyl of (2), C3-C40Cycloalkyl of, C4-C40Alkylcycloalkyl or cycloalkylalkyl, C2-C40Alkenyl of (C)6-C40And the acyclic-CH group in these groups2-optionally (optinally) substituted by-O-, -CO-, -NH-, -S-or 1, 4-phenylene;
(B) a cation-reactive type compound and a radical-reactive type compound including at least one unsaturated double bond-containing compound and at least one epoxy group-containing compound;
(C) a cationic photoinitiator;
(D) optionally, a free radical photoinitiator.
The hybrid photocuring composition provided by the invention has good response to light in the wavelength range of 200-500nm, and suitable light sources include (but are not limited to) mercury lamps, halogen lamps, electrodeless lamps, LED lamps, lasers and the like.
In view of its excellent properties, the photocurable composition of the present invention can be applied to paints, coatings, inks, molding materials, and the like, and can be specifically applied to the production of: coating materials coated on base materials such as plastics, metals, glass, ceramics, wood, walls, optical fibers and the like; protective film materials such as hard coat agents, antifouling films, antireflection films, and impact damping films; a photocurable adhesive, an adhesive, a photodegradable coating material, a coating film, a molded article; optical recording media such as hologram materials; optical molding resins, for example, inks (resins) for 3D printing, photoresists for electronic circuit and semiconductor manufacturing, photoresists for electronic materials such as color filters, black matrices, dry films, etc. in displays, and the like; interlayer insulating film, light extraction film, brightness enhancement film, sealing material; printing inks for screen printing, offset printing, gravure printing and the like, photocurable inks for inkjet printing; optical members such as lenses, lens arrays, optical waveguides, light guide plates, light diffusion plates, and diffraction elements; optical spacers, rib walls, nanoimprinting material; and so on.
Detailed Description
The components of the hybrid photocurable composition of the present invention mainly comprise components (a) to (D), which belong to the class of compounds known in the art. Through the matching use of the components, the photocuring composition has excellent response to light sources (such as mercury lamps and LED lamps) in the wavelength range of 200-500nm, and has the advantages of high curing speed, excellent developing property and pattern integrity, high hardness of a cured film, strong adhesive force on a base material, low cost and excellent application effect.
The photocurable composition of the present invention mainly comprises components (a) to (D), each of which will be described in more detail below.
< component (A) Anthracene ester sensitizer >
The anthracene ester sensitizer used as the component (A) is selected from a compound with a structure shown in a formula (I) and/or a macromolecular compound taking the compound of the formula (I) as a main structure:
Figure BDA0000966921830000041
R1and R2Each independently represents hydrogen, nitro, cyano, halogen, C1-C40Straight or branched alkyl of (2), C1-C40Alkoxy of (2), or-O-CO-RGroup, and R1And R2At least one of which is an-O-CO-R group, R represents C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C40Containing an ester group, C2-C40Containing epoxy groups, halogens, C3-C20Alkyl substituted by halogen of (1);
R3、R4、R5、R6、R7、R8、R9、R10each independently represents hydrogen, nitro, cyano, halogen, C1-C40Straight or branched alkyl of (2), C3-C40Cycloalkyl of, C4-C40Alkylcycloalkyl or cycloalkylalkyl, C2-C40Alkenyl of (C)6-C40And the acyclic-CH group in these groups2-may be optionally substituted by-O-, -CO-, -NH-, -S-or 1, 4-phenylene.
Herein, acyclic-CH2-means-CH not in a cyclic structure2-, i.e. excluding-CH in cyclic structures2-. For example, R mentioned above3-R10The "non-cyclic-CH" in (1)2- "includes-CH in straight-chain or branched alkyl2-CH in the alkyl structure of alkylcycloalkyl and cycloalkylalkyl2-CH in-alkenyl and aryl2-。
Preferably, in the structure represented by the formula (I), R1And R2Each independently represents hydrogen, nitro, cyano, halogen, C1-C20Straight or branched alkyl of (2), C1-C20Alkoxy of (a), or a-O-CO-R group, and R1And R2At least one of which is an-O-CO-R group, R represents C3-C10Cycloalkyl of, C4-C14Alkylcycloalkyl or cycloalkylalkyl, C3-C20Containing an ester group, C3-C20Containing epoxy groups, halogens, C3-C20Alkyl substituted by halogen.
In the optional groups of R, the ester group-containing group means that the group contains at least one-CO-O-or-O-CO-, and may be, for example, a group containing a (meth) acrylate group; preferably, the other moieties of the ester-containing group, besides the ester group, belong to the alkyl structure and/or the alkenyl structure. The epoxy-containing group means that the group contains at least one epoxy group; preferably, the other moieties of the epoxy-containing group, except the epoxy group, are of alkyl structure.
Further preferably, in the structure represented by the formula (I), R1And R2Each independently represents hydrogen, nitro, cyano, halogen, C1-C10Straight or branched alkyl of (2), C1-C10Alkoxy of (a), or a-O-CO-R group, and R1And R2At least one of which is an-O-CO-R group, R being selected from the following groups:
Figure BDA0000966921830000061
wherein h is 0-3, i is 1-4, and when h is 0, the hydrogen on the cycloalkyl group may optionally be replaced by C1-C4Alkyl substituted;
