WO2018010605A1 - 混杂型光敏树脂及其制备方法 - Google Patents

混杂型光敏树脂及其制备方法 Download PDF

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WO2018010605A1
WO2018010605A1 PCT/CN2017/092228 CN2017092228W WO2018010605A1 WO 2018010605 A1 WO2018010605 A1 WO 2018010605A1 CN 2017092228 W CN2017092228 W CN 2017092228W WO 2018010605 A1 WO2018010605 A1 WO 2018010605A1
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group
photosensitive resin
linear
compound
branched
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PCT/CN2017/092228
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English (en)
French (fr)
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钱晓春
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常州强力先端电子材料有限公司
常州强力电子新材料股份有限公司
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Priority to EP17826941.1A priority Critical patent/EP3486724B1/en
Priority to KR1020197003745A priority patent/KR102141769B1/ko
Priority to JP2018568217A priority patent/JP6680910B2/ja
Publication of WO2018010605A1 publication Critical patent/WO2018010605A1/zh
Priority to US16/246,379 priority patent/US10642155B2/en

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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • C08F20/68—Esters
    • 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
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/12—Esters of phenols or saturated alcohols
    • C08F22/20—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2648—Alkali metals or compounds thereof
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • 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
    • 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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur

Definitions

  • the invention belongs to the field of organic chemistry, and in particular relates to a hybrid photosensitive resin and a preparation method thereof.
  • the initiation system used in the radiation curing technology mainly includes a radical curing system and a cationic curing system.
  • the free radical curing system has a fast curing speed and many kinds of initiators.
  • the research is deeper and the related theories are more mature, but there are also insurmountable defects, such as: large volume shrinkage during curing, which seriously affects the coating on the substrate. Adhesion; Oxygen inhibition phenomenon is more serious, the surface of the thin coating is difficult to cure; for the dead angle that is not irradiated by ultraviolet light, it can not be cured at all, and so on.
  • the cationic curing system has small volume shrinkage after curing, and has strong adhesion, and there is no problem of oxygen inhibition during curing. For deeper parts or parts that are not irradiated by ultraviolet light, the curing can be effectively cured by post-cure. It is slow in curing speed, low in production efficiency, and suitable for a small variety of initiators.
  • Hybrid photosensitive resin is an important research direction to overcome such defects.
  • JP2011168561A discloses a compound having a plurality of oxetane functional groups and an acryloxy functional group, which has a faster curing speed and a higher hardness.
  • JP2011168561A discloses a compound having a plurality of oxetane functional groups and an acryloxy functional group, which has a faster curing speed and a higher hardness.
  • such compounds have poor flexibility and poor adhesion, which greatly affects the performance of the photosensitive material.
  • the object of the present invention is to provide a hybrid photosensitive resin with good application performance and a preparation method thereof.
  • the photosensitive resin contains an oxetane functional group and a (meth)acryloyloxy functional group, and the functionality is controllable and controllable.
  • the curing speed is fast, and there is no oxygen inhibition problem, and
  • the cured film has high hardness, good flexibility, and good adhesion and heat resistance.
  • the hybrid photosensitive resin of the present invention has a structure represented by the following formula (I):
  • R 1 represents a C 1 -C 40 linear or branched m-valent alkyl group, a C 2 -C 20 m-valent alkenyl group, or a C 6 -C 40 m-valent aryl group, wherein -CH 2 - Optionally substituted with an oxygen atom, -NH- or 1,4-phenylene, provided that two -O- are not directly attached; and, optionally, one or more of these groups
  • the hydrogen atoms may each be independently substituted with a group selected from an alkyl group, a halogen, and a nitro group;
  • R 2 represents a C 1 -C 20 linear or branched alkylene group, and -CH 2 - in the main chain may be optionally substituted by an oxygen atom, provided that two -O- are not directly linked, and optionally , one or more hydrogen atoms in the group may each be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group;
  • R 3 represents hydrogen, halogen, nitro, C 1 -C 20 linear or branched alkyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl, C 4 -C An alkylcycloalkyl group of 20 , an alkenyl group of C 2 -C 10 , or an aryl group of C 6 -C 20 , optionally, one or more of the hydrogen atoms of these groups may be independently selected from each other Substituted by a group of an alkyl group, a halogen, or a nitro group;
  • R represents hydrogen or methyl
  • n an integer from 1-8.
  • the m-valent linking group R 1 couples m oxetane functional groups and m (meth)acryloyloxy functional groups into a single unit.
  • R 1 represents a C 1 -C 40 linear or branched m-valent alkyl group, a C 2 -C 10 linear or branched m-valent alkenyl group, or a C 6 -C 30 a m-valent aryl group, wherein -CH 2 - may be optionally substituted by an oxygen atom, -NH- or 1,4-phenylene, provided that the two -O- are not directly linked; and optionally, these One or more hydrogen atoms in the group may each be independently substituted with a group selected from the group consisting of an alkyl group, a halogen, and a nitro group.
  • R 1 may be selected from the following structures:
  • R 2 represents a C 1 -C 10 linear or branched alkylene group, and -CH 2 - in the main chain may be optionally substituted by an oxygen atom, provided that the two -O- are not directly bonded.
  • R 2 represents a C 1 -C 6 straight or branched alkylene group, and -CH 2 - in the main chain may be optionally substituted by an oxygen atom, provided that two -O- are not directly linked .
  • R 3 represents hydrogen, C 1 -C 10 linear or branched alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 An alkylcycloalkyl group, a C 2 -C 8 alkenyl group, or a phenyl group. Further preferably, R 3 represents a C 1 -C 4 linear or branched alkyl group, or a C 4 -C 8 cycloalkylalkyl group.
  • m is preferably an integer of from 1 to 6, more preferably an integer of from 1 to 4.
  • C 1 -C 10 includes C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , "integer of 1-4" includes 1, 2, 3, 4.
  • the present invention also relates to a process for producing a hybrid photosensitive resin represented by the above formula (I), which comprises a hydroxyl group-containing compound represented by the formula (II) and an oxetane group represented by the formula (III).
  • the base compound is a starting material and includes the following steps:
  • reaction formula is as follows:
  • the intermediate is reacted with (meth)acrylic acid or (meth) acrylate in the presence of a catalyst to obtain a product;
  • R 4 represents hydrogen or a C 1 -C 4 alkyl group (e.g., CH 3 , CH 3 CH 2 , CH 3 CH 2 CH 2 , etc.).
