CN108957950A - The UV Photocurable composition of the photoinitiator of aminoketones containing fluorenes - Google Patents
The UV Photocurable composition of the photoinitiator of aminoketones containing fluorenes Download PDFInfo
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- CN108957950A CN108957950A CN201711472418.2A CN201711472418A CN108957950A CN 108957950 A CN108957950 A CN 108957950A CN 201711472418 A CN201711472418 A CN 201711472418A CN 108957950 A CN108957950 A CN 108957950A
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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
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- 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
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a kind of UV Photocurable compositions of photoinitiator of aminoketones containing fluorenes.The UV Photocurable composition includes: the unsaturated photopolymerizable compound of dilute category and photoinitiator；Wherein, photoinitiator includes the compound or its derivative compound with the structure as shown in general formula (I),
Description
Technical field
The present invention relates to UV light radiation free radical polymerization new material technology fields, in particular to a kind of amino containing fluorenes
The UV Photocurable composition of ketone-type photoinitiators.
Background technique
1988, patent EP284561 disclosed application of the alpha-amido ketone compounds as photoinitiator, finally selected
2- dimethylamino -2- benzyl -1- (4- morphlinophenyl) -1- butanone is as commercially produced product.But the photoinitiator has one
It is a it is clearly disadvantageous be that solubility is small, prepare difficult, the low-temperature stability of compound composition is poor, is more than especially with concentration
When 5%.2001,2- methyl-1-[4- (methyl thio) phenyl]-2- (4- was disclosed in patent document JP2001348412A
Quinoline base) the liquid curable resin composition of -1- acetone (trade name Irgacure 907) as photoinitiator component.But
Aromatic ring system contains methyl mercapto in the compound structure, therefore generates bad smell after being inevitably present illumination cracking,
There is the problems such as serious xanthochromia in cured article, this is that cannot be applied in fields such as food packaging, varnish paint, white inks
's.
In view of the foregoing drawbacks, in recent years, also there is relevant report for the research of 907 photoinitiator substitute of Irgacure,
Such as a series of alpha-amido ketone compounds of biphenyl derivatives are disclosed in number of patent application CN101724099, wherein 1-
([1,1- xenyl] -4- base) -2- methyl -2- morpholinopropane -1- ketone is effective substitute of Irgacure 907.The chemical combination
Object be free of element sulphur, applied to embodied in UV radical photopolymerization curing system excellent yellowing resistance, illumination decompose after not
Bad smell can be generated.But find in practical applications, the photoinitiator dissolubility is poor, easily distils, can be to production equipment
It is polluted with light source, so being not a perfect substitute.
These problems are in the field of business to be attracted extensive attention, the problems such as because of the odor profiles of photoinitiator, xanthochromia, toxicity significantly
UV coating, UV ink are limited in various fields such as furniture, electric appliance, automobile interior decoration, cigarette, food, medicine and cosmetics
Using.Exploitation can effectively solve the above problems and have in economy and environment friendly the photocurable composition of advantage competition power
Object is one of the important topic that the current industrial field faces.
Summary of the invention
The present invention is intended to provide a kind of UV Photocurable composition of the photoinitiator of aminoketones containing fluorenes, to improve UV photocuring
The anti-yellowing property of composition.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of photoinitiator of aminoketones containing fluorenes
UV Photocurable composition.The UV Photocurable composition includes: the unsaturated photopolymerizable compound of dilute category and photoinitiator；Its
In, photoinitiator includes the compound or its derivative compound with the structure as shown in general formula (I),
Wherein,
A represents hydrogen, halogen, nitro, C1-C20Linear or branched alkyl group, C3-C10Alkyl-cycloalkyl, C4-C10Alkyl
Naphthenic base or cycloalkyl-alkyl,-COR6Or-CO-CR2R3R4Group, wherein optional ,-CH2By O, N, S or C
(=O) it is replaced；
R1Represent hydrogen, halogen, C1-C20Linear or branched alkyl group, C4-C20Cycloalkyl-alkyl or C2-C20Alkenyl,
Optionally, R1In-CH2Replaced, the R by O, N, S or C (=O)1Between can cyclization；
R2And R3Separately represent C1-C20Linear or branched alkyl group, C3-C20Naphthenic base, C4-C20Naphthenic base
Alkyl, C4-C20Alkyl-cycloalkyl, C6-C20Aryl, C6-C20Alkylaryl, wherein one or more hydrogen in these groups
Can be independently of one another replaced alkyl, halogen, hydroxyl, nitro, and optional, R2And R3In-CH2By O, N, S or C
(=O) it is replaced, and R2And R3It can be mutually cyclic；
R4N- morpholinyl, N- piperidyl, N- pyrrole radicals or N- dialkyl group are represented, wherein one or more of these groups
Hydrogen atom can be replaced halogen, hydroxyl；
R5、R5' C is represented independently of one another1-C20Linear chain or branched chain alkyl, C4-C20Naphthenic base, C2-C20Alkene
Base, C6-C20Aryl, C6-C20Alkylaryl, wherein one or more hydrogen in these groups can be independently of one another by alkane
Base, halogen, hydroxyl, replaced nitro, and optionally ,-the CH in these groups2It can be replaced by-O-；Or R5And R5' can
To be connected with each other or form five yuan or hexatomic ring by-O- ,-S- ,-NH-；
R6It represents unsubstituted or by one or more C1-C20Alkyl, halogen, cyano, SR7、OR8Substituted phenyl；
R7And R8Independently represent hydrogen, C1-C20Linear or branched alkyl group.