-(CH2)j-CO-O-CkH2k+1or- (CH)2)j-O-CO-CkH2k+1Wherein j is 1-4, k is 1-6;
-(CH2)r-O-CO-CH＝CH2wherein r is 1-5;
Figure BDA0000966921830000062
wherein m is 1-3, n is 0-5;
Figure BDA0000966921830000063
wherein x is 1-3, y is 1-2, and z is 0-3;
Figure BDA0000966921830000064
wherein p is 1-5, q is 0-5;
Cl、F、Br、-(CH2)s(CH2)tCCl、-(CH2)s(CH2)tCF、-(CH2)s(CH2)tcbr, wherein s ═ 1-6, t ═ 1-6;
and h, j, r, m, x, y, p, s, t may optionally be replaced by C1-C4Alkyl groups are substituted. Of these radicals, CkH2k+1、CnH2n+1、CzH2z+1And CqH2q+1Represents a linear or branched alkyl group having the corresponding number of carbon atoms; carbon number values include end values and integer values therebetween, e.g. h-0-3 means that h may be 0, 1,2 or 3; these are well defined and obvious to those skilled in the art.
Preferably, in the structure represented by the formula (I), R3、R4、R5、R6、R7、R8、R9、R10Each independently represents hydrogen, nitro, cyano, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C10Alkenyl of (C)6-C20And the acyclic-CH group in these groups2-may be optionally substituted by-O-, -CO-or 1, 4-phenylene.
Further preferably, R3、R4、R5、R6、R7、R8、R9、R10Each independently represents hydrogen, nitro, cyano, halogen, C1-C12Straight or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Alkylcycloalkyl or cycloalkylalkyl, C2-C6Alkenyl of (C)6-C10And the acyclic-CH group in these groups2-is optionally substituted by-O-or-CO-.
In the present invention, the compound having the structure represented by formula (I) can be obtained commercially or can be conveniently prepared by a conventionally known method. For example, reference may be made to the methods described in CN104991418A, CN105001081A, CN105037587A, JP2013107848A, the entire contents of which are incorporated herein by reference.
As an optional anthracene ester sensitizer, the macromolecular compound with the compound of formula (I) as a main structure can be a macromolecular compound formed by polymerization (including homopolymerization and copolymerization), esterification or ester exchange reaction of the compound of formula (I). The corresponding synthesis methods can refer to the contents described in the Chinese patent applications with publication numbers CN104991418A and CN105001081A, which are incorporated herein by reference in their entireties.
Illustratively, the anthracene ester sensitizer as component (a) may be one or a combination of two or more of the compounds represented by the following structures:
Figure BDA0000966921830000081
Figure BDA0000966921830000091
Figure BDA0000966921830000101
Figure BDA0000966921830000111
Figure BDA0000966921830000121
in the hybrid photocurable composition of the present invention, the anthracene ester sensitizer as the component (a) may be a combination of one or more compounds selected from compounds having a structure represented by formula (I) and/or macromolecular compounds having a structure mainly represented by the compound of formula (I). The content of the anthracene ester sensitizer of the component (A) in the composition is 0.001-10% by mass, preferably 0.01-5% by mass, more preferably 0.1-2% by mass.
< cation-reactive type Compound and radical-reactive type Compound of component (B) >
The cation reactive compound and the radical reactive compound of component (B) in the present invention include at least one unsaturated double bond-containing compound and at least one epoxy group-containing compound. The compound may be in the form of monomers, prepolymers, oligomers, polymers, and the like.
The unsaturated double bond-containing compound is selected from (methyl) acrylic ester compounds and/or alkenyl ether compounds.
The (meth) acrylate compound may be selected from: alkyl (meth) acrylates, hydroxy (meth) acrylates, (meth) acrylates of poly (alkylene glycols), (meth) acrylates of trihydric or higher polyhydric alcohols or dicarboxylic acid modifications thereof, (meth) acrylates of epoxy acrylates, urethane (meth) acrylates, polyester acrylates, (meth) acrylates of polymers hydroxylated at the ends, and (meth) acrylates of oligomeric resins such as urethane resins, silicone resins, and spiro-alkane resins.
The (meth) acrylate compound is preferably one or a combination of two or more of alkyl (meth) acrylate, (meth) acrylate of (poly) alkylene glycol, (meth) acrylate of tri or more polyhydric alcohol, epoxy acrylate, urethane (meth) acrylate, from the viewpoint of compatibility and use effects such as curing efficiency, developability, film hardness, substrate adhesion, and the like.
Without limitation, the (meth) acrylate-based compound may be selected from one or a combination of two or more of the following compounds: methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, bisphenol A epoxy acrylate resin, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, and mixtures thereof, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
The alkenyl ether compound can be selected from vinyl ether, 1-propenyl ether, 1-butenyl ether, and 1-pentenyl ether, preferably vinyl ether. More preferably, the vinyl ether compound may be one or a combination of two or more selected from triethylene glycol divinyl ether, 1, 4-cyclohexyldimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glycerol carbonate vinyl ether, dodecyl vinyl ether, and the like.
The compound containing the epoxy group is selected from glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin, aliphatic epoxy resin and oxetane compound.