  • the catalyst used in the reaction of the step (1) may be: an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like; an alkali metal salt of an alcohol such as sodium methoxide, potassium ethoxide, sodium t-butoxide or the like; alkali metal carbon An acid salt such as sodium carbonate, potassium carbonate or the like; an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; an alkyl metal lithium compound such as butyl lithium, phenyl lithium or the like; an amine lithium compound such as two Lithium isopropylamino, lithium hexamethyldisilazide, and the like.
  • the amount of the catalyst used can be easily determined by those skilled in the art, and preferably, the amount of the catalyst is from 0.1 to 20%, more preferably from 1 to 20%, based on the mole of the compound of the formula (II).
  • the reaction system of the step (1) may optionally contain an organic solvent depending on the kind of the raw material.
  • the type of the solvent to be used is not particularly limited as long as it can dissolve the reaction raw material without adversely affecting the reaction, and may be, for example, a nitrile solvent such as acetonitrile, propionitrile or benzonitrile; N,N-dimethylformamide, N An amide solvent such as N-dimethylacetamide or N-methylpyrrolidone; an ether solvent such as tetrahydrofuran or dioxane; or an aromatic solvent such as benzene, toluene or xylene. These solvents can be used separately One type may be used in combination of two or more types, and the total amount may be appropriately adjusted depending on the uniformity and agitation of the reaction system, which is easily determined by those skilled in the art.
  • the reaction temperature of the step (1) is usually from 25 to 200 ° C, preferably from 50 to 150 ° C.
  • the reaction pressure is usually normal pressure.
  • the pH was adjusted to neutral, filtered, washed with water, extracted, and distilled under reduced pressure to give an intermediate compound.
  • the intermediate compound is subjected to an esterification reaction with (meth)acrylic acid or a transesterification reaction with a (meth) acrylate to obtain a compound of the formula (I).
  • the reaction in the step (2) is carried out in an organic solvent containing a catalyst, and the type of the solvent is not particularly limited as long as it can dissolve the reaction raw material without adversely affecting the reaction, such as an aromatic solvent such as benzene, toluene or xylene.
  • the solvent may be used singly or in combination of two or more. The total amount may be appropriately adjusted depending on the homogeneity and agitation of the reaction system, which is easily determined by those skilled in the art.
  • the catalyst used in the esterification reaction may be a mineral acid such as hydrochloric acid, phosphoric acid, boric acid, concentrated sulfuric acid or the like, or an organic acid such as p-toluenesulfonic acid or methanesulfonic acid.
  • the catalyst used in the transesterification reaction may be a titanate compound such as 2-ethylhexyl titanate, tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate. One or a combination of two or more of tetraisobutyl titanate or the like.
  • the amount of the catalyst used can be readily determined by those skilled in the art.
  • the amount of the catalyst is from 0.05 to 5% by weight, more preferably from 0.1 to 2% by weight, based on the amount of the intermediate compound.
  • the reaction temperature is usually from 0 to 200 ° C, preferably from 50 to 150 ° C. After completion of the reaction, the mixture was washed with water until neutral, and the solvent was evaporated under reduced pressure to give the title compound.
  • the hybrid photosensitive resin of the present invention contains a plurality of oxetane functional groups and (meth)acryloyloxy functional groups. Through structural optimization, functional groups echo each other, resulting in the resin is very suitable for free radical-cationic photocuring systems, fast curing, no oxygen inhibition, and high hardness, flexibility, adhesion Excellent heat resistance.
  • the curing properties of the photosensitive resin of the present invention were tested by using the compound of the above examples as an example with a photoinitiator.
  • pure cation system or pure free radical system with the same functionality was used as the comparison object, including: monofunctional cationic monomer phenyl glycidyl ether (960, Hubei Jusheng Technology Co., Ltd.), difunctional cation Monomer bisphenol A epoxy resin (E51, Jiangsu Sanmu Group), trifunctional cationic monomer 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester (TDE-85, Tianjin Jin Donghua factory); monofunctional free radical monomer acrylic acid ⁇ -hydroxyethyl ester (HEA, Sartomer), bifunctional free radical monomer 1,6-hexanediol diacrylate (HDDA, Sadoma) ), a trifunctional free radical monomer trimethylolpropane triacrylate (TMPTA, Sartomer).
  • monofunctional cationic monomer phenyl glycidyl ether 960, Hubei Jusheng Technology Co., Ltd.
  • the cationic initiator used was PAG-202 and the free radical initiator was 184.
  • the structure was as follows:
  • the raw materials were selected according to the formulation shown in Table 2, and stirred uniformly in a dark room, and then sampled on a PET film and coated with a 25# wire bar to form a coating film having a film thickness of about 25 ⁇ m.
  • the coated PET film was placed in a crawler exposure machine (RW-UV.70201, wavelength 300-500 nm) for exposure, and the energy received for one exposure was 80 mj/cm 2 , and the curing of each group was recorded. The minimum energy required.
  • the bottom curing speed is measured by the finger licking method. That is, the coating is lightly rubbed with a nail, so that no peeling off, no bottoming phenomenon means that the bottom layer is completely cured.
  • Formula 1 Formula 2
  • Formula 3 Formula 4
  • Formula 5 Formula 6 960 6g - - - - - E-51 - 6g - - - - TDE-85 - - 6g - - - -
  • the hybrid photosensitive resin of the present invention has a clear advantage in curing efficiency when combined with a radical-cationic photoinitiator, and the energy required for curing is significantly lower than that of having the same cation. Or free radical functional monomer, there is no oxygen inhibition problem.
  • the photosensitive resin of the present invention has a generally superior curing speed in the case of equivalent functionality.
  • the properties of the hybrid photosensitive resin of the present invention after curing into a film were evaluated by application to an exemplary photocurable composition mainly including film hardness, adhesion, flexibility, and heat resistance (measured by glass transition temperature). among them,
  • the photocurable composition of the present invention is prepared in the following proportions:
  • Photosensitive resin of the present invention 98 parts by mass
  • Free radical initiator 184 1 part by mass
  • the photocurable composition of Comparative Example 1 was prepared in the following ratios:
  • the photocurable composition of Comparative Example 2 was prepared in the following ratios:
  • Free radical initiator 184 2 parts by mass
  • the photocurable composition of Comparative Example 3 was prepared in the following ratios:
  • Photocuring polymerizable monomer Compound A, 98 parts by mass
  • Free radical initiator 184 1 part by mass
  • the compound A is a compound disclosed in JP2011168561A, and the structure is as follows:
  • the formulation composition was uniformly stirred in a dark room, and coated on a glass substrate with a 25# wire bar to obtain a coating having a thickness of about 25 ⁇ m, and then placed on a crawler exposure machine (RW-UV.70201, wavelength 300-500 nm).