Further, dilute dosage for belonging to unsaturated photopolymerizable compound is 5-95 mass parts, and the dosage of photoinitiator is
0.05-15 mass parts.
Further, dilute dosage for belonging to unsaturated photopolymerizable compound is 10-90 mass parts, and the dosage of photoinitiator is
1-10 mass parts.
Further, with the structure as shown in general formula (I) photoinitiator selected from by
One of group of composition is a variety of.
Further, the derivative compound of the photoinitiator with the structure as shown in general formula (I), which is included in, keeps formula (I)
Under the premise of conjunction object main structure is constant, derivative compound obtained from replacing or be connected to each other as its branch.
Further, derivative compound has such as logical formula (II) or (III) compound represented:
Wherein, M represents dimerization
And the linking group formed, it can be dead key, C1-C10Linear chain or branched chain alkylidene, C6-C12Arlydene or inferior heteroaryl,
Optionally ,-the CH in M2Replaced sulphur, oxygen, NH or carbonyl, optionally, hydrogen atom is by OH or NO2It is replaced.
Further, derivative compound is
Further, the photoinitiator with the structure as shown in general formula (I) or its derivative compound are two or more changes
Close the mixture of object.
Further, the unsaturated photopolymerizable compound of dilute category is monomeric compound or oligomer.
Further, the unsaturated photopolymerizable compound of dilute category is the compound comprising a carbon-carbon double bond, preferably third
Enoic acid ester compounds or methacrylate compound；Or the unsaturated photopolymerizable compound of dilute category be comprising two and two with
The compound of upper carbon-carbon double bond, preferably alkyl diol, the acrylate of polyalcohol or methacrylate or polyester are more
First alcohol, polyether polyol, epoxy resin polyalcohol, the acrylate of polyurethane polyol, vinyl ethers and unsaturated binary
The unsaturated polyester (UP) of carboxylic acid multicomponent alcohol.
Further, when UV Photocurable composition is as UV etching resisting ink or UV solder mask purposes, dilute category for using
At least one of unsaturated photopolymerizable compound compound contains alkali solubility group, preferably carboxylic resin.
Further, carboxylic resin is (methyl) acrylate, ethylene unsaturated carboxylic acid or (methyl) acrylic acid
Ester based polymer；
Preferably, (methyl) acrylate is selected from by (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third
Olefin(e) acid butyl ester, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid diethylaminoethyl, (first
Base) acrylate dimethylamino ethyl ester, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid chaff
One of base ester, group of (methyl) glycidyl acrylate composition are a variety of；
Preferably, ethylene unsaturated carboxylic acid is selected from is rested in peace acid, maleic acid, horse by acrylic acid, methacrylic acid, vinyl
Come acid alkyl ester, fumaric acid, itaconic acid, butenoic acid, cinnamic acid, acrylic acid dimer, monomer and cyclic acid anhydride with hydroxyl
Addition product, ω-carboxyl-polycaprolactone-(methyl) acrylate composition one of group or a variety of, more preferably (first
Base) acrylic acid；
Preferably, (methyl) acrylic ester polymer be selected from by (methyl) acrylamide, (methyl) n-butyl acrylate,
One of styrene, vinyl naphthalene, (methyl) acrylonitrile, group of vinyl-acetic ester, vinyl cyclohexane composition are a variety of.
Further, UV Photocurable composition further includes other photoinitiators, it is preferred that other photoinitiators are selected from by two
Benzophenone, benzil dimethyl ketal, 2- hydroxy-2-methyl -1- phenyl-propanone, 1- hydroxy-cyclohexyl-phenyl -one, isopropyl
Base thioxanthene, (2,4,6- trimethyl-benzoyl) diphenyl phosphine oxide and bis- (2,4,6- trimethylbenzoyl)-phenyl oxygen
Change one of group of phosphine composition or a variety of.
Further, UV Photocurable composition further includes sensitizer；Preferably, sensitizer is pyrazoline compounds, a word used for translation
Pyridine class compound, anthracene compound, coumarin kind compound or tertiary amine compounds；It is furthermore preferred that the dosage of sensitizer is 0-5
Mass parts, it is further preferred that the dosage of sensitizer is 0-2 mass parts.
Further, UV Photocurable composition further includes colorant, and colorant is inorganic pigment or organic pigment, colorant
Dosage be 0-50 mass parts, it is preferred that the dosage of colorant be 0-20 mass parts.
Further, UV Photocurable composition further includes that additive includes surfactant, wetting agent, dispersing agent, rheology
One of modifying agent, defoaming agent or storage reinforcing agent are a variety of；Preferably, the dosage of additive is 0-5 mass parts, more preferably
, the dosage of additive is 0-3 mass parts.
According to another aspect of the present invention, it is oily in UV coating and UV to provide a kind of any of the above-described kind of UV Photocurable composition
The application of black aspect.