The epoxy group-containing compound is preferably a glycidyl ether type epoxy resin such as a bisphenol A type epoxy resin and an aliphatic glycidyl ether resin, an aliphatic epoxy resin or an oxetane compound, in view of compatibility and use effects such as curing efficiency, developability, film hardness, substrate adhesion and the like.
The epoxy group-containing compound may be exemplified by 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate, bis (3, 4-epoxycyclohexylmethyl) oxalate, trimethylolpropane glycidyl ether, 1, 2-epoxy-4-vinylcyclohexane, 2' - [ (1-methylethylene) bis (4, 1-phenylenecarboxaldehyde)]Homopolymers of diepoxyethane (bisphenol A epoxy resin), 3-oxiranyl 7-oxabicyclo [4,1,0]Heptane, ethylene glycol diglycidyl ether, C12-C14Alkyl glycidyl ethers, 3-methyl-3-vinylhydroxymethyloxetane, 3-methyl-3-vinylpolyethoxylated 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-Hydroxymethyl oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 1, 3-bis [ (3-ethyl-3-oxetanylmethoxy) methyl]Propane, 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, and the like.
In addition to the above classes, the epoxy-containing compound may be selected from or include compounds having the following structure:
Figure BDA0000966921830000151
Figure BDA0000966921830000161
Figure BDA0000966921830000171
from the viewpoint of priority in performance, as the reactive compound, a (meth) acrylate compound is suitable for a radical type photo-curing system, an epoxy group-containing compound is suitable for a cationic type photo-curing system, and an alkenyl ether compound is suitable for both. Besides the need of optimizing the component types, the good hybrid system has a large influence on the application effect due to the proportion of the components. In the present invention, the content of the (meth) acrylate compound is preferably 20 to 60%, the content of the alkenyl ether compound is preferably 0 to 40%, and the content of the epoxy group-containing compound is preferably 10 to 50% based on the total mass of the component (B).
In the hybrid type photocurable composition of the present invention, the content of the component (B) is 10 to 90%, preferably 40 to 90%, in mass%.
< cationic photoinitiator of component (C) >
The cationic photoinitiator of component (C) may be one or a combination of two or more of aryldiazonium salts, iodonium salts, sulfonium salts, and arylferrocenium salts.
In the photocuring system, the cation/radical reactive compound and the photoinitiator have high correspondence, the cation reactive compound generally needs the cation photoinitiator to initiate polymerization, and the radical reactive compound needs the radical photoinitiator, so that a good effect can be obtained. In the hybrid photocuring composition, the activity of a cationic photoinitiator is greatly improved under the sensitization of a sensitizer, and the cationic reactive compound can be rapidly initiated to be crosslinked and cured. In this process, the reaction system containing the iodonium salt and/or sulfonium salt cationic photoinitiator simultaneously releases radicals to further initiate the radical reactive compound in component (B). That is, when the component (C) includes an iodonium salt and/or sulfonium salt type photoinitiator, it also has a partial function of a radical type while functioning as a cationic photoinitiator.
In view of the cost and the effect of the compounding use, such as the photoinitiation efficiency and the curing speed, the component (C) is preferably an iodonium salt and/or sulfonium salt type photoinitiator, and particularly preferably a compound having a structure represented by the following formula (II) and/or (III):
Figure BDA0000966921830000191
wherein R is11And R12Each independently represents hydrogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl or alkylcycloalkyl of (A), and acyclic-CH in these groups2-optionally substituted by-O-, -S-or 1, 4-phenylene;
R13and R14Each independently represents hydrogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl or alkylcycloalkyl, C6-C20And the acyclic-CH group in these groups2-optionally substituted by-O-, -S-or 1, 4-phenylene;
R15represents C6-C20Aryl of (C)1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl or alkylcycloalkyl, substituted or unsubstituted phenylthiophenyl, and the acyclic-CH in these groups2-optionally substituted by-O-, -S-or 1, 4-phenylene;
X-each independently represents PF6 -、SbF6 -、CF3SO3 -、C4F9SO3 -、C8F17SO3 -、(SO2C4F9)2N-Or B (C)6M5)4 -(M represents H, F, Cl, Br).
As a preferred structure, compounds having the structures represented by the formulae (II) and (III):
R11and R12Each independently represents hydrogen, C1-C12Straight or branched alkyl of (2), C4-C10Cycloalkylalkyl or alkylcycloalkyl of (A), and acyclic-CH in these groups2-is optionally substituted by-O-;
R13and R14Each independently represents hydrogen, C1-C10Straight or branched alkyl of (2), C4-C10Cycloalkylalkyl or alkylcycloalkyl, C6-C12And the acyclic-CH group in these groups2-optionally substituted by-O-, -S-or 1, 4-phenylene;
R15represents C6-C10Aryl, substituted or unsubstituted phenylthiophenyl, and acyclic-CH in these groups2-may be optionally substituted by-O-, -S-or 1, 4-phenylene.
More preferably, the iodonium salt and sulfonium salt photoinitiators have the following structures:
Figure BDA0000966921830000201
Figure BDA0000966921830000211
Figure BDA0000966921830000221