  • the film was fully exposed 10 times, the single exposure was 80 mj/cm 2 , and then tested after being placed for 24 hours.
  • the cured films of the present invention and comparative examples were tested under the conditions of a temperature of 23 ° C and a relative humidity of 50%.
  • the pencil hardness evaluation method specified in GB/T6739-2006 the pencil is inserted into the test instrument and fixed with a clip to protect it. With the level, the tip of the pencil is placed on the surface of the paint film and pushed at least 7mm away from you at a speed of 1mm/s. If no scratches appear, repeat the experiment in the untested area and replace the pencil with a higher hardness until it appears.
  • the hardness of the coating is indicated by the hardness of the hardest pencil which does not scratch the coating until at least 3 mm long.
  • the cured films of the present invention and comparative examples were tested under the conditions of a temperature of 23 ° C and a relative humidity of 50%.
  • the coating film is cut into a hundred grid, the cutting edge should be drawn with the substrate when cutting, and the cutting edge should be sharp, and the cutting edge and the coating film become 45. Degree angle.
  • Use a soft brush to remove the paint scraps stick the 3M transparent tape on the lined 100 grids, and apply force to make the tape firmly adhere to the film surface and the cross-section.
  • Level 0 The cutting edge is completely smooth and has no shedding
  • Level 1 There is a little coating peeling off at the intersection of the incisions, but the cross-cut area is not affected by significantly more than 5%;
  • Level 2 There is a coating peeling off at the intersection of the incision and/or along the edge of the incision, which is significantly affected by more than 5%, but not significantly greater than 15%;
  • Level 3 The coating peels off partially or completely along the cutting edge with large fragments, and/or partially or completely peels off at different parts of the lattice.
  • the affected cross-cut area is significantly greater than 15%, but not significantly greater than 35%;
  • Level 4 The coating peels off along the cutting edge, and/or some of the squares are partially or completely detached, and the affected cross-cut area is significantly greater than 35%, but not significantly greater than 65%;
  • Level 5 The degree of peeling exceeds level 4.
  • the cured films of the examples and the comparative examples were tested at a temperature of 23 ° C and a relative humidity of 70%, and the outer side of the tinplate coated with the cured coating was based on the GB/T1731-93 paint film flexibility test method. Winding on the rod shaft of 10, 5, 4, 3, 2, 1 mm in the longitudinal direction, bending for 2-3 s, observing with a magnifying glass, indicating the photocured coating with the diameter of the smallest rod axis broken by the coating layer Flexibility.
  • the glass transition temperature of the cured film obtained by the present invention and the comparative example was measured by a differential scanning calorimeter (PE DSC 8000) under the conditions of a nitrogen atmosphere at a rate of 10 ° C/min from -20 ° C to 200 ° C. Maintained at 200 ° C for 1 min, then cooled from 200 ° C to -20 ° C at a rate of 10 ° C / min, held at -20 ° C for 1 min, then heated at -20 ° C to 200 ° C at a rate of 10 ° C / min, thereby measuring Glass transition temperature Tg (°C).
  • PE DSC 8000 differential scanning calorimeter
  • the hybrid photosensitive resin of the present invention is applied to a radical-cationic curing system, which can impart a significantly higher hardness, better adhesion, flexibility and more to the cured film than E51 and TMPTA. Good heat resistance; and compared to the same kind of compound A, it also shows better application performance in these four aspects.