Further, UV ink includes UV etching resisting ink, UV solder mask, flexo ink and offset ink etc..The present invention
The amino ketone photoinitiator containing fluorenes UV Photocurable composition, have high sensitivity, noresidue after development, pattern integrity is good, and
And coating odorlessness or low smell after solidifying, in addition anti-yellowing property is also very excellent.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
A kind of typical embodiment according to the present invention provides a kind of UV photocuring group of photoinitiator of aminoketones containing fluorenes
Close object.The UV Photocurable composition includes: the unsaturated photopolymerizable compound of dilute category and photoinitiator；Wherein, photoinitiator packet
Compound or its derivative compound with the structure as shown in general formula (I) are included,
Wherein,
A represents hydrogen, halogen, nitro, C1-C20Linear or branched alkyl group, C3-C10Alkyl-cycloalkyl, C4-C10Alkyl
Naphthenic base or cycloalkyl-alkyl,-COR6Or-CO-CR2R3R4Group, wherein optional ,-CH2By O, N, S or C
(=O) it is replaced；
R1Represent hydrogen, halogen, C1-C20Linear or branched alkyl group, C4-C20Cycloalkyl-alkyl or C2-C20Alkenyl,
Optionally, R1In-CH2Replaced, the R by O, N, S or C (=O)1Between can cyclization；
R2And R3Separately represent C1-C20Linear or branched alkyl group, C3-C20Naphthenic base, C4-C20Naphthenic base
Alkyl or C4-C20Alkyl-cycloalkyl, C6-C20Aryl, C6-C20Alkylaryl, wherein one or more of these groups
Hydrogen can be independently of one another replaced alkyl, halogen, hydroxyl, nitro, and optional, R2And R3In-CH2By O, N, S or C
(=O) it is replaced, and R2And R3It can be mutually cyclic；
R4N- morpholinyl, N- piperidyl, N- pyrrole radicals or N- dialkyl group are represented, wherein one or more of these groups
Hydrogen atom can be replaced halogen, hydroxyl；
R5、R5' C is represented independently of one another1-C20Linear chain or branched chain alkyl, C4-C20Naphthenic base, C2-C20Alkene
Base, C6-C20Aryl, C6-C20Alkylaryl, wherein one or more hydrogen in these groups can be independently of one another by alkane
Base, halogen, hydroxyl, replaced nitro, and optionally ,-the CH in these groups2It can be replaced by-O-；Or R5And R5' can
To be connected with each other or form five yuan or hexatomic ring by-O- ,-S- ,-NH-；
R6It represents unsubstituted or by one or more C1-C20Alkyl, halogen, cyano, SR7、OR8Substituted phenyl；
R7And R8Independently represent hydrogen, C1-C20Linear or branched alkyl group.Amino ketones containing fluorenes of the invention is light-initiated
The UV Photocurable composition of agent has high sensitivity, and noresidue after development, pattern integrity is good, and coating odorlessness after solidification
Or low smell, in addition anti-yellowing property is also very excellent.
UV Photocurable composition preparation process of the invention is simple, and a kind of typical embodiment, above-mentioned according to the present invention
Component is uniformly mixed in darkroom or yellow fluorescent lamp environment.
A kind of typical embodiment according to the present invention, UV Photocurable composition further include other photoinitiators, it is preferred that
Other photoinitiators are selected from by benzophenone, benzil dimethyl ketal, 2- hydroxy-2-methyl -1- phenyl-propanone, 1- hydroxyl -
Cyclohexyl-phenyl -one, isopropyl thioxanthone anthracene, (2,4,6- trimethyl-benzoyl) diphenyl phosphine oxide and bis- (2,4,6- tri-
Methyl benzoyl)-phenyl phosphine oxide composition one of group or a variety of.
A kind of typical embodiment according to the present invention, UV Photocurable composition further include colorant, and colorant is inorganic
Pigment or organic pigment, the dosage of colorant are 0-50 mass parts, it is preferred that the dosage of colorant is 0-20 mass parts.
A kind of typical embodiment according to the present invention, UV Photocurable composition further include additive, and additive includes table
One of face activating agent, wetting agent, dispersing agent, rheology modifier, defoaming agent or storage reinforcing agent are a variety of.
UV Photocurable composition each component of the invention will be described in more details below.
1) the unsaturated photopolymerizable compound of dilute category
It is dilute to belong to unsaturated photopolymerizable compound: the compound of dilute category unsaturated bond with free redical polymerization, it can be with
For monomeric compound (low molecular weight) or oligomer (higher molecular weight).
Compound comprising a carbon-carbon double bond, preferred acrylate compound, methacrylate compound, such as:
The acrylate or methacrylate of monohydric alcohol: methyl acrylate, butyl acrylate, 2-EHA, acrylic acid
Cyclohexyl, isobornyl acrylate, hydroxy-ethyl acrylate, methyl methacrylate and acrylonitrile, N- dialkylacrylamides,
N-vinyl pyrrolidone, vinyl benzene, vinylacetate, vinyl ethers.
Comprising two and the compound of more than two carbon-carbon double bond, comprising: alkyl diol, polyalcohol acrylate or
Methacrylate or polyester polyol, polyether polyol, epoxy resin polyalcohol, polyurethane polyol acrylate,
The unsaturated polyester (UP) of vinyl ethers and unsaturated dicarboxylic acid polyalcohol, for example, polyethyleneglycol diacrylate, neopentyl glycol
Diacrylate, trimethylolpropane trimethacrylate, more ethoxylated trimethylolpropane triacrylates, pentaerythrite four
Acrylate, dipentaerythritol hexaacrylate, polyester oligomer acrylate, urethane oligomer acrylate, aromatic series
Epoxy Resin Acrylate, maleic acid polyglycol ester.