in the photocurable composition of the present invention, when two or more cationic photoinitiators are selected, they may be a combination of two or more compounds of the same type (e.g., iodonium salts or sulfonium salts), or a combination of compounds of different types. The content of the cationic photoinitiator of the component (C) in the composition is 0.001-20% by mass, preferably 0.1-10%.
< component (D) radical type photoinitiator >
The iodonium salt and/or sulfonium salt type photoinitiator has a practical function of radical initiation in use, in which case the radical type photoinitiator is not an essential component of the hybrid photocurable composition of the present invention. However, it is expected that the photocuring performance is further improved by adding a suitable radical photoinitiator to the hybrid system and using the two photoinitiators in combination. On the other hand, when the component (C) is an aryl diazonium salt and/or an aryl ferrocenium salt, the hybrid photocurable composition of the present invention needs to contain a radical type photoinitiator in order to facilitate the crosslinking curing of the radical reactive compound and ensure the overall photocuring effect of the system.
Common free radical photoinitiators include dialkoxybenzophenones, α -hydroxyalkylbenzophenones, α -aminoalkylbenzophenones, acylphosphine oxides, benzophenones, benzoins, benzils, heterocyclic arones, oxime ester photoinitiators, and the like.
The radical type photoinitiator as component (D) is preferably benzophenone, α -hydroxyalkylbenzone and/or α -aminoalkylbenzophenone, benzil based on the consideration of the cost, the effect of the co-use such as photoinitiation efficiency, curing speed and the like.
Illustratively, the radical photoinitiator as component (D) is one or a combination of two or more of the compounds represented by the following structures:
Figure BDA0000966921830000231
Figure BDA0000966921830000241
in the photocurable composition of the present invention, when two or more radical photoinitiators are used, the two or more photoinitiators may be combined in the same compound or may be combined in different compounds. The content of the radical type photoinitiator of component (D) in the composition is 0 to 20% by mass, preferably 0.1 to 10% by mass.
< component (E) other Components >
In addition to the above components (a) to (D), it will be apparent to those skilled in the art that organic and/or inorganic auxiliaries commonly used in the art, including but not limited to pigments, leveling agents, dispersants, curing agents, surfactants, solvents, etc., may be optionally added to the photocurable composition of the present invention according to the product application requirements. In addition, other sensitizers and/or photoinitiators may be added to the composition for compounding without adversely affecting the application of the composition.
According to application requirements, one or more macromolecules or high molecular compounds can be optionally added into the composition to improve the application performance of the composition in the using process, and the macromolecules or high molecular compounds can be polyalcohol or polyester polyol; polymers having no reactive functional group, which are generally resins having acidic functional groups such as phenolic hydroxyl groups and carboxyl groups, may also be optionally added.
< preparation of Photocurable composition >
The components are weighed according to the amount and then uniformly mixed to obtain the photocuring composition.
At present, commercial products in the field of photocuring, particularly middle-high-end products, are mainly imported, most of the products have patent technologies and high product prices, domestic enterprises lack core technologies and independent intellectual property rights, and the development and research and development layout of the enterprises are greatly limited under a strict technical barrier. According to the invention, through component optimization, the obtained hybrid type photocuring composition has a large range of photosensitive wavelength and a good photocuring effect, can be applied to various aspects such as paint, coating, printing ink, forming material and the like by combining the advantages of two types of photocuring systems of a free radical type and a cationic type, and has strong technical and market competitiveness.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.
Unless otherwise specified, the parts are parts by weight hereinafter. The meaning of each abbreviation is as follows:
A1：
Figure BDA0000966921830000261
A2：
Figure BDA0000966921830000262
A3：
Figure BDA0000966921830000263
A4：
Figure BDA0000966921830000271
b1: trimethylolpropane triacrylate;
b2: bisphenol a epoxy acrylate resin (SM 6105-80);
b3: 4-hydroxybutyl vinyl ether (HBVE);
b4: trimethylolpropane tri (3-ethyl-3-oxetanylmethyl) ether; b5: 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate;
C1：
Figure BDA0000966921830000272
C2：
Figure BDA0000966921830000273
D1:
Figure BDA0000966921830000274
D2：
Figure BDA0000966921830000275
1. photocurable composition formulation
The photocurable compositions were formulated as shown in table 1 below.
TABLE 1
Figure BDA0000966921830000281
2. Performance testing
(1) Film formation test under high-pressure mercury lamp