  • the novel hybrid photosensitive resin compound provided by the present invention combines the advantages of cationic curing and radical curing, has high curing efficiency, is excellent in hardness, adhesion, flexibility and heat resistance of the cured film, and has a simple synthesis method. There are many varieties, which have a good impetus to the promotion and application of light curing.

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Abstract

一种混杂型光敏树脂及其制备方法，该混杂型光敏树脂含有氧杂环丁烷官能团和（甲基）丙烯酰氧基官能团，功能性基团之间彼此呼应且官能度可调可控，非常适用于自由基-阳离子光固化体系，固化速度快，不存在氧阻聚问题，且固化膜硬度高，柔韧性好，附着性和耐热性优异。

Description

[根据细则37.2由ISA制定的发明名称]　混杂型光敏树脂及其制备方法 技术领域
本发明属于有机化学领域，具体涉及一种混杂型光敏树脂及其制备方法。
背景技术
根据固化机理，辐射固化技术所用的引发体系主要有自由基型固化体系和阳离子型固化体系两种。自由基型固化体系固化速度快，引发剂种类多，对其研究较为深入，相关理论较为成熟，但也存在难以克服的缺陷，如：固化时体积收缩较大，严重影响涂层对基材的附着性；氧阻聚现象较严重，薄涂层表面固化困难；对于紫外光辐射不到的死角，完全不能固化，等等。阳离子型固化体系固化后体积收缩小，附着力强，且固化过程中不存在氧阻聚的问题，对于较深的部位或紫外光辐射不到的部位，可通过后固化有效的固化完全，缺点是固化速度慢，生产效率不高，且适用的引发剂种类较少。
近年来，针对自由基型引发体系和阳离子型引发体系的不同特点，出现了自由基-阳离子混合聚合体系，能够有效综合自由基固化和阳离子固化的优点，从而制得性能优良的固化产品。然而，适用于这类固化体系的预聚物种类不多，选择性有限，且体系中自由基光固化树脂和阳离子光固化树脂的固化速度很难达到同步固化，从而导致固化后的产品硬度及附着性不佳。
混杂型光敏树脂是克服此类缺陷的重要研究方向。目前已有一些关于混杂型光敏树脂的专利报道，例如，JP2011168561A公开了一种具有多个氧杂环丁烷官能团和丙烯酰氧基官能团的化合物，其具有较快的固化速度和较高的硬度，但是该类化合物柔韧性差，附着性不够好，很大程度上影响了感光材料的性能。
发明内容
针对现有技术的不足，本发明的目的在于提供一种应用性能好的混杂型光敏树脂及其制备方法。该光敏树脂含氧杂环丁烷官能团和(甲基)丙烯酰氧基官能团，且官能度可调可控，应用于自由基-阳离子固化体系时固化速度快，不存在氧阻聚问题，且固化膜硬度高，柔韧性好，附着性和耐热性佳。
为了实现上述目的，本发明的混杂型光敏树脂，具有如下通式(I)所示结构：
Figure PCTCN2017092228-appb-000001
R1表示C1-C40的直链或支链的m价烷基、C2-C20的m价链烯基、或C6-C40的m价芳基，其中的-CH2-可任选地(optionally)被氧原子、-NH-或者1,4-亚苯基所取代，条件是两个-O-不直接相连；并且任选地，这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代；
R2表示C1-C20的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连，并且任选地，基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代；
R3表示氢、卤素、硝基、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C2-C10的链烯基、或C6-C20的芳基，任选地，这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代；
R表示氢或者甲基；
m表示1-8的整数。
在上述通式(I)所示结构中，m价连接基团R1将m个氧杂环丁烷官能团和m个(甲基)丙烯酰氧基官能团衔接成一个整体。
作为优选技术方案，R1表示C1-C40的直链或支链的m价烷基、C2-C10的直链或支链的m价链烯基、或C6-C30的m价芳基，其中的-CH2-可任选地被氧原子、-NH-或者1,4-亚苯基所取代，条件是两个-O-不直接相连；且任选地，这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代。
示例性地，R1可选自下列结构：
C1-C12的直链或支链的1-4价烷基、
Figure PCTCN2017092228-appb-000002
CH3-O-CH2CH2*、
Figure PCTCN2017092228-appb-000003
Figure PCTCN2017092228-appb-000004
*CH2CH2NHCH2CH2*、
Figure PCTCN2017092228-appb-000005
优选地，R2表示C1-C10的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连。
进一步优选地，R2表示C1-C6的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连。
优选地，R3表示氢、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C10的环烷基烷基、C4-C10的烷基环烷基、C2-C8的链烯基、或苯基。进一步优选地，R3表示C1-C4的直链或支链烷基、或C4-C8的环烷基烷基。
m优选为1-6的整数，更优选1-4的整数。
本发明公开的内容中，除另有说明，相关术语具有本领域通常理解的含义。数值范围包括端点值和端点值之间的所有点值，例如“C1-C10”包括C1、C2、C3、C4、C5、C6、C7、C8、C9、C10，“1-4的整数”包括1、2、3、4。
相应地，本发明还涉及上述通式(I)所示混杂型光敏树脂的制备方法，该方法以通式(II)所示含羟基化合物和通式(III)所示含氧杂环丁烷基化合物为起始原料，包括以下步骤：
Figure PCTCN2017092228-appb-000006
(1)开环反应
将通式(II)化合物和通式(III)化合物在催化剂存在条件下反应，得到中间体；其反应式如下：
Figure PCTCN2017092228-appb-000007
(2)酯化/酯交换反应
将中间体与(甲基)丙烯酸或(甲基)丙烯酸酯在催化剂存在条件下反应，得到产物；
Figure PCTCN2017092228-appb-000008
其中，R4表示氢或C1-C4烷基(如CH3、CH3CH2、CH3CH2CH2等)。
步骤(1)反应中使用的催化剂可以是：碱金属氢氧化物，如氢氧化钠、氢氧化钾等；醇的碱金属盐，如甲醇钠、乙醇钾、叔丁醇钠等；碱金属碳酸盐，如碳酸钠、碳酸钾等；碱金属碳酸氢盐，如碳酸氢钠、碳酸氢钾等；烷基金属锂化合物，如丁基锂、苯基锂等；胺基锂化合物，如二异丙基氨基锂、六甲基二硅氨基锂等。催化剂的用量对本领域技术人员而言是容易确定的，优选地，催化剂用量为通式(II)化合物的摩尔量的0.1-20％，更优选1-20％。
根据原料种类，步骤(1)的反应体系可任选地包含有机溶剂。对适用的溶剂种类没有特别限定，只要能够溶解反应原料且不对反应产生负面影响即可，例如可以是：乙腈、丙腈、苄腈等腈类溶剂；N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮等酰胺类溶剂；四氢呋喃、二氧杂环己烷等醚类溶剂；苯、甲苯、二甲苯等芳香族溶剂。这些溶剂可以单独 一种使用，也可以是两种以上混合使用，总用量可根据反应体系的均一性和搅拌性进行适当调节，这对本领域技术人员而言是容易确定的。