When UV Photocurable composition is as UV etching resisting ink or UV solder mask purposes, the dilute category unsaturation used can light
At least one of polymerizable compound compound contains alkali solubility group, this kind of compound other than it can be initiated cross-linked polymeric,
It also wants to have developer solution used in development treatment process (common alkaline-based developer) when forming picture pattern solvable
Xie Xing, preferably carboxylic resin.Especially by (methyl) acrylate, ethylene unsaturated carboxylic acid and other copolymerisable monomers
(methyl) acrylic ester polymer made of copolymerization.Described (methyl) acrylate can be (methyl) methyl acrylate,
(methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (first
Base) acrylic acid diethylaminoethyl, (methyl) acrylate dimethylamino ethyl ester, (methyl) hydroxy-ethyl acrylate, (methyl) third
Olefin(e) acid hydroxypropyl acrylate, (methyl) acrylic acid furfuryl group ester, (methyl) glycidyl acrylate, these (methyl) acrylate can be single
It solely uses, can also be used in combination.The ethylene unsaturated carboxylic acid be preferably acrylic acid, methacrylic acid,
Vinyl is rested in peace acid, maleic acid, alkyl maleates, fumaric acid, itaconic acid, butenoic acid, cinnamic acid, acrylic acid dimer, tool
Have hydroxyl monomer (such as (methyl) acrylic acid -2- hydroxyl ethyl ester etc.) and cyclic acid anhydride (such as: maleic anhydride or phthalic acid
Acid anhydride, two contracting acid anhydrides of hexamethylene) addition product, ω-carboxyl-polycaprolactone-(methyl) acrylate etc..Wherein from copolymerizable or
The consideration of the viewpoints such as cost, dissolubility, particularly preferred (methyl) acrylic acid.These ethylene unsaturated carboxylic acids can be used alone,
It can also be used in combination.Other described copolymerisable monomers are preferably (methyl) acrylamide, (methyl) acrylic acid
N-butyl, styrene, vinyl naphthalene, (methyl) acrylonitrile, vinyl-acetic ester, vinyl cyclohexane, these monomers can be single
It solely uses, can also be used in combination.
These carbon-carbon double bond compounds not only can be used alone, can with it is two or more be used in mixed way or mixture between
It can carry out pre- copolymerization and form oligomer for compositions formulated use.It is present in free-radical polymerised resin in Photocurable composition
Dosage be 5-95 mass parts, preferably from about 10-90 mass parts.
2) with the photoinitiator of the structure as shown in general formula (I)
As photoinitiator used in Photocurable composition of the present invention, including at least has fluorenes shown in logical formula (I)
One of compound of structure or derivatives thereof compound based on class compound:
Wherein,
A represents hydrogen, halogen, nitro, C1-C20Linear or branched alkyl group, C3-C10Alkyl-cycloalkyl, C4-C10Alkyl
Naphthenic base or cycloalkyl-alkyl,-COR6Or-CO-CR2R3R4Group, wherein optional ,-CH2By O, N, S or C
(=O) it is replaced；
R1Represent hydrogen, halogen, C1-C20Linear or branched alkyl group, C4-C20Cycloalkyl-alkyl or C2-C20Alkenyl,
Optionally, R1In-CH2Replaced, the R by O, N, S or C (=O)1Between can cyclization；
R2And R3Separately represent C1-C20Linear or branched alkyl group, C3-C20Naphthenic base, C4-C20Naphthenic base
Alkyl, C4-C20Alkyl-cycloalkyl, C6-C20Aryl, C6-C20Alkylaryl, wherein one or more hydrogen in these groups
Can be independently of one another replaced alkyl, halogen, hydroxyl, nitro, and optional, R2And R3In-CH2By O, N, S or C
(=O) it is replaced, and R2And R3It can be mutually cyclic；
R4N- morpholinyl, N- piperidyl, N- pyrrole radicals or N- dialkyl group are represented, wherein one or more of these groups
Hydrogen atom can be replaced halogen, hydroxyl；
R5、R5' C is represented independently of one another1-C20Linear chain or branched chain alkyl, C4-C20Naphthenic base, C2-C20Alkene
Base, C6-C20Aryl, C6-C20Alkylaryl, wherein one or more hydrogen in these groups can be independently of one another by alkane
Base, halogen, hydroxyl, replaced nitro, and optionally ,-the CH in these groups2It can be replaced by-O-；Or R5And R5' can
To be connected with each other or form five yuan or hexatomic ring by-O- ,-S- ,-NH-；
R6It represents unsubstituted or by one or more C1-C20Alkyl, halogen, cyano, SR7、OR8Substituted phenyl；
R7And R8Independently represent hydrogen, C1-C20Linear or branched alkyl group.
Preferably, fluorenes amino ketone compound shown in formula (I) includes with compound shown in flowering structure:
The derivative compound of structure, which refers to, based on compound shown in formula (I) is keeping formula (I) compound main structure
Under the premise of constant, derivative obtained from replacing or be connected to each other as its branch.Make in the present invention as photoinitiator
Used time, the derivative compound of the structure based on compound shown in formula (I) are the chemical combination as shown in following formula (II), (III)
Object:
Formula (II) and formula (III) are the dimer of formula (I), and M, which indicates dimerization and the linking group that is formed, to be sky
Key, C1-C10Linear chain or branched chain alkylidene, C6-C12Arlydene or inferior heteroaryl ,-the CH in M2Optionally by sulphur, oxygen, NH
Or replaced carbonyl, hydrogen atom is optionally by OH or NO2It is replaced.
Illustratively, above-mentioned derivative compound can be the compound of having structure:
In some cases, it is advantageous using the mixture of initiator described in two or more.
Certainly, the photoinitiator with the structure as shown in general formula (I) can also mix with other known photoinitiators and make
With.