Stirring the photocuring composition under a yellow light lamp, taking the photocuring composition out of a PET template, rolling and coating the mixture to form a film, and drying the film at 90 ℃ for 5min to remove the solvent to form a coating film with the film thickness of about 2 mu m. Cooling the substrate with the coating film to room temperature, attaching a mask plate, and irradiating with a high-pressure mercury lamp (model RW-UV70201 exposure machine, light intensity 50 mW/cm)2) The coating was exposed to light for 30 seconds. Visually observed to evaluate the film formation in the exposed area.
Then soaking in 1% NaOH water solution at 25 deg.C for 30s for development, washing with ultrapure water, and air drying; and then post-baking for 30min in an oven at 240 ℃ to obtain the pattern transferred by the mask plate. The pattern on the substrate was observed with a Scanning Electron Microscope (SEM) to evaluate developability and pattern integrity.
The evaluation criteria for film formation were as follows:
○, the surface of the film is smooth;
◎, the film surface has flaws;
●: the film formation was impossible.
The evaluation criteria for developability were as follows:
○ No residue was observed in the unexposed parts;
◎ A small but acceptable amount of residue was observed in the unexposed parts;
●: a clear residue was observed in the unexposed parts.
The evaluation criteria for pattern integrity were as follows:
○ No pattern defects were observed;
◎, small part of the pattern is observed to have some defects;
●: many pattern defects were clearly observed.
The evaluation results are shown in table 2.
TABLE 2
Figure BDA0000966921830000301
Note: "-" is because film formation was impossible, and thus evaluation was impossible.
(2) Film formation test under LED light source
Stirring the photocuring composition under a yellow light lamp, taking the photocuring composition out of a PET template, rolling and coating the mixture to form a film, and drying the film at 90 ℃ for 5min to remove the solvent to form a coating film with the film thickness of about 2 mu m. Cooling the substrate with the coating film to room temperature, attaching a mask plate, and adopting a wavelength of 395nm and a light intensity of 1500mW/cm2The LED light source of (1) was exposed to light with the distance between the substrate on which the coating film was formed and the lamp tube kept at 10cm, and the primary curing time was measured.
The primary curing time refers to the time when the surface hardness of the material is not marked by a 1H China high-grade drawing pencil under the irradiation of an LED light source, and the primary curing time can be used for measuring the initiation efficiency of the photoinitiator.
After the primary curing, the same development and post-baking steps as in (1) above were performed, and the developability and pattern integrity were evaluated using the same criteria.
The test results are shown in table 3 below.
TABLE 3
Figure BDA0000966921830000311
(3) Curing shrinkage test
The photocurable compositions of examples 1-6 were cured without using a mask, with reference to the application and curing conditions described in (2) above. And calculating the ratio of the volume difference before and after primary curing to the volume before curing by referring to the relevant regulations of international standard ISO3521, and calculating the shrinkage rate.
The results are shown in Table 4 below.
TABLE 4
Figure BDA0000966921830000312
(4) Adhesion test of substrates
The adhesion of the photocurable compositions to different substrates was tested by means of a QFH paint film scriber, using the procedure of the hundred-grid scribing method, referred to the "test of scratching of films of GBT9286-1998 paints and varnishes", as represented by the photocurable composition of example 1.
The specific method comprises the following steps:
uniformly coating the photocuring composition on different substrates, respectively curing under a high-pressure mercury lamp and an LED lamp source (the coating and curing conditions are as described in the above (1) and (2), exposing for 30s under the high-pressure mercury lamp and exposing for 3s under an LED light source without using a mask plate), standing at room temperature for 24h for aging after curing is completed, then transversely and longitudinally scribing 1 knife by using a hundred-grid knife to form 100 fine grids, then respectively brushing for five times in the diagonal direction of a brush, pasting a 3M600 adhesive tape on a notch and then pulling the notch open, observing the condition of a grid area by using a magnifier, and evaluating the adhesion degree of the coating film on the substrates by evaluating the integrity degree of the coating film in the grids. The more complete the coating film in the squares, the stronger the adhesion.
The evaluation criteria are as follows:
a: the edges of the cuts are completely smooth, and the edges of the grids are not peeled off;
b: small pieces are peeled off at the intersection of the cuts, and the actual damage in the grid scribing area is less than or equal to 5 percent;
c: the edges and/or intersections of the cuts are peeled off, and the area of the cuts is 5% -30% (5% is not included);
d: and partial peeling or whole peeling is carried out along the edge of the cut, or partial lattices are peeled off by whole pieces. The area of exfoliation was over 30%.
The evaluation results are shown in table 5 below.
TABLE 5
Figure BDA0000966921830000331
The test results in tables 2-5 show that the hybrid photocuring composition has good photocuring effect under mercury lamps and LED light sources, high sensitivity, high curing speed, low shrinkage, good developability and pattern integrity, high coating hardness and strong adhesive force on different substrates.