步骤(1)的反应温度通常为25-200℃，优选50-150℃。对反应压力没有特别限制，一般情况下常压即可。反应结束后，调节pH至中性，过滤、水洗、萃取、减压蒸馏，得到中间体化合物。
步骤(2)中，中间体化合物与(甲基)丙烯酸进行酯化反应、或者与(甲基)丙烯酸酯进行酯交换反应，从而得到通式(I)化合物。
步骤(2)的反应在含有催化剂的有机溶剂中进行，对溶剂种类没有特别限定，只要能够溶解反应原料且不对反应产生负面影响即可，如苯、甲苯、二甲苯等芳香族溶剂。溶剂可以单独一种使用，也可以是两种以上混合使用，总用量可根据反应体系的均一性和搅拌性进行适当调节，这对本领域技术人员而言是容易确定的。
酯化反应中使用的催化剂可以是无机酸，如：盐酸、磷酸、硼酸、浓硫酸等，也可以是有机酸，如：对甲苯磺酸、甲磺酸等。酯交换反应中使用的催化剂可以是钛酸酯类化合物，如钛酸-2-乙基己酯、钛酸四甲酯、钛酸四乙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异丁酯等中的一种或两种以上的组合。催化剂的用量对本领域技术人员而言是容易确定的，优选地，催化剂用量为中间体化合物的0.05-5wt％，更优选0.1-2wt％。
反应温度通常为0-200℃，优选50-150℃。反应结束后，水洗至中性，减压蒸馏除去溶剂，得到目标化合物。
本发明的混杂型光敏树脂包含多个氧杂环丁烷官能团和(甲基)丙烯酰氧基官能团。通过结构优化，功能性基团之间彼此呼应，导致该树脂非常适用于自由基-阳离子光固化体系，固化速度快，不存在氧阻聚问题，且固化膜硬度高，柔韧性好，附着性和耐热性优异。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
制备实施例
实施例1
(1)中间体1a的制备：
Figure PCTCN2017092228-appb-000009
向装有搅拌装置、温度计、回流冷凝管的250ml四口烧瓶中加入23g乙醇和2g氢氧化钠，搅拌升温至50℃，滴加86g 3-乙基-3-[(环氧乙烷基甲氧基)甲基]氧杂环丁烷，1h滴加完，继续搅拌反应，气相跟踪至乙醇含量不再变化，停止加热，调节pH至中性，过滤，水洗，萃取，减压蒸馏得到103g中间体1a。
(2)化合物1的制备：
Figure PCTCN2017092228-appb-000010
向装有回流冷凝管的250ml四口烧瓶中加入100g中间体1a、33g丙烯酸、0.2g对甲苯磺酸及100ml甲苯，加热回流反应跟踪至不再有水带出，停止反应。降温，水洗至中性，减压蒸馏除去溶剂，得到目标产物120g。
化合物1的结构通过GC-MS和1H-NMR得到确认。
MS(m/e)：272(M)
1H-NMR(CDCl3，500MHz)：δ0.96(3H，m)，δ1.13(2H，m)，δ1.25(2H，m)，δ3.29(2H，s)，δ3.42(2H，m)，δ3.61(4H，d)，δ4.61(1H，m)，δ4.66(4H，s)，δ5.82-6.42(3H，m)。
实施例2
(1)中间体2a的制备：
Figure PCTCN2017092228-appb-000011
向装有搅拌装置、温度计、回流冷凝管的1000ml四口烧瓶中加入265g原料1、4g氢氧化钠及300ml甲苯，搅拌升温至80℃，滴加258g 3-乙基-3-[(环氧乙烷基甲氧基)甲基]氧杂环丁烷，1.5h滴加完，继续搅拌反应，气相跟踪至原料1含量不再变化，停止加热，调节pH至中性，过滤，水洗、萃取，减压蒸馏得到507g中间体2a。
(2)化合物2的制备：
Figure PCTCN2017092228-appb-000012
向装有回流冷凝管的四口烧瓶中加入100g中间体2a、24.7g甲基丙烯酸、0.2g对甲苯磺酸及130ml甲苯，加热回流反应至不再有水带出，停止反应。降温，水洗至中性，减压蒸馏除去溶剂，得到目标化合物116g。
化合物2的结构通过GPC和IR得到确认。
GPC：
Figure PCTCN2017092228-appb-000013
IR(KBr)，ν/cm-1：981(s，
Figure PCTCN2017092228-appb-000014
)，1630(s，C＝C)，1200(m，C-O-C)，1720(s，C＝O)。
实施例3
参照实施例1和2的方法，由相应试剂合成具有表1中所示结构的化合物3-11：
表1
Figure PCTCN2017092228-appb-000015
Figure PCTCN2017092228-appb-000016
性能测试
1、固化性能测试
以上述实施例的化合物为例，配以光引发剂，对本发明所述光敏树脂的固化性能进行测试。
测试过程中，以具有相同官能度的纯阳离子体系或纯自由基体系作为比较对象，包括：单官能度阳离子单体苯基缩水甘油醚(960，湖北巨胜科技有限公司)、双官能度阳离子单体双酚A型环氧树脂(E51，江苏三木集团)、三官能度阳离子单体4,5-环氧环己烷-1,2-二甲酸二缩水甘油酯(TDE-85，天津津东化工厂)；单官能度自由基单体丙烯酸-β-羟乙酯(HEA，沙多玛)、双官能度自由基单体1,6-己二醇二丙烯酸酯(HDDA，沙多玛)、三官能度自由基单体三羟甲基丙烷三丙烯酸酯(TMPTA，沙多玛)。
测试中，使用的阳离子引发剂为PAG-202，自由基引发剂为184，其结构如下：
Figure PCTCN2017092228-appb-000017
(1)测试1—阳离子单体
参照表2所示配方选取原料，在暗室中搅拌均匀后，取样于PET膜，25#线棒涂布，形成膜厚约25μm的涂膜。将涂有涂层的PET膜置于履带式曝光机(RW-UV.70201，波长300-500nm)中进行曝光，曝光单次所接受的能量为80mj/cm2，记录各组配方固化完全所需的最低能量。
参照漆膜干燥时间测试标准GB/T 1728-1979中指触法来评价表面固化速度，即用手指轻触涂层，以表面滑爽，不粘手表示表面固化完全；采用指抠法测量底部固化速度，即用指甲轻抠涂层，以无脱落，无露底现象表示底层固化完全。
对本发明化合物与具有相应阳离子官能度的单体的固化性能进行测试。
表2
  配方1 配方2 配方3 配方4 配方5 配方6
960 6g - - - - -
E-51 - 6g - - - -
TDE-85 - - 6g - - -
化合物1 - - - 6g - -
化合物4 - - - - 6g -
化合物5 - - - - - 6g
PAG202 0.12g 0.12g 0.12g 0.06g 0.06g 0.06g
184 - - - 0.06g 0.06g 0.06g
曝光量 5次 4次 4次 2次 2次 1次
(2)测试2—自由基单体
依据表3所示配方，并参照测试1所示方法，对本发明化合物与具有相应自由基官能度的单体的固化性能进行测试。
表3
Figure PCTCN2017092228-appb-000018
从表2-3的结果可以看到，本发明的混杂型光敏树脂在配以自由基-阳离子光引发剂时，在固化效率方面具有明显优势，固化完全所需的能量明显低于具有相同阳离子或自由基官能度的单体，不存在氧阻聚问题。在同等官能度情况下，本发明的光敏树脂具有普遍更优的固化速度。
2、固化成膜后性能测试
通过应用于示例性光固化组合物，对本发明的混杂型光敏树脂固化成膜后的性能进行评价，主要包括膜硬度、附着性、柔韧性和耐热性(以玻璃化转变温度衡量)。其中，
本发明的光固化组合物按如下比例进行制备：
本发明的光敏树脂       98质量份
阳离子引发剂PAG-202     1质量份
自由基引发剂184         1质量份；
对比例1的光固化组合物按如下比例进行制备：
阳离子聚合单体E-51      98质量份
阳离子引发剂PAG-202     2质量份；
对比例2的光固化组合物按如下比例进行制备：
自由基聚合单体TMPTA   98质量份
自由基引发剂184         2质量份；
对比例3的光固化组合物按如下比例进行制备：
光固化聚合单体即化合物A         98质量份
阳离子引发剂PAG-202            1质量份
自由基引发剂184                1质量份
其中，化合物A是JP2011168561A中公开的化合物，结构如下：
Figure PCTCN2017092228-appb-000019
将配方组合物于暗室中搅拌均匀，以25#线棒分别涂布在玻璃基板上，获得厚度约为25μm的涂层，然后置于履带式曝光机(RW-UV.70201，波长300-500nm)中充分曝光10次，单次曝光为80mj/cm2，然后放置24h后进行测试。
(1)铅笔硬度测试