3) other photoinitiators
Such as: camphorquinone, benzophenone (BP), benzophenone derivates, such as 2,4,6- tri-methyl benzophenones, 2- first
Base benzophenone, 2 methyl benzophenone, 3- methyl benzophenone, 4- methyl benzophenone, 2- methyl base carbonyl benzophenone,
4,4 '-bis- (chloromethyl) benzophenone, 4- chlorobenzophenone, 4- phenyl benzophenone, 3,3 '-dimethyl -4- methoxyl groups-hexichol
Ketone, [4- (4- methylphenyl-sulfanyl) phenyl]-phenyl ketone, 2- benzoyl methyl benzoate, 3- methyl -4 '-phenyl hexichol
Ketone, 2,4,6- trimethyl -4 '-phenyl benzophenone, 4,4 '-bis- (dimethylamino) benzophenone, 4,4 '-bis- (diethyl
Amino) benzophenone, ketal compound, such as benzil dimethyl ketal (651)；Acetophenone, acetophenone derivs, such as α-
Hydroxycycloalkylphenyl ketone, such as 2- hydroxy-2-methyl -1- phenyl-propanone (1173), 1- hydroxy-cyclohexyl-phenyl -one
(184)；1- [4- (2- hydroxyl-oxethyl)-phenyl] -2- hydroxy-2-methyl -1- propyl- 1- ketone (2959)；2- hydroxyl -1- { 4- [4-
(2- hydroxy-2-methyl-propiono)-benzyl]-phenyl } -2- methyl -propyl- 1- ketone (127)；2- hydroxyl -1- { 4- [4- (2- hydroxyl
Base -2- methyl-propanoyl)-phenoxy group]-yl } -2- methyl -propyl- 1- ketone；Dialkoxy acetophenones, Alpha-hydroxy-or alpha-amido benzene
Ethyl ketone, such as (4- methylthio phenyl formoxyl)-1- methyl-1-morpholino ethane (907), (4- morpholino benzoyl)-1- benzyl
Base -1- dimethylaminopropanecompounds (369), (4- morpholino benzoyl) -1- (4- methylbenzyl) -1- dimethylaminopropanecompounds
(379), (4- (2- hydroxyethyl) amino benzoyl) -1- benzyl -1- dimethylaminopropanecompounds), 2- benzyl -2- dimethylamino
Base -1- (3,4- Dimethoxyphenyl) -1- butanone；Thioxanthone and its derivative, such as isopropyl thioxanthone anthracene (ITX), 2- chlorine
The chloro- 4- propoxyl group thioxanthone (CPTX) of thioxanthone (CTX), 1-, 2,4- diethyl thioxanthone (DETX)；Benzoin alkyl
Ether and benzil ketals, phenyl glyoxylic acid ester and its derivative, such as oxo-phenyl-acetic acid 2- (2- Hydroxy-ethoxy)-second
Base ester, the phenyl glyoxylic acid ester of dimerization, such as oxo-phenyl-acetic acid 1- methyl -2- [2- (2- oxo-phenyl acetoxyl group) -
Propoxyl group]-ethyl ester (754)；Other oxime esters, such as 1,2- octadione- 1- [4- (thiophenyl) phenyl] -2- (4- benzoyl
Oxime) (OXE01), ethyl ketone 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -1- (4- acetyl group oxime)
(OXE02), 9H- thioxanthene -2- formaldehyde 9- oxo -2- (O- acetyl group oxime)；Monoacylphosphine oxides, such as (2,4,6- trimethyls-benzene
Formoxyl) diphenyl phosphine oxide (TPO)；Bis-acylphosphine oxides, such as double-(2,6- dimethoxy-benzoyl)-(2,4,4-
Trimethyl-pentyl) phosphine oxide, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides (819), bis- (2,4,6- trimethylbenzenes
Formoxyl) -2,4- diamyl phenyl-phosphine oxide；Hexa-aryl bi-imidazole/coinitiator system, for example, with 2- sulfydryl benzo thiophene
Adjacent chlorine hexaphenyl-bis- imidazoles etc. that azoles combines.
It is worth noting that the photoinitiator with the structure as shown in general formula (I) is except formula (I), formula (II) and formula (III)
Except compound, it is particularly suitable for that one or more is applied in combination with BP, 651,1173,184, ITX, TPO and 819 etc..
Photoinitiator is the photoinitiator and dosage of other photoinitiators in Photocurable composition with the structure as shown in general formula (I)
For 0.05-15 mass parts, preferably 1-10 mass parts.
4) sensitizer
In addition, in Photocurable composition of the invention, higher sensitivity or in order to match with LED light source in order to obtain,
Also it can further include sensitizer.