Claims (13)

1. A radical-cation hybrid photocurable composition comprising the following components:
(A) an anthracene ester sensitizer selected from compounds having a structure represented by formula (I):
Figure FDA0002123938940000011
wherein,
R1and R2Represents a group-O-CO-R, R being selected from the following groups:
Figure FDA0002123938940000012
wherein h is 0-3, i is 1-4, and when h is 0, the hydrogen on the cycloalkyl group may optionally be replaced by C1-C4Alkyl substituted;
-(CH2)j-CO-O-CkH2k+1or- (CH)2)j-O-CO-CkH2k+1Wherein j is 1-4, k is 1-6;
Figure FDA0002123938940000013
wherein m is 1-3, n is 0-5;
Figure FDA0002123938940000014
wherein x is 1-3, y is 1-2, and z is 0-3;
Figure FDA0002123938940000015
wherein p is 1-5, q is 0-5;
and h, j, m, x, y, p are optionally substituted by C1-C4Alkyl substituted;
R3、R4、R5、R6、R7、R8、R9、R10each independently represents hydrogen, C1-C12Straight or branched alkyl of (2), C6-C10And the acyclic-CH group in these groups2-is optionally substituted by-O-or-CO-;
(B) a cation-reactive type compound and a radical-reactive type compound including at least one unsaturated double bond-containing compound and at least one epoxy group-containing compound;
wherein the unsaturated double bond-containing compound is selected from (methyl) acrylate compounds and/or alkenyl ether compounds; and,
based on the total mass of the component (B), the content of the (methyl) acrylic ester compound is 20-60%, the content of the alkenyl ether compound is 0-40%, and the content of the epoxy group-containing compound is 10-50%;
(C) a cationic photoinitiator selected from iodonium salt and/or sulfonium salt photoinitiators;
(D) optionally, a free radical photoinitiator.
2. The hybrid photocurable composition of claim 1 wherein: the (meth) acrylate compound is selected from the group consisting of an alkyl (meth) acrylate, a hydroxy (meth) acrylate, a (meth) acrylate of a (poly) alkylene glycol, a (meth) acrylate of a tri or higher polyhydric alcohol or a dicarboxylic acid modification thereof, an epoxy acrylate, a urethane (meth) acrylate, a polyester acrylate, a (meth) acrylate of a terminal-hydroxylated polymer, and a (meth) acrylate of an oligomeric resin.
3. The hybrid photocurable composition of claim 1 or 2, wherein: the (meth) acrylate compound is one or a combination of two or more of alkyl (meth) acrylate, (meth) acrylate of poly (alkylene glycol), (meth) acrylate of trihydric or higher polyhydric alcohol, epoxy acrylate, and urethane (meth) acrylate.
4. The hybrid photocurable composition of claim 1 wherein: the alkenyl ether compounds are selected from vinyl ether, 1-propenyl ether, 1-butenyl ether, and 1-pentenyl ether compounds.
5. The hybrid photocurable composition of claim 1 or 4, wherein: the alkenyl ether compound is selected from vinyl ether compounds.
6. The hybrid photocurable composition of claim 5 wherein: the vinyl ether compound is selected from one or the combination of more than two of triethylene glycol divinyl ether, 1, 4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glycerol carbonate vinyl ether and dodecyl vinyl ether.
7. The hybrid photocurable composition of claim 1 wherein: the compound containing the epoxy group is selected from glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin, aliphatic epoxy resin and oxetane compound.
8. The hybrid photocurable composition of claim 1 or 7, wherein: the epoxy group-containing compound is selected from glycidyl ether epoxy resin, aliphatic epoxy resin and oxetane compound.
9. The cationic photocurable composition according to claim 1, characterized in that: the cationic photoinitiator of component (C) is selected from compounds having the structures shown in the following formulas (II) and/or (III):
Figure FDA0002123938940000041
wherein R is11And R12Each independently represents hydrogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl or alkylcycloalkyl of (A), and acyclic-CH in these groups2-optionally substituted by-O-, -S-or 1, 4-phenylene;
R13and R14Each independently represents hydrogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl or alkylcycloalkyl, C6-C20And the acyclic-CH group in these groups2-optionally substituted by-O-, -S-or 1, 4-phenylene;
R15represents C6-C20Aryl of (C)1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl or alkylcycloalkyl, substituted or unsubstituted phenylthiophenyl, and the acyclic-CH in these groups2-optionally substituted by-O-, -S-or 1, 4-phenylene;
X-each independently represents PF6 -、SbF6 -、CF3SO3 -、C4F9SO3 -、C8F17SO3 -、(SO2C4F9)2N-Or B (C)6M5)4 -Wherein M represents H, F, Cl or Br.
10. The hybrid photocurable composition of claim 9 wherein:
R11and R12Each independently represents hydrogen, C1-C12Straight or branched alkyl of (2), C4-C10Cycloalkylalkyl or alkylcycloalkyl of (A), and acyclic-CH in these groups2-is optionally substituted by-O-;
R13and R14Each independently represents hydrogen, C1-C10Straight or branched alkyl of (2), C4-C10Cycloalkylalkyl or alkylcycloalkyl, C6-C12And the acyclic-CH group in these groups2-optionally substituted by-O-, -S-or 1, 4-phenylene;
R15represents C6-C10Aryl, substituted or unsubstituted phenylthiophenyl, and acyclic-CH in these groups2-may be optionally substituted by-O-, -S-or 1, 4-phenylene.
11. The hybrid photocurable composition according to claim 1, wherein the radical photoinitiator of component (D) is selected from the group consisting of benzophenones, α -hydroxyalkylbenzophenones and/or α -aminoalkylbenzophenones, benzils.
12. Use of the hybrid photocurable composition according to any one of claims 1-11 in the field of photocuring.
13. Use according to claim 12, characterized in that: the fields of photocuring include paints, coatings, inks and molding materials.
CN201610238062.5A 2016-04-15 2016-04-15 Free radical-cation hybrid photocuring system and application thereof Active CN107325237B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201610238062.5A CN107325237B (en) 2016-04-15 2016-04-15 Free radical-cation hybrid photocuring system and application thereof
PCT/CN2017/077367 WO2017177795A1 (en) 2016-04-15 2017-03-20 Free radical-cation hybrid photocuring system and applications thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610238062.5A CN107325237B (en) 2016-04-15 2016-04-15 Free radical-cation hybrid photocuring system and application thereof