在温度23℃，相对湿度50％的条件下对本发明和对比例的固化膜进行测试。以GB/T6739-2006中规定的铅笔硬度评价方法为标准，将铅笔插入试验仪器中并用夹子将其固定，保 持水平，铅笔的尖端放在漆膜表面上，以1mm/s的速度朝离开自己的方向推动至少7mm距离，如果未出现划痕，在未测试区域重复实验，更换较高硬度的铅笔直至出现至少3mm长的划痕为止，以没有使涂层出现划痕的最硬的铅笔的硬度表示涂层的硬度。
(2)附着性测试
在温度23℃，相对湿度50％的条件下对本发明和对比例的固化膜进行测试。以GB/T9286-1998中规定的漆膜划格评价方法为标准，将涂膜切割为百格，刀尖在切割时要划及底材，并且刀尖要锋利，刀尖与涂膜成45度角。用软毛刷刷去漆屑，将3M透明胶带粘在划好的百格上，并施力使胶带牢固的粘在涂膜面及划格部位。在2min内，拿住3M胶带的一端，并呈60度角度，在1秒内平稳地撕离胶带，并按下述标准进行评价。
0级：切割边缘完全平滑无一脱落；
1级：在切口交叉处有少许涂层脱落，但交叉切割面积受影响不能明显大于5％；
2级：在切口交叉处和/或沿切口边缘有涂层脱落，受影响明显大于5％，但不能明显大于15％；
3级：涂层沿切割边缘部分或全部以大碎片脱落，和/或在格子不同部位上部分或全部剥落，受影响的交叉切割面积明显大于15％，但不能明显大于35％；
4级：涂层沿切割边缘大碎片剥落，和/或一些方格部分或全部脱落，受影响的交叉切割面积明显大于35％，但不能明显大于65％；
5级：剥落的程度超过4级。
(3)柔韧性
在温度23℃，相对湿度70％的条件下对实施例和对比例的固化膜进行测试，以GB/T1731-93漆膜柔韧性测试方法为依据，将涂有固化涂层的马口铁板的外侧沿长度方向依次卷绕在10、5、4、3、2、1毫米的棒轴上，弯曲2-3s，用放大镜观察，以涂料层破坏的最小的棒轴的直径来表示光固化涂层的柔韧性。
(4)耐热性测试
利用差示扫描量热仪(PE DSC8000)测试本发明和对比例得到的固化膜的玻璃化转变温度，测试条件：氮气氛围，以10℃/min的速率从-20℃加热至200℃，在200℃保持1min，然后以10℃/min的速率从200℃冷却至-20℃，在-20℃保持1min，接着在以10℃/min的速率从-20℃加热至200℃，从而测得玻璃化转变温度Tg(℃)。
测试和评价结果汇总于表4中。
表4
Figure PCTCN2017092228-appb-000020
从表4可以看到，本发明的混杂型光敏树脂应用于自由基-阳离子固化体系，相比于E51和TMPTA，能够赋予固化膜明显更高的硬度、更佳的附着性、柔韧性和更好的耐热性；并且相比于同类化合物A，在这四个方面也表现出了更好的应用性能。
综上所述，本发明提供的新型混杂型光敏树脂化合物综合了阳离子固化和自由基固化的优点，固化效率高，固化膜硬度、附着性、柔韧性和耐热性优异，且合成方法简单，品种多，对光固化领域的推广应用有很好的推动作用。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种混杂型光敏树脂，其特征在于，所述混杂型光敏树脂具有如下通式(I)所示结构：
    Figure PCTCN2017092228-appb-100001
    R1表示C1-C40的直链或支链的m价烷基、C2-C20的m价链烯基、或C6-C40的m价芳基，其中的-CH2-可任选地被氧原子、-NH-或者1,4-亚苯基所取代，条件是两个-O-不直接相连；并且任选地，这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代；
    R2表示C1-C20的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连，并且任选地，基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代；
    R3表示氢、卤素、硝基、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C2-C10的链烯基、或C6-C20的芳基，任选地，这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代；
    R表示氢或者甲基；
    m表示1-8的整数。
  2. 根据权利要求1所述的混杂型光敏树脂，其特征在于，R1表示C1-C40的直链或支链的m价烷基、C2-C10的直链或支链的m价链烯基、或C6-C30的m价芳基，其中的-CH2-可任选地被氧原子、-NH-或者1,4-亚苯基所取代，条件是两个-O-不直接相连；且任选地，这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代。
  3. 根据权利要求1或2所述的混杂型光敏树脂，其特征在于，R1选自下列结构：
    C1-C12的直链或支链的1-4价烷基、
    Figure PCTCN2017092228-appb-100002
    Figure PCTCN2017092228-appb-100003
  4. 根据权利要求1所述的混杂型光敏树脂，其特征在于，R2表示C1-C10的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连；优选地，R2表示C1-C6的直链或支链亚烷基，其主链中的-CH2-可任选地被氧原子取代，条件是两个-O-不直接相连。
  5. 根据权利要求1所述的混杂型光敏树脂，其特征在于，R3表示氢、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C10的环烷基烷基、C4-C10的烷基环烷基、C2-C8的链烯基、苯基；优选地，R3表示C1-C4的直链或支链烷基、或C4-C8的环烷基烷基。
  6. 根据权利要求1所述的混杂型光敏树脂，其特征在于，m为1-6的整数，优选1-4的整数。
  7. 权利要求1至6中任一项所述的混杂型光敏树脂的制备方法，其特征在于，以通式(II)所示含羟基化合物和通式(III)所示含氧杂环丁烷基化合物为起始原料，所述制备方法包括以下步骤：
    Figure PCTCN2017092228-appb-100004
    (1)开环反应
    将通式(II)化合物和通式(III)化合物在催化剂存在条件下反应，得到中间体；其反应式如下：
    Figure PCTCN2017092228-appb-100005
    (2)酯化/酯交换反应
    将所述中间体与(甲基)丙烯酸或(甲基)丙烯酸酯在催化剂存在条件下反应，得到产物；
    Figure PCTCN2017092228-appb-100006
    其中，R4表示氢或C1-C4烷基。
  8. 根据权利要求7所述的制备方法，其特征在于，步骤(1)反应中使用的催化剂选自碱金属氢氧化物、醇的碱金属盐、碱金属碳酸盐、碱金属碳酸氢盐、烷基金属锂化合物、和胺基锂化合物中的一种或两种以上的组合。
  9. 根据权利要求7所述的制备方法，其特征在于，步骤(2)中，将所述中间体与(甲基)丙烯酸进行酯化反应、或者与(甲基)丙烯酸酯进行酯交换反应，从而得到产物；所述酯化反应中使用的催化剂为无机酸或有机酸，所述酯交换反应中使用的催化剂是钛酸酯类化合物。
  10. 权利要求1至6中任一项所述的混杂型光敏树脂在自由基-阳离子光固化体系中的应用。
PCT/CN2017/092228 2016-07-13 2017-07-07 混杂型光敏树脂及其制备方法 WO2018010605A1 (zh)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019218335A (ja) * 2018-05-30 2019-12-26 住友化学株式会社 化合物、樹脂、レジスト組成物及びレジストパターンの製造方法
KR20210031726A (ko) * 2018-07-12 2021-03-22 샹조우 트론리 뉴 일렉트로닉 머티리얼즈 컴퍼니 리미티드 에폭시 변성 아크릴 수지, 이의 제조 방법, 에폭시 변성 아크릴 수지를 함유하는 에너지 경화성 조성물 및 응용
CN113620985A (zh) * 2021-08-13 2021-11-09 合肥工业大学 一种含硅的氧杂环丁烷衍生物及其制备方法和应用

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109305947B (zh) * 2017-07-27 2023-01-13 常州强力先端电子材料有限公司 一种氧杂环丁烷类单体化合物及其制备方法
CN110713763A (zh) * 2018-07-12 2020-01-21 常州强力电子新材料股份有限公司 可能量固化的丙烯酸树脂组合物及其应用
CN110713561A (zh) * 2018-07-12 2020-01-21 常州强力电子新材料股份有限公司 环氧改性的丙烯酸树脂及其制备方法
CN110845736A (zh) * 2018-08-21 2020-02-28 常州强力电子新材料股份有限公司 可能量固化的环氧接枝改性的有机硅树脂、含有其的可能量固化组合物及应用
CN109535303B9 (zh) * 2018-12-03 2022-07-19 东莞长联新材料科技股份有限公司 一种光固化低聚物，其制备方法和含有其的织物表面处理液及使用方法
CN111909118B (zh) * 2019-05-07 2022-05-17 常州强力先端电子材料有限公司 氧杂环丁烷化合物、光固化组合物、油墨及其应用
CN112111064A (zh) * 2019-06-21 2020-12-22 湖北固润科技股份有限公司 一种可混杂光固化的含多硅的氧杂环丁烷类单体及其制备和应用
CN111007699B (zh) * 2019-12-28 2023-07-14 阜阳欣奕华材料科技有限公司 一种感光性树脂及其制备方法和应用
WO2022210246A1 (ja) * 2021-03-29 2022-10-06 東レ株式会社 エポキシ樹脂組成物、エポキシ樹脂硬化物及びそれを用いた被覆繊維強化樹脂成形品
CN115304484B (zh) * 2022-08-11 2023-07-04 同济大学 三衣康酸衍生五官能度杂化单体及其制备方法和应用
CN115651589B (zh) * 2022-11-07 2024-03-19 深圳市优宝新材料科技有限公司 双固化胶黏剂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030017341A1 (en) * 2001-03-07 2003-01-23 3M Innovative Properties Company Adhesives and adhesive compositions containing thioether groups
CN101776846A (zh) * 2009-01-14 2010-07-14 北京光创物成材料科技有限公司 激光造型专用光固化组份
CN102782072A (zh) * 2010-03-09 2012-11-14 汉高公司 用于压敏粘合剂的阳离子的可uv交联的丙烯酸聚合物
WO2015085428A1 (en) * 2013-12-13 2015-06-18 Transfert Plus, Société En Commandite Insertion polynorbornene-based thermoset resins
CN104745104A (zh) * 2013-12-25 2015-07-01 东亚合成株式会社 光固化性粘接剂组合物、偏光板及其制造方法、光学构件以及液晶显示装置

Family Cites Families (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2895931A (en) 1958-03-31 1959-07-21 Hercules Powder Co Ltd Method for preparation of 3,3-disubstituted oxetane polymers
US3111470A (en) 1961-04-07 1963-11-19 Grace W R & Co Preparation of polymer of 3, 3-bis-(chloromethyl) oxetane
NL283094A (zh) 1961-09-14
US3341475A (en) 1962-08-28 1967-09-12 Hercules Inc Vulcanizable copolymers of oxetanes and halogen substituted epoxides
US4946992A (en) 1988-06-20 1990-08-07 Ciba-Geigy Corporation Heteroatom containing perfluoroalkyl terminated neopentyl glycols and compositions therefrom
US5362848A (en) 1992-12-11 1994-11-08 Aerojet-General Corporation Preparation and polymerization of initiators containing multiple oxetane rings: new routes to star polymers
JP3047800B2 (ja) 1995-11-20 2000-06-05 東亞合成株式会社 側鎖にオキセタニル基を含有する重合体の製造方法
FR2758557B1 (fr) * 1997-01-21 1999-11-12 Toagosei Co Ltd Compose ayant un groupe oxetanyle, son procede de preparation et composition de durcissement
US6096903A (en) 1997-03-25 2000-08-01 Ivoclar Ag Hydrolysable and polymerizable oxetane silanes
DE19736471A1 (de) 1997-08-21 1999-02-25 Espe Dental Ag Lichtinduziert kationisch härtende Zusammensetzungen und deren Verwendung
DE69941954D1 (de) 1998-07-09 2010-03-11 Jsr Corp Oxetanderivate, oxetancopolymer, und verfahren zur herstellung von oxetanderivaten
DE60031238D1 (de) 1999-08-12 2006-11-23 Mitsui Chemicals Inc Lichthärtbare harzzusammensetzung für dichtungsmaterialien und verfahren zum dichten
JP2001081182A (ja) * 1999-09-09 2001-03-27 Nippon Shokubai Co Ltd 重合性樹脂および重合性樹脂組成物
JP2003212965A (ja) 2002-01-28 2003-07-30 Brother Ind Ltd 活性エネルギー線硬化型組成物
KR100948534B1 (ko) 2002-04-15 2010-03-23 도아고세이가부시키가이샤 활성 에너지선 경화형 수지 조성물 및 그 경화물
EP1518899A3 (en) 2003-09-18 2005-08-03 Fuji Photo Film Co., Ltd. Photocurable adhesive and bonding process employing same
EP1679328A1 (en) 2003-09-18 2006-07-12 Kaneka Corporation Photocuring resin composition containing organic polymer having epoxy group and/or oxethane group-containing silicon group at end, and method for producing same
JP2006008791A (ja) 2004-06-24 2006-01-12 Konica Minolta Medical & Graphic Inc 活性光線硬化型組成物、活性光線硬化型インク、それを用いた画像形成方法及びインクジェット記録装置
US7230055B2 (en) 2004-07-29 2007-06-12 National Starch And Chemical Investment Holding Corporation Compositions containing oxetane compounds for use in semiconductor packaging
JP2006104307A (ja) * 2004-10-04 2006-04-20 Nippon Oil Corp 重合性液晶組成物およびこの組成物を用いた液晶フィルム
US20060223978A1 (en) 2005-04-04 2006-10-05 Shengqian Kong Radiation- or thermally-curable oxetane barrier sealants
US7927671B2 (en) * 2006-09-21 2011-04-19 Chisso Corporation Trifunctional compound, composition and polymer thereof
US20080103226A1 (en) 2006-10-31 2008-05-01 Dsm Ip Assets B.V. Photo-curable resin composition
KR100837409B1 (ko) 2006-11-30 2008-06-12 삼성전자주식회사 옥세탄-함유 화합물, 이를 포함한 포토레지스트 조성물,상기 포토레지스트 조성물을 이용한 패턴 형성 방법 및잉크젯 프린트 헤드
JP2009114337A (ja) * 2007-11-07 2009-05-28 Taiyo Ink Mfg Ltd 多分岐硬化性樹脂及びその硬化物
DE102009021913A1 (de) 2009-05-19 2010-12-02 Byk-Chemie Gmbh Terminal ungesättigte, oxetan-basierte Makromonomere und Verfahren zu deren Herstellung
JP5579533B2 (ja) 2009-08-27 2014-08-27 富士フイルム株式会社 新規なオキセタン化合物、活性エネルギー線硬化型組成物、活性エネルギー線硬化型インク組成物、及びインクジェット記録方法
KR101084799B1 (ko) 2009-09-08 2011-11-21 삼성에스디아이 주식회사 배터리 팩
JP2011157514A (ja) 2010-02-03 2011-08-18 Brother Industries Ltd カチオン重合型インク
US8981040B2 (en) * 2010-02-12 2015-03-17 Daicel Corporation Cationically polymerizable resin, cationically polymerizable resin composition, and cured products thereof
JP5531668B2 (ja) * 2010-02-22 2014-06-25 Ｄｉｃ株式会社 （メタ）アクリロイル基含有オキセタン化合物及びそれを含む硬化性組成物
WO2011129268A1 (ja) 2010-04-16 2011-10-20 ダイセル化学工業株式会社 ラジカル重合性樹脂、ラジカル重合性樹脂組成物、及びその硬化物
US9822088B2 (en) 2011-03-30 2017-11-21 The United States Of America As Represented By The Administrator Of Nasa Anisotropic copoly(imide oxetane) coatings and articles of manufacture, copoly(imide oxetane)s containing pendant fluorocarbon moieties, oligomers and processes therefor
KR101422659B1 (ko) 2011-05-12 2014-07-23 한국생산기술연구원 신규 옥세탄계 화합물, 그 제조방법, 및 이를 포함하는 디스플레이 기판용 복합시트
JP5723213B2 (ja) * 2011-05-16 2015-05-27 株式会社ダイセル カチオン重合性樹脂組成物、及びその硬化物
JP2014224205A (ja) 2013-05-17 2014-12-04 日東電工株式会社 光学部品用光硬化型樹脂組成物およびそれを用いた光学部品、並びに光学部品の製法
CN104447635B (zh) 2014-10-31 2017-09-15 常州强力电子新材料股份有限公司 一种含氧杂环丁烷基团的酯化合物及其制备方法
US9575409B2 (en) 2014-11-26 2017-02-21 Promerus, Llc Photoimageable compositions containing oxetane functionality
CN104774312B (zh) * 2015-04-28 2017-09-19 烟台德邦科技有限公司 一种可混杂固化树脂及其合成方法
JP6286396B2 (ja) 2015-08-13 2018-02-28 株式会社ダイセル 硬化性組成物及びその硬化物
CN107619399B (zh) * 2016-07-13 2021-04-27 常州强力先端电子材料有限公司 多官能度氧杂环丁烷类化合物及其制备方法
CN109305947B (zh) * 2017-07-27 2023-01-13 常州强力先端电子材料有限公司 一种氧杂环丁烷类单体化合物及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030017341A1 (en) * 2001-03-07 2003-01-23 3M Innovative Properties Company Adhesives and adhesive compositions containing thioether groups
CN101776846A (zh) * 2009-01-14 2010-07-14 北京光创物成材料科技有限公司 激光造型专用光固化组份
CN102782072A (zh) * 2010-03-09 2012-11-14 汉高公司 用于压敏粘合剂的阳离子的可uv交联的丙烯酸聚合物
WO2015085428A1 (en) * 2013-12-13 2015-06-18 Transfert Plus, Société En Commandite Insertion polynorbornene-based thermoset resins
CN104745104A (zh) * 2013-12-25 2015-07-01 东亚合成株式会社 光固化性粘接剂组合物、偏光板及其制造方法、光学构件以及液晶显示装置

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019218335A (ja) * 2018-05-30 2019-12-26 住友化学株式会社 化合物、樹脂、レジスト組成物及びレジストパターンの製造方法
KR20210031726A (ko) * 2018-07-12 2021-03-22 샹조우 트론리 뉴 일렉트로닉 머티리얼즈 컴퍼니 리미티드 에폭시 변성 아크릴 수지, 이의 제조 방법, 에폭시 변성 아크릴 수지를 함유하는 에너지 경화성 조성물 및 응용
JP2021524528A (ja) * 2018-07-12 2021-09-13 常州強力電子新材料股▲分▼有限公司ＣＨＡＮＧＺＨＯＵ ＴＲＯＮＬＹ ＮＥＷ ＥＬＥＣＴＲＯＮＩＣ ＭＡＴＥＲＩＡＬＳ Ｃｏ．， Ｌｔｄ． エポキシ変性アクリル樹脂、その製造方法、エネルギー硬化性のエポキシ変性アクリル樹脂含有組成物および使用
JP7245315B2 (ja) 2018-07-12 2023-03-23 常州強力電子新材料股▲分▼有限公司 エポキシ変性アクリル樹脂、その製造方法、エネルギー硬化性のエポキシ変性アクリル樹脂含有組成物および使用
KR102559076B1 (ko) * 2018-07-12 2023-07-24 샹조우 트론리 뉴 일렉트로닉 머티리얼즈 컴퍼니 리미티드 에폭시 변성 아크릴 수지, 이의 제조 방법, 에폭시 변성 아크릴 수지를 함유하는 에너지 경화성 조성물 및 응용
CN113620985A (zh) * 2021-08-13 2021-11-09 合肥工业大学 一种含硅的氧杂环丁烷衍生物及其制备方法和应用

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