The type of sensitizer can be pyrazoline compounds, acridine compound, anthracene compound, Coumarins chemical combination
Object, tertiary amine compounds etc..It specifically can illustratively enumerate: 1- phenyl -3- (4- t-butyl styrene base) -5- (uncle 4-
Butyl phenyl) pyrazoline, 1- phenyl -3- xenyl -5- (4- tert-butyl-phenyl) pyrazoline；9- phenylacridine, 9- are to methylbenzene
Aminomethyl phenyl acridine, 9- Chloro-O-Phenyl acridine between base acridine, 9-；2- ethyl anthracene -9,10- two (4- chlorobutanoate), 1,2,3-
Trimethyl anthracene -9,10- dioctyl ester, 2- ethyl anthracene -9,10- diethylester, 2- ethyl anthracene -9,10- two (3- cyclohexylpropionic acid ester)；3,
3'- carbonyl bis- (7- diethylamine cumarins), 3- benzoyl -7- diethylamine cumarin, bis- (the 7- methoxyl group tonka-beans of 3,3'- carbonyl
Element), 7- (lignocaine) -4- methylcoumarin；N, N- be bis--[4- (2- styryl -1- base)-phenyl]-N, bis- (the 2- second of N-
- 6 aminomethyl phenyl of base) the double phenyl -4,4- diamines of -1,1-, N, N- is bis--[4- (2- styryl -1- base) -4 '-aminomethyl phenyl]-N,
Double phenyl -4,4- diamines of bis- (- 6 aminomethyl phenyl of 2- the ethyl) -1,1- of N- etc..
Dosage of the sensitizer in Photocurable composition is 0-5 mass parts, preferably 0-2 mass parts.
5) colorant
It may include one or more pigment in UV Photocurable composition as colorant.Pigment can be any color, including
But be not limited to black, blue, brown, cyan, green, white, purple, magenta, red, orange and yellow and they mix
The spot color of object.Pigment can be inorganic pigment or organic pigment.
Organic pigment present in UV Photocurable composition can be perylene, phthalocyanine dyestuffs (such as phthalocyanine green, phthalocyanine
It is blue), cyanine pigment (Cy3, Cy5 and Cy7), naphthalene phthalocyanine color, nitroso pigments, azo pigments, diazo pigment, diazonium be condensed face
Material, basic dye pigments, alkali blue pigment, indigo pigment, root skin red pigment, Kui quinacridone pigment, isoindolenone pigments, two
Oxazines pigment, carbazole dioxazine violet pigment, alizarine lake pigment, phthalic amide pigment, carmine lake pigment, tetrachloro are different
The mixture or more of indolinone pigment, purple cyclic ketones pigment, anthraquinone pigment and quinophthalone pigments and both the above or more
Derivative.
Inorganic pigment includes in Photocurable composition, such as metal oxide (such as titanium dioxide, electric conductivity titanium dioxide
Titanium), ferriferous oxide (such as red iron oxide, yellow iron oxide, black iron oxide and transparent ferric oxide), aluminum oxide, silicon oxygen
Compound, carbon black pigment, metal sulfide, metal chloride and they two or more mixture.
Dosage of the colorant in Photocurable composition is 0-50 mass parts, preferably 0-20 mass parts.
6) additive
According to the demand of different application, other components or additive may be optionally present in Photocurable composition, to improve
The property and performance of coating or ink.Additive include but is not limited to surfactant, wetting agent, dispersing agent, rheology modifier,
One of defoaming agent or storage reinforcing agent are a variety of.
Dosage of the additive in Photocurable composition is 0-5 mass parts, preferably 0-3 mass parts.
Photocurable composition of the invention is in polymerization reaction by assigning ultraviolet light, luminous ray, near infrared ray etc., electricity
The energy of the generations such as beamlet and polymerize, the available polymer as target.As the light source for assigning energy, preferably have
The light source of the dominant wavelength to shine in the wavelength region of 250nm to 450nm.As in the wavelength region of 250nm to 450nm
The example of the light source of luminous dominant wavelength can enumerate ultrahigh pressure mercury lamp, high-pressure sodium lamp, medium pressure mercury lamp, mercury xenon lamp, metal halide
Object lamp, high-power metallic halide lamp, xenon lamp, pulsed illumination xenon lamp, deuterium lamp, Led lamp, fluorescent lamp, Nd-YAG3 times of wave laser,
The various light sources such as He-Cd laser, N_2 laser, Xe-Cl excimer laser, Xe-F excimer laser, semiconductor excitation Solid State Laser.
Answering for the UV Photocurable composition of the photoinitiator of aminoketones containing fluorenes is further described combined with specific embodiments below
With system, evaluation method and standard are as follows:
One, developability observes pattern on substrate with scanning electron microscope (SEM), does not observe residual in unexposed portion
Object (zero) observes a small amount of residue in unexposed portion, but residual quantity can receive (◎), observed in unexposed portion it is bright
Aobvious residue (●), pattern is either with or without defect according to the observation for pattern integrity, without defect (Δ), fraction defect (), tight
Weight defect (▲)；
Two, the remaining smell of cured film is evaluated by nose news, and test result is divided into 1 (odorlessness), 2 (flavoursome), 3
(penetrating odor) three grades；
Three, xanthochromia carries out total transmissivity scanning, scanning by using color difference meter (U.S. Ai Seli X-Rite Color i7)
Wavelength 400-700nm reads △ b value and evaluates xanthochromia, and the smaller xanthochromia that represents of △ b is more unobvious, otherwise xanthochromia is more serious；
Four, adhesive force evaluation is referring to GB9286-88 " cross cut test of paint and varnish paint film ", by drawing lattice experimental method
Evaluate film adhesive quality.It is divided into 0-5 grades (totally 6 grades) according to extent of the destruction, wherein preferably 0 grade, film surface is not appointed
One small lattice falls off；5 grades to be very poor, film surface produces serious peeling.
In following discussions, each component is measured in the preparation of UV Photocurable composition by weight percentage, and with
Irgacure 907 and APi-307 is as the Reference Example compound under equal conditions.
Wherein 907 and 307 structural formula is as follows:
One: UV coating of embodiment
Application conditions: place before carrying out substrate horse mouthful patch referring to " GB/T 9271-2008 paint and varnish standard test plate (panel) "
Then the formula stirred evenly in darkroom 25# bar is coated with on horse mouthful patch by reason, coating layer thickness is about 25 μm, is exposed
Striation part: RW-UV.70201 crawler type exposure machine, radiation wavelength 250-450nm, aging condition: exposure is placed on 80 DEG C of bakings
Case toasts for 24 hours, and test result is as follows shown in table 1:
Table 1
Two: UV etching resisting ink of embodiment
Printing condition: 100T silk screen, 8-10 μm of thickness of dry film, baking condition: 75 DEG C are toasted 20 minutes, conditions of exposure: RW-
UV.70201 crawler type exposure machine, radiation wavelength 250-450nm, development conditions: 1% sodium carbonate liquor, 30 ± 2 DEG C of developments
40s, test result is as follows shown in table 2:
Table 2
Three: UV solder mask of embodiment
A, B component is uniformly mixed by 3:1, places half an hour.Printing condition: 36-43T silk-screen, 12-15 μm of thickness of dry film,
Preliminary drying condition: 75 DEG C of first face 20 minutes, the second face 25 minutes；Conditions of exposure: RW-UV.70201 crawler type exposure machine, radiation
Wavelength is 250-450nm；Development conditions: 0.5% sodium hydroxide solution, 30 ± 2 DEG C of development 60s, test result is as follows 3 institute of table
Show:
Table 3
Example IV: UV flexo ink
The above raw material is uniformly mixed in darkroom, is applied on white card boards with 5 μm of thickness, conditions of exposure: RW-
UV.70201 crawler type exposure machine, radiation wavelength 250-450nm, test result is as follows shown in table 4:
Table 4
Five: UV offset ink of embodiment
The above raw material is uniformly mixed in darkroom, is applied to plastic basis material with 2 μm of thickness, conditions of exposure: RW-UV.70201
Crawler type exposure machine, radiation wavelength 250-450nm, test result is as follows shown in table 5:
Table 5
The Photocurable composition of the amino ketone photoinitiator of the invention containing fluorenes it can be seen from embodiment 1-5 experimental result
Applied in photocureable coating and ink, light-cured performance is good, and yellowing resistance is good, and odorlessness remains after solidification, and comprehensive performance is excellent
It is different.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (18)
1. a kind of UV Photocurable composition of the photoinitiator of aminoketones containing fluorenes characterized by comprising dilute category unsaturation can light
Polymerizable compound and photoinitiator；Wherein, the photoinitiator include with the structure as shown in general formula (I) compound or its spread out
Raw compounds,
Wherein,
A represents hydrogen, halogen, nitro, C1-C20Linear or branched alkyl group, C3-C10Alkyl-cycloalkyl, C4-C10Alkyl-cycloalk
Base or cycloalkyl-alkyl,-COR6Or-CO-CR2R3R4Group, wherein optional ,-CH2By O, N, S or C (=
O) replaced；
R1Represent hydrogen, halogen, C1-C20Linear or branched alkyl group, C4-C20Cycloalkyl-alkyl or C2-C20Alkenyl, it is optional
, R1In-CH2Replaced, the R by O, N, S or C (=O)1Between can cyclization；
R2And R3Separately represent C1-C20Linear or branched alkyl group, C3-C20Naphthenic base, C4-C20Cycloalkyl-alkyl,
C4-C20Alkyl-cycloalkyl, C6-C20Aryl, C6-C20Alkylaryl, but wherein one or more hydrogen in these groups that
This is independently replaced alkyl, halogen, hydroxyl, nitro, and optional, R2And R3In-CH2By O, N, S or C (=O)
It is replaced, and R2And R3It can be mutually cyclic；
R4N- morpholinyl, N- piperidyl, N- pyrrole radicals or N- dialkyl group are represented, wherein one or more hydrogen in these groups are former
Son can be replaced halogen, hydroxyl；
R5、R5' C is represented independently of one another1-C20Linear chain or branched chain alkyl, C4-C20Naphthenic base, C2-C20Alkenyl,
C6-C20Aryl, C6-C20Alkylaryl, wherein one or more hydrogen in these groups can be independently of one another by alkyl, halogen
Element, hydroxyl, replaced nitro, and optionally ,-the CH in these groups2It can be replaced by-O-；Or R5And R5' can be each other
It is connected or five yuan or hexatomic ring is formed by-O- ,-S- ,-NH-；
R6It represents unsubstituted or by one or more C1-C20Alkyl, halogen, cyano, SR7、OR8Substituted phenyl；
R7And R8Independently represent hydrogen, C1-C20Linear or branched alkyl group.
2. UV Photocurable composition according to claim 1, which is characterized in that the unsaturated photopolymerization chemical combination of dilute category
The dosage of object is 5-95 mass parts, and the dosage of the photoinitiator is 0.05-15 mass parts.
3. UV Photocurable composition according to claim 2, which is characterized in that the unsaturated photopolymerization chemical combination of dilute category
The dosage of object is 10-90 mass parts, and the dosage of the photoinitiator is 1-10 mass parts.
4. UV Photocurable composition according to claim 1, which is characterized in that described that there is the structure as shown in general formula (I)
Photoinitiator be selected from by
One of group of composition is a variety of.
5. UV Photocurable composition according to claim 1, which is characterized in that described that there is the structure as shown in general formula (I)
Photoinitiator derivative compound be included in keep formula (I) compound main structure it is constant under the premise of, taken by its branch
Generation or derivative compound obtained from being connected to each other.
6. UV Photocurable composition according to claim 5, which is characterized in that the derivative compound has such as general formula
(II) or (III) compound represented: Wherein, M represents dimerization and is formed
Linking group can be dead key, C1-C10Linear chain or branched chain alkylidene, C6-C12Arlydene or inferior heteroaryl, optionally, M
In-CH2Replaced sulphur, oxygen, NH or carbonyl, optionally, hydrogen atom is by OH or NO2It is replaced.
7. UV Photocurable composition according to claim 6, which is characterized in that the derivative compound is
8. UV Photocurable composition according to claim 1, which is characterized in that described that there is the structure as shown in general formula (I)
Photoinitiator or its derivative compound be two or more compounds mixture.
9. UV Photocurable composition according to claim 1, which is characterized in that the unsaturated photopolymerization chemical combination of dilute category
Object is monomeric compound or oligomer.
10. UV Photocurable composition according to claim 1, which is characterized in that the unsaturated phtotpolymerizable combination of dilute category
Conjunction object is the compound comprising a carbon-carbon double bond, preferably acrylate compounds or methacrylate compound；Or
It is described that dilute to belong to unsaturated photopolymerizable compound be the preferably alkane comprising two and the compound of more than two carbon-carbon double bonds
Base dihydric alcohol, the acrylate of polyalcohol or methacrylate or polyester polyol, polyether polyol, epoxy resin are polynary
Alcohol, the acrylate of polyurethane polyol, vinyl ethers and unsaturated dicarboxylic acid polyalcohol unsaturated polyester (UP).
11. UV Photocurable composition according to claim 1, which is characterized in that when the UV Photocurable composition conduct
When UV etching resisting ink or UV solder mask purposes, at least one of unsaturated photopolymerizable compound of dilute category used chemical combination
Object contains alkali solubility group, preferably carboxylic resin.
12. UV Photocurable composition according to claim 11, which is characterized in that the carboxylic resin is (methyl)
Acrylate, ethylene unsaturated carboxylic acid or (methyl) acrylic ester polymer；
Preferably, described (methyl) acrylate is selected from by (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third
Olefin(e) acid butyl ester, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid diethylaminoethyl, (first
Base) acrylate dimethylamino ethyl ester, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid chaff
One of base ester, group of (methyl) glycidyl acrylate composition are a variety of；
Preferably, the ethylene unsaturated carboxylic acid is selected from is rested in peace acid, maleic acid, horse by acrylic acid, methacrylic acid, vinyl
Come acid alkyl ester, fumaric acid, itaconic acid, butenoic acid, cinnamic acid, acrylic acid dimer, monomer and cyclic acid anhydride with hydroxyl
Addition product, ω-carboxyl-polycaprolactone-(methyl) acrylate composition one of group or a variety of, more preferably (first
Base) acrylic acid；
Preferably, described (methyl) acrylic ester polymer be selected from by (methyl) acrylamide, (methyl) n-butyl acrylate,
One of styrene, vinyl naphthalene, (methyl) acrylonitrile, group of vinyl-acetic ester, vinyl cyclohexane composition are a variety of.
13. UV Photocurable composition according to claim 1, which is characterized in that the UV Photocurable composition further includes
Other photoinitiators, it is preferred that other described photoinitiators are selected from by benzophenone, benzil dimethyl ketal, 2- hydroxyl -2-
Methyl-1-phenyl-propanone, 1- hydroxy-cyclohexyl-phenyl -one, isopropyl thioxanthone anthracene, (2,4,6- trimethyl-benzoyl) two
One of group of phenyl phosphine oxide and bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides composition is a variety of.
14. UV Photocurable composition according to claim 1, which is characterized in that the UV Photocurable composition further includes
Sensitizer；
Preferably, the sensitizer is pyrazoline compounds, acridine compound, anthracene compound, coumarin kind compound
Or tertiary amine compounds；
It is furthermore preferred that the dosage of the sensitizer is 0-5 mass parts, it is further preferred that the dosage of the sensitizer is 0-2 matter
Measure part.
15. UV Photocurable composition according to claim 1, which is characterized in that the UV Photocurable composition further includes
Colorant, the colorant are inorganic pigment or organic pigment, and the dosage of the colorant is 0-50 mass parts, it is preferred that institute
The dosage for stating colorant is 0-20 mass parts.
16. UV Photocurable composition according to claim 1, which is characterized in that the UV Photocurable composition further includes
Additive, the additive include in surfactant, wetting agent, dispersing agent, rheology modifier, defoaming agent or storage reinforcing agent
It is one or more；Preferably, the dosage of the additive is 0-5 mass parts；It is furthermore preferred that the dosage of the additive is 0-
3 mass parts.
17. a kind of UV Photocurable composition as described in any one of claims 1 to 16 is in terms of UV coating and UV ink
Using.
18. application according to claim 17, which is characterized in that the UV ink includes UV etching resisting ink, UV welding resistance oil
Ink, flexo ink and offset ink.
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| CN110819224A (en) * | 2018-08-09 | 2020-02-21 | 江苏百赛飞生物科技有限公司 | Coating composition, protective coating based on coating composition and coated product |
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| CN114591241A (en) * | 2022-03-14 | 2022-06-07 | 内蒙古扬帆新材料有限公司 | Intramolecular sensitization macromolecule photoinitiator containing pyrazoline and alpha-aminoketone, and preparation method and application thereof |
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