Publications (2)

Publication Number Publication Date
CN107325237A CN107325237A (en) 2017-11-07
CN107325237B true CN107325237B (en) 2020-04-21

Family

ID=60042348

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610238062.5A Active CN107325237B (en) 2016-04-15 2016-04-15 Free radical-cation hybrid photocuring system and application thereof

Country Status (2)

Country Link
CN (1) CN107325237B (en)
WO (1) WO2017177795A1 (en)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019159908A1 (en) * 2018-02-13 2019-08-22 川崎化成工業株式会社 Compound having polycyclic aromatic skeleton, and endoperoxide compound of same
CN108329657A (en) * 2018-03-09 2018-07-27 北京瑞达科博技术有限公司 Free radical-Cationic Hybrid curing glass fiber reinforcement plastic feed composition
CN110389499A (en) * 2018-04-17 2019-10-29 常州格林感光新材料有限公司 A kind of Photocurable composition and its application
CN110713593A (en) * 2018-07-12 2020-01-21 常州强力电子新材料股份有限公司 Epoxy modified polyester resin, preparation method thereof, composition containing epoxy modified polyester resin and application thereof
WO2020054874A1 (en) * 2018-09-15 2020-03-19 川崎化成工業株式会社 Photopolymerization sensitizer
WO2020054116A1 (en) * 2018-09-15 2020-03-19 川崎化成工業株式会社 Photopolymerization sensitizer
CN110964383A (en) * 2018-09-30 2020-04-07 常州格林感光新材料有限公司 Radiation curing composition
CN109575681B (en) * 2018-11-09 2022-04-19 中山布瑞特环保油墨有限公司 Water-based free radical-cation hybrid photocuring ink and application thereof
WO2020121384A1 (en) * 2018-12-10 2020-06-18 川崎化成工業株式会社 Photopolymerization sensitizer having migration resistance
JP7237282B2 (en) * 2019-03-29 2023-03-13 エア・ウォーター・パフォーマンスケミカル株式会社 Photopolymerization sensitizer with migration resistance
JP7276652B2 (en) * 2019-04-11 2023-05-18 エア・ウォーター・パフォーマンスケミカル株式会社 Photoradical curing oxygen inhibition reducing agent, photoradical polymerizable composition containing photoradical curing oxygen inhibition reducing agent, coating film containing photoradical curing oxygen inhibition reducing agent and curing method thereof
JP2020176254A (en) * 2019-04-15 2020-10-29 川崎化成工業株式会社 Photopolymerizable composition, coating film containing the photopolymerizable composition, and curing method therefor
WO2021121135A1 (en) * 2019-12-19 2021-06-24 常州强力电子新材料股份有限公司 Photoinitiator, preparation method therefor and application thereof, and photocurable composition
CN111234606A (en) * 2020-02-15 2020-06-05 苏州星烁纳米科技有限公司 Packaging ink and light-emitting device
CN112062896B (en) * 2020-08-25 2022-05-31 南方科技大学 Energy-absorbing 3D printing material, preparation method thereof and energy-absorbing device
CN112126275A (en) * 2020-09-16 2020-12-25 四川乐凯新材料有限公司 Photocurable composition for PCB containing alkenyl ether and/or oxetane and radical polymerizable compound
CN112180680A (en) * 2020-09-16 2021-01-05 四川乐凯新材料有限公司 Radical-cation hybrid photocurable composition and photosensitive dry film resist
CN112094365B (en) * 2020-09-16 2023-04-25 湖北固润科技股份有限公司 Photocurable composition containing infrared absorbing photosensitizer, initiator and alkenyl ether and/or oxetane compound
CN113024690B (en) * 2020-12-30 2023-08-11 艾坚蒙(安庆)科技发展有限公司 Photoinitiator composition, photo-curing composition and photo-curing product
CN113583550A (en) * 2021-07-28 2021-11-02 深圳市金达盛化工有限公司 Preparation and application method of LED cold light curing coating material
CN116554762A (en) * 2023-06-07 2023-08-08 焦作卓立膜材料股份有限公司 Photo-curing organic silicon back coating material and preparation method thereof, thermal transfer carbon ribbon back coating and preparation method thereof, and thermal transfer carbon ribbon

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104991418A (en) * 2015-06-24 2015-10-21 常州强力电子新材料股份有限公司 Sensitizer used for UV-LED photo-curing, preparing method thereof and application thereof
CN105001081A (en) * 2015-06-24 2015-10-28 常州强力电子新材料股份有限公司 Anthracene-series sensitizer and application of same in UV-LED light-curing system
CN105037587A (en) * 2015-06-24 2015-11-11 常州强力先端电子材料有限公司 Sensitizer applicable to UV-LED photocuring system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104991418A (en) * 2015-06-24 2015-10-21 常州强力电子新材料股份有限公司 Sensitizer used for UV-LED photo-curing, preparing method thereof and application thereof
CN105001081A (en) * 2015-06-24 2015-10-28 常州强力电子新材料股份有限公司 Anthracene-series sensitizer and application of same in UV-LED light-curing system
CN105037587A (en) * 2015-06-24 2015-11-11 常州强力先端电子材料有限公司 Sensitizer applicable to UV-LED photocuring system

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"混杂光固化体系的原理及应用";陈明 等;《感光科学与光化学》;20010831;第19卷(第3期);208-216页 *

Also Published As

Publication number Publication date
CN107325237A (en) 2017-11-07
WO2017177795A1 (en) 2017-10-19

Similar Documents

Publication Publication Date Title
CN107325237B (en) Free radical-cation hybrid photocuring system and application thereof
CN107300830B (en) Novel photocuring composition and application thereof
CN107300832B (en) Photo-curing composition and application thereof
CN107300831B (en) Curable composition applied to LED photocuring
CN107300829B (en) Cationic photocuring system and application of composition thereof
CN107300833B (en) Free radical photocuring system and application of composition thereof
JP5844416B2 (en) Method for producing photocured product of photosensitive composition
KR101721254B1 (en) Dual photoinitiator, photocurable composition, use thereof and process for producing a three dimensional article
KR20130016045A (en) Polymer compounds comprising dye and curable resin composition comprising the same
KR101367572B1 (en) Polymer compounds comprising dye and curable resin composition comprising the same
CN104854155B (en) Photocurable composition
CN111324009A (en) Photocurable composition and use thereof
JP2019026833A (en) Curable resin composition
CN111909118B (en) Oxetane compound, photocurable composition, ink and use thereof
CN110824836A (en) Cationic photocurable composition and application thereof
US7935739B2 (en) Cationic curable composition and cured product thereof
CN108319111B (en) Photosensitive resin composition for liquid crystal display
CN112180680A (en) Radical-cation hybrid photocurable composition and photosensitive dry film resist
CN112011213A (en) Photo-curing printing ink and application thereof
CN108319109B (en) Application of photosensitive resin composition in manufacturing printed circuit board
CN115612000B (en) Infrared light sensitive photo-curing composition
CN118420811A (en) Photoinitiation system and free radical cation hybrid type photocuring composition containing photoinitiation system
CN118388683A (en) Cationic photoinitiation system and photocuring composition containing same
CN110819203A (en) Cationic photocuring composition and application thereof in photocuring field
JP6781738B2 (en) Active energy ray-curable composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant