CN103901725B - A kind of light curing resin composition - Google Patents
A kind of light curing resin composition Download PDFInfo
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- CN103901725B CN103901725B CN201410158610.4A CN201410158610A CN103901725B CN 103901725 B CN103901725 B CN 103901725B CN 201410158610 A CN201410158610 A CN 201410158610A CN 103901725 B CN103901725 B CN 103901725B
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Abstract
A kind of light curing resin composition, including at least following components:(a) 20 to 90 quality % binder polymer;(b) photopolymerizable compound with ethene unsaturated bond that 5 to 60 quality % one or more can be compatible with component (a) binder polymer;(c) 0 to 20 quality % additive and/or adjuvant;And (d) 0.01 to 20 quality % Photoepolymerizationinitiater initiater, the Photoepolymerizationinitiater initiater includes compound shown at least one following general structural formula:
Description
Technical field
The invention belongs to photocuring technology field, and in particular to a kind of light curing resin composition.
Background technology
Colour filter is indispensable structure member in LCD assembly and solid-state image pickup component.As display device,
LCD assembly is compared to kinescope（Cathode-ray tube (Cathode RayTube:CRT)）For smaller (compact)
And it is not a halfpenny the worse in aspect of performance, therefore just gradually replacing as television image, computer picture and other display equipment
CRT.And in recent years, it is big that the Development trend of LCD assembly develops into picture from the smaller monitor purposes of conventional picture
And require TV (TV) purposes with high-quality image quality.Compared with being used for the LCD assembly of monitor in the past, for TV
LCD assembly requirement have higher-quality image quality.In addition, present mobile phone and auto-navigation system (car
Navigation system) monitor dimension of LCD assembly that uses is less and less, it is also desirable to higher aobvious of resolution ratio
Show component.On the other hand, the colour filter for solid-state image pickup component is also required to the higher degree that becomes more meticulous.
The colouring agent of solidification compound in colour filter（Organic pigment etc.）Reaching can carry after more tiny particle requirement
High above-mentioned high image quality contrast（Such as publication of Japanese Patent Publication No. 3120547）, and be that reinforcing excitation then needs to improve filter
The colouring agent of solidification compound and pigment dispersing agent amount in color device, i.e., the photopolymerization that must be reduced in solidification compound trigger
Agent and the content of photopolymerization monomer, and improve yellowing-resistant property.However, when the content of above-mentioned Photoepolymerizationinitiater initiater and monomer
Reduction, can cause sensing optical activity to decline and then produce harmonic analysis rate and increase pattern line-width, and other negative effect display groups
The problem of part.In commercial Application, this is more obvious for the influential effect of giant display scale components.
Therefore, high sensing optical activity light-cured resin formula is researched and developed, excellent UV resistant is provided using Photoepolymerizationinitiater initiater
With resisting high-temperature yellowing to meet above-mentioned high image quality contrast（contrast）With the demand such as excitation, with very high economy
And social value.
Also, photocurable resin constituent can be used for light-emitting diode component, can be carried in response to the design of high integration
For higher luminous power.In addition, photocurable resin constituent manufacture method is simple, therefore can reduce cost, industry is improved
Competitiveness application.Furthermore, control photocurable resin constituent thickness uniformity meet lightening design advantage and can
The industrialization of light fixture is realized more easily.
Currently, the R＆D work on photocurable resin constituent has had published in the report of many, component
Structure is included but not only in following three kinds of aspects, illustrated here.
The first, the substitution structure by carboxyl, for example：JP2006028127-A, US2011256457-A1,
JP2011228103-A, CN102222798-A, JP2007233136-A, JP2004325785-A, JP2007119685-A,
JP4650211-B2, JP2007119686-A, JP4650212-B2, JP2008076852-A, JP2007248516-A,
JP2003121997-A, JP3913022-B2,2011-M90139,2011-D76227, JP2008076852-A,
JP2007248516-A, SU1321730-A, JP2002311586-A, JP2008076852-A, JP2008064890-A,
JP2007248516-A, WO200177070-A, WO200177070-A1, AU200158308-A, JP4650211-B2 etc..
Second, by ketone group or substituted-phenyl structure open report, for example：US2008180503-A1,
EP1958994-A1, JP2008208321-A, JP2008064890-A, JP2007248516-A, US2008180503-A1,
EP1958994-A1, JP2008208321-A, JP2008064890-A, JP2007248516-A etc..
The third, the substitution structure by imido grpup, for example：WO2009068322-A1, EP2065039-A1,
WO2002102336-A, WO2002102336-A1, DE10129545-A1, DE20211496-U1, JP2008102486-A,
CN101149562-A, JP2008064890-A, P2008076852-A, JP2007310027-A, JP2007119686-A,
JP4650212-B2, JP2011033793-A, JP2008076852-A, JP2007248516-A, WO2009068322-A1,
EP2065039-A1, JP2007119686-A, JP4650212-B2, JP2004325785-A etc..
(Taiwan Patent I279645 publication numbers are referred in prior document), are had been reported and are added using drawing color triphenyl methane
It is added in dry film photoresistance, will not be because of color when the photoresistance is produced color after ultraviolet exposure for recognizing whether to be exposed
The heat endurance of forming agent is not enough and un-desired color is produced when causing laminated, and reduce exposed and unexposed region it
Color contrast, but the patent document is not provided suitable for transparent and white photocurable resin constituent component formula.
(US20050531482, US2006100298A1 are referred in prior document), are had been reported the new component of research and development and are applied to
Improve the dissolubility of specific light trigger in preparation, therefore improve the storage stability containing light trigger and preparation, but not
The transparent invention with the white photocurable resin constituent xanthochromia of resistance to UV and high temperature xanthochromia can be strengthened by providing.In prior document
(referring to US20090995699, US2011134554A1), has been reported in their invention, Photoepolymerizationinitiater initiater mixing
Thing can improve resolution ratio and lightsensitivity after the development of photocurable resin constituent, lift curing rate, but do not carry
For the transparent invention with the white photocurable resin constituent xanthochromia of resistance to UV and high temperature xanthochromia can be strengthened.
(US20020088222, US6803392B1 are referred in prior document), are had been reported in their invention, the light
Polymerization initiator mixtures include a kind of aqueous, stable storing, non-settling photoinitiator suspended substance, are applicable to water-soluble
Property photocurable resin constituent formula, but not providing can strengthen transparent with the white resistance to UV of photocurable resin constituent
The invention of xanthochromia and high temperature xanthochromia.
(US19960754708, US5807905A are referred in prior document), are had been reported and are found that in their invention
Poly- borate can include Photoepolymerizationinitiater initiater mixture composition, utilize poly- boric acid in addition to it can do bactericide and fungicide
Salt is separately or individually used with initiator or electron acceptor as a kind of Photoepolymerizationinitiater initiater, but not providing can strengthen transparent
With the invention of the white photocurable resin constituent xanthochromia of resistance to UV and high temperature xanthochromia.
In application of the transparent type with white type photocurable resin constituent, if the component of addition is yellow intolerant to UV and high temperature
Become, such as Photoepolymerizationinitiater initiater is not enough because of its heat endurance, can cause photocurable resin constituent that color is presented on base material
Aberration.This is the problem of pole is to be solved.
In order to promote in terms of production efficiency and durability, photocurable resin constituent need have high sense rotation
Photosensitiveness, color inhibition and excellent engineering properties.For example, in photolithography (photolithography) formation pattern or utilizing full exposure
When light is into insulating protective film, high sensing optical activity plays the part of very important role.In addition, in order to which liquid crystal display to be avoided is by outer
Damaged to hit, and show its intrinsic performance, as support applications column separation material and be used as diaphragm purposes
Protection dope layer and passivating film just it is necessary to have excellent engineering properties.Therefore, it is a kind of with excellent sense optically-active when using
During the Photoepolymerizationinitiater initiater of property, i.e., can quickly and preferably it solve the above problems.Use this that there is excellent sense optically-active in addition, working as
Property Photoepolymerizationinitiater initiater when, even if being conducive to when using a small amount of Photoepolymerizationinitiater initiater, also result in enough light consolidate
Change degree, so be likely to decrease the pollution sources of liquid crystal, promote the conservation rate (retention rate) of pattern.
In the light trigger of white or transparent sensing optical activity composition, the commercially available Photoepolymerizationinitiater initiater of most typically is 2,4,
6 (trimethylbenzoyl) diphenyl phosphine oxides (TPO), because it has very wide absorption region, its effective absorption peak is
350-400nm, is absorbed to 420nm or so always, and the relatively general common light trigger of its absworption peak is partially long.It can be generated after illumination
Two free radicals of benzoyl and phosphoryl, can play the function of triggering polymerization, and it also has photobleaching, can make coating not
The characteristic of flavescence, with low volatilization, is used for White system, still, because effective absorption peak is partially long, therefore, in ultraviolet
Under laser curing velocity it is slow, and cause using must above lift its usage amount in the application of sensing optical activity composition.
In recent years, commercially available oxime ester Photoepolymerizationinitiater initiater, Irgacure OXE01 and Irgacure OXE02 (can be from Ciba
Spy is bought with chemical company) it is relative in photocuring degree improve many, so focus is placed on as there is color sensation rotation
The application of photosensitiveness composition, but because these Photoepolymerizationinitiater initiaters are sufficiently expensive, for the consideration of economic aspect, it is impossible to by it
Using to being enough to show enough photocuring degree, and if the consumption lifting of this Photoepolymerizationinitiater initiater will have influence on photocuring
The non yellowing characteristic of composition.
The content of the invention
To solve the above-mentioned transparent technical problem with the white photocurable resin constituent xanthochromia of resistance to UV and high temperature xanthochromia, this
Invention provides a kind of light curing resin composition.
It should be noted that " (methyl) acrylate " in this specification mean it is " acrylate " and corresponding
" methacrylate ".Similarly, " (methyl) acrylic acid " means " acrylic acid " and corresponding " methacrylic acid ",
" (methyl) acryloyl group " means " acryloyl group " and corresponding " methylacryloyl ".
As the light curing resin composition of the present invention, following components is included:
(a) 20 to 90 quality % binder polymer;
(b) what 5 to 60 quality % one or more can be compatible with component (a) binder polymer has ethene not
The photopolymerizable compound of saturated bond;
(c) 0 to 20 quality % additive;And
(d) 0.01 to 20 quality % Photoepolymerizationinitiater initiater, the Photoepolymerizationinitiater initiater includes chemical combination shown in following formula (1)
Thing:
Wherein When exposure energies are less than 350mj/cm2Time, described light curing resin composition tool is less than 4 Yellow angle value.
As (a) binder polymer, it can include, for example acrylic resin, styrene resin, epoxy resin, acid amides
Resin, amideepoxy resin, alkyd resin, phenolic resin, ester resin, polyurethane resin, by epoxy resin and (methyl) propylene
The Epocryl of the reaction acquisition of acid, the sour modified epoxy obtained by the reaction of Epocryl and acid anhydrides
Acrylate etc..These resins with independent a kind or can combine mode of more than two kinds to use.From alkali-developable and film
From the viewpoint of formative is excellent, acrylic resin is preferably used, more preferably the acrylic resin contains from (methyl) propylene
The monomer unit of acid and (methyl) alkyl acrylate is used as construction unit.Herein, " acrylic resin " means a kind of polymer, institute
State polymer and mainly contain the monomeric unit from the polymerizable monomer with (methyl) acryloyl group.In addition, in this specification
" (methyl) acrylic acid " mean " acrylic acid " and corresponding " methacrylic acid ", " (methyl) alkyl acrylate " is meant
" alkyl acrylate " and corresponding " alkyl methacrylate ".
For aforesaid propylene acid resin, it can be used by being carried out certainly to the polymerizable monomer with (methyl) acryloyl group
The resin for being polymerize by base and being manufactured.The acrylic resin with independent a kind or can combine mode of more than two kinds to use.
As the above-mentioned polymerizable monomer with (methyl) acryloyl group, for example, it can include:Diacetone acrylamide etc.
Acrylic amine, (methyl) alkyl acrylate, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylate ethyl ester,
(methyl) acrylic acid diethyllaminoethyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid -2,2,2- trifluoroethyls
Ester, (methyl) acrylic acid -2,2,3,3- tetrafluoros propyl diester, (methyl) acrylic acid, α-smell (methyl) acrylic acid, α-chlorine (methyl) third
Olefin(e) acid, β-furyl (methyl) acrylic acid, β-styryl (methyl) acrylic acid etc..
In addition, for aforesaid propylene acid resin, except the polymerism list as described above with (methyl) acryloyl group
Outside body, the one kind or two or more polymerizable monomer in also copolymerizable following polymerizable monomer:Styrene, vinyltoluene,
The polymerizable styrene derivative that α-methylstyrene etc. is substituted in alpha-position or aromatic ring, acrylonitrile, vinyl are just
The esters of the vinyl alcohols such as butyl ether, maleic acid, maleic anhydride, monomethyl maleate, ethyl maleate, maleic acid list isopropyl ester
Deng maleic mono-ester, fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid etc..
As above-mentioned (methyl) alkyl acrylate, for example, include:The compound represented by following formulas (2), at these
Hydroxyl, epoxy radicals, halogen etc. have been may replace on the alkyl of compound.
CH2=C(R1)-COOR2(2)
Herein, R1Represent hydrogen atom or methyl, R2Represent carbon number 1-12 alkyl.It is used as above-mentioned carbon number 1-12
Alkyl, can for example include methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, hendecane
Base, dodecyl and their constitutional isomer.
As the compound represented by above-mentioned formula (2), for example, include (methyl) methyl acrylate, (methyl) acrylic acid
Ethyl ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (first
Base) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) acrylic acid nonyl ester, (first
Base) decyl acrylate, (methyl) acrylic acid hendecane ester, (methyl) acrylic acid hendecane ester.They can be with independent a kind or group
Mode of more than two kinds is closed to use.
In addition, for (a) binder polymer, from the viewpoint of making alkali-developable better, preferably with carboxyl.
For the ratio for the carboxyl that binder polymer has, from the sight for realizing alkali-developable and alkali tolerance balance
Point considers that the polymerizable monomer with carboxyl is relative to the ratio of used whole polymerizable monomers, preferably 20-90 matter
%, particularly preferably more preferably 20-80 mass %, 20-70 mass % are measured, extremely preferred is 20-60 mass %.If should have carboxylic
Then there is the poor tendency of alkali-developable in the ratio of the polymerizable monomer of base, less than 20 mass % if it exceeds 90 mass % then have alkali
The tendency of poor resistance.
For the weight average molecular weight of binder polymer, from the viewpoint for the balance for realizing mechanical strength and alkali-developable
Consider, preferably 5000-300000, more preferably 20000-150000, particularly preferably 30000-100000.With regard to Weight-average molecular
For amount, there is the tendency of resistance to development fluidity reduction if small foot 5000, if it exceeds 300000 have developing time change
Long tendency.It should be noted that the weight average molecular weight in the present invention is:By gel permeation chromatography (GPC) come it is determining,
According to the value conversed using the standard curve that polystyrene standard is made.
These binder polymers, which can be used alone, or to be combined mode of more than two kinds to use by a kind.By two or more
Combine and the binder polymer under service condition, for example, can include:Binder of more than two kinds comprising different copolymer composition
Polymer, the binder polymer of more than two kinds of different weight average molecular weight, the binder of more than two kinds polymerization of different decentralization
Thing.
Then, the photopolymerizable compound for having ethylene unsaturated bond to (b) is illustrated.
As the photopolymerizable compound with ethylene unsaturated bond, comprising the monomer for having ethylene unsaturated bond, for example may be used
Include:By making α, beta-unsaturated carboxylic acid carries out reacting the compound so as to obtain, double (the 4- ((first of such as 2,2- with polyalcohol
Base) acryloxy polyethoxy) phenyl) propane, double (the poly- propoxyl group of 4- (methyl) acryloxy) phenyl of 2,2-) propane,
Bisphenol-A system (methyl) acroleic acid esterifications such as double (4- (the poly- propoxyl group of (methyl) acryloxy polyethoxy) phenyl) propane of 2,2-
Compound, by making α, the compound that beta-unsaturated carboxylic acid is reacted and obtained with the compound containing glycidyl, with urine
The carbamate monomers such as (methyl) acrylate compounds of alkane key, γ-chloro- β-hydroxy propyl-Beta '-(methyl) acryloxy
Ethyl phthalate, beta-hydroxyethyl-β '-(methyl) acryloyl-oxyethyl phthalic acid ester, β-hydroxy propyl-Beta '-(first
Base) acryloyl-oxyethyl phthalic acid ester, (methyl) alkyl acrylate etc..They may be used alone or in combination two or more
To use.
As double (4- ((methyl) acryloxy polyethoxy) phenyl) propane of above-mentioned 2,2-, for example, it can include:2,
Double (4- ((methyl) acryloxy diethoxy) phenyl) propane of 2-, the double (4- (ethoxies of (methyl) acryloxy four of 2,2-
Base) phenyl) propane, double (4- (methyl) acryloxies tetraethoxy) phenyl of 2,2-) propane, double (4- (methyl) propylene of 2,2-
The ethyoxyl of acyloxy five) phenyl) propane, double (4- (ethyoxyl of (methyl) the propylene acyloxy six) phenyl) propane of 2,2-, 2,2- are double
Double (ethyoxyl of 4- (methyl) acryloxy eight) benzene of (4- (ethyoxyl of (methyl) acryloxy seven) phenyl) propane, 2,2-
Base) propane, double (ethyoxyl of 4- (methyl) acryloxy nine) phenyl of 2,2-) propane, double (4- (methyl) acryloxies of 2,2-
Ten ethyoxyls) phenyl) propane, double (ethyoxyl of 4- (methyl) acryloxy 11) phenyl of 2,2-) propane, the double (4- of 2,2-
(diethoxy of (methyl) acryloxy ten) phenyl) propane, double (triethoxy of 4- (methyl) acryloxy ten) benzene of 2,2-
Base) propane, double (tetraethoxy of 4- (methyl) the propylene acyloxy ten) phenyl of 2,2-) propane, double (4- ((methyl) acrylic acid of 2,2-
The ethyoxyl of epoxide 15) phenyl) propane, double (ethyoxyl of 4- (methyl) acryloxy 16) phenyl of 2,2-) propane.At them
Among, for double (4- (ethyoxyl of the methacryloxy five) phenyl) propane of 2,2-, can commercially it obtain " BPE-500 "
(Xin Zhong villages chemical industry Co. Ltd. system, trade name), it is double (4- (ethyoxyl of methacryloxy 15) phenyl) with regard to 2,2-
For propane, can commercially it obtain " BPE-1300 " (Xin Zhong villages chemical industry Co. Ltd. system, trade name).They can be independent
Using or combine two or more and use.
As above by α is made, beta-unsaturated carboxylic acid is carried out reacting the compound so as to obtain with polyalcohol, for example, can arranged
Enumerate:Polyethylene glycol two (methyl) acrylate that the quantity of ethylidene is 2-14, the quantity of propylidene are poly- the third the two of 2-14
Alcohol two (methyl) acrylate, the polyethylene glycol polypropylene glycol that the quantity of ethylidene is 2-14 and the quantity of propylidene is 2-14
Two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three
Hydroxymethyl-propane ethyoxyl three (methyl) acrylate, trimethylolpropane diethoxy three (methyl) acrylate, three hydroxyl first
Base propane triethoxy three (methyl) acrylate, trimethylolpropane tetraethoxy three (methyl) acrylate, trihydroxy methyl
Propane five ethyoxyl three (methyl) acrylate, tetramethylol methane three (methyl) acrylate, (first of tetramethylol methane four
Base) acrylate, propylidene quantity be 2-14 polypropylene glycol two (methyl) acrylate, dipentaerythritol five (methyl) third
Olefin(e) acid vinegar, dipentaerythritol six (methyl) acrylate.
As above-mentioned carbamate monomer, for example, it can include:β have hydroxyl (methyl) acrylic monomers with
IPDI, 2,6- toluene di-isocyanate(TDI)s, 2,4 toluene diisocyanate, the isocyanic acid of 1,6- hexa-methylenes two
The addition reaction of the diisocyanate cpds such as ester, three [(methyl) acryloxy tetraethylene glycol isocyanato-] six methylenes
Base isocyanuric acid ester, EO modified urethanes two (methyl) acrylate, EO, PO modified urethane two (methyl) propylene
Acid esters etc..It should be noted that " EO " represents that the compound that oxirane, EO have been modified has the block structure of Oxyranyle
(block structure).In addition, " PO " represents expoxy propane, the compound that PO has been modified has the block of expoxy propane base
Structure.As EO modified polyurethanes two (methyl) acrylate, for example, it can enumerate " UA-11 " (Xin Zhong villages chemical industry strain formula meeting
Society's system, trade name).In addition, as EO, PO modified urethane two (methyl) acrylate, such as can enumerate " UA-13 "
(Xin Zhong villages chemistry lower industry Co. Ltd. system, trade name).
As the monomer with glycidyl, (methyl) glycidyl acrylate can be enumerated, to ethenylphenyl
Glycidol ether etc..As the monomer with carboxyl, the unsaturated monoacid such as (methyl) acrylic acid, itaconic acid, richness can be enumerated
Monoesters, monoamides of the unsaturated dibasic acids such as horse acid, maleic acid and its acid anhydrides and these unsaturated dibasic acids etc..As with
Sulfonic monomer, can enumerate (methyl) sulfoethyl acrylate, (methyl) acrylamido methyl propane sulfonic acid, vinyl sulphur
Acid, vinyl methyl sulfonic acid, isopropenyl pyrovinic acid, to the alcohol after (methyl) acrylic acid addition of ethylene oxide or expoxy propane
The sulfuric ester trade name work RS-30 of manufacture (such as Sanyo Chemical Industries, Ltd.), (methyl) acryloyl-oxyethyl sulphur
Acid, monoalkyl sulfosuccinate and the ester, monoalkyl sulfosuccinate and (methyl) propylene of the compound with pi-allyl
Reaction product of acid glycidyl ester etc..As the polymerism unsaturated monomer with phosphonate group, vinyl phosphorus can be enumerated
Acid, list (2- ethoxys) (methyl) acrylate of mono phosphoric acid ester (2- ethoxys) (methyl) acrylate, mono alkyl phosphate etc..
These carboxyls, sulfonic group can also be neutralized with alkali metal, alkaline-earth metal or amine.It is used as the alkali for neutralization
Metal can enumerate sodium, potassium, lithium etc.;Calcium, magnesium etc. can be enumerated as alkaline-earth metal;Ammonia, methylamine, two can be enumerated as amine
Methylamine, trimethylamine, ethamine, diethylamine, triethylamine, MEA, diethanol amine, triethanolamine etc..
Polymerization when, can further as needed and with can be with these above-mentioned monomer copolymerizations monomer.As copolymerizable
Monomer, for example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl)
Acrylic acid-2-ethyl caproite, dimethyl aminoethyl (methyl) acrylate, diethylamino ethyl (methyl) acrylate,
Phenoxyethyl (methyl) acrylate, (methyl) benzyl acrylate, isophorone base (methyl) acrylate, adamantyl
(methyl) acrylate, (methyl) cyclohexyl acrylate, styrene, α-methylstyrene, acrylonitrile, vinyl acetate ester etc..
Alternatively, it is also possible to use the multifunctional type monomer with two or more double bonds.It is multifunctional as these
The concrete example of type monomer, can enumerate methylene diacrylamine, methylene diacrylamine, ethylenebisacrylamide, Asia
Ethyl DMAA, glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol acrylate, two
Glycolmethacrylate, divinylbenzene, diallyl acrylamide, triallyl isocyanurate, three acrylic acid seasons
Penta tetrol etc..Relative to the whole monomers for constituting hydrophilic resin, the amount of these multifunctional type monomers is preferably 5-60 mass %,
More preferably 5-50 mass %.
The content ratio of photopolymerizable compound, relative to the total amount of binder polymer and photopolymerizable compound
100 mass parts, preferably 5-60 mass parts, more preferably 5-50 mass parts.If the content ratio is held less than 5 mass parts
Easily there is the not good tendency of film, if it exceeds under the collection that 60 mass parts are then taken as film roll, existing and being difficult to preserve
Tendency.
Then (d) Photoepolymerizationinitiater initiater is illustrated.
As the Photoepolymerizationinitiater initiater of unsaturated allyl compound system photopolymerization reaction, component (d) includes following formula (1) institute
Show compound（That is, PBG-325）：
Except chemical combination beyond the region of objective existence shown in formula (1), component (d) can also be containing other Photoepolymerizationinitiater initiater to be used in combination, example
It can such as include:Diphenyl (2,4,6- trimethylbenzoyls) phosphine oxide, benzophenone, N, N '-'-two of tetramethyl -4,4
Aminobenzophenone (Michler's keton (Michler's ketone)), N, N '-tetraethyl -4,4 '-diaminobenzophenone, 4- methoxies
Base -4 '-dimethylamino benzopheone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butanone -1,2- methyl isophthalic acids-[4-
(methyl mercapto) phenyl) -2- morpholinoes-the grade of acetone -1 aromatic ketone, 2- ethyl green onions quinone, phenanthrenequione, 2- tert-butyl group green onions quinone, prestox green onion
Quinone, 1,2- benzo green onions quinone, 2,3- benzo green onions quinone, 2- phenyl green onions quinone, 2,3- diphenyl green onions quinone, l- chlorine green onions quinone, 2- methyl green onions quinone, 1,
The quinones such as 4- naphthoquinones, 9,10- phenanthrenequione, 2-MNQ, 2,3- dimethyl green onion quinones, benzoin methylether, benzoin ethyl ether,
The benzoin ether compound such as benzoin phenylate, the benzoin compound such as benzoin, methylbenzoin, ethyl benzoin, 1,2- is pungent
Alkane diketone -1- [4- (phenyl) phenyl) -2- (0- benzoyl oximes), l- [9- ethyls -6- (2- methyl benzoyls) -9H-
Carbazole -3- bases] oxime ester compound such as ethyl ketone 1- (0- acetyl group oxime), the benzil derivatives such as benzil dimethyl ketal, 2- is adjacent
Chlorphenyl) -4,5- diphenyl-imidazoles dimer, (methoxyphenyl) imidazole dimers of 2- (Chloro-O-Phenyl) -4,5- two, 2- be (adjacent
Fluorophenyl) -4,5- diphenyl-imidazoles dimer, 2- (o-methoxyphenyl) -4,5- diphenyl-imidazoles dimer, 2- is (to methoxy
Base phenyl) 2,4, the 5- triarylimidazoles dimers such as -4,5- diphenyl-imidazole dimers, 9- phenylacridines, 1,7- it is double (9,9 ' -
Acridinyl) acridine derivatives, N-phenylglycine, N-phenylglycine derivative, coumarin series compounds, oxazole system such as heptane
Compound.In addition, the aryl substituent of 22,4,5- triarylimidazoles can produce symmetrical compound with identical, also may be used
To be different so as to produce asymmetric compound.In addition, as the combination of diethyl thioxanthone and dimethylaminobenzoic acid, can
Combine thioxanthones based compound and tertiary amine compound.Wherein, from the viewpoint of the transparency, more preferably 2- benzyls -2- diformazan ammonia
Base -1- (4- morpholino phenyls)-butanone -1 grade aromatic ketone compound, 1,2- octanediones -1- [4- (phenyl) phenyl] -
The oxime ester compounds such as 2- (0- benzoxies oxime).They are used alone or combine two or more to use.
The content ratio of Photoepolymerizationinitiater initiater, relative to the total amount 100 of binder polymer and photopolymerizable compound
Mass parts, preferably 0.01 to 20 mass parts, more preferably 0.01-15 mass parts, particularly preferably 0.01-10 mass parts.Such as
Really then there is the tendency that photo sensitivity becomes insufficient in the content ratio less than 0.01 mass parts;If it exceeds 20 mass parts, then deposit
In the absorption increase when exposure at the surface of photaesthesia resin bed so as to which internal photocuring becomes insufficient tendency.
Light curing resin composition can contain (c) additive, can be as needed, individually containing a kind or combine two or more
Following material:The plasticizer such as para toluene sulfonamide, filler, defoamer, fire retardant, stabilizer, adaptation imparting agent, levelling
Agent, stripping accelerator, antioxidant, spices, preparation, thermal cross-linking agent etc..For the addition of these additives, relative to
The mass parts of total amount 100 of binder polymer and photopolymerizable compound, respectively preferably 0 to 20 mass parts.
For light curing resin composition, (c) additive containing a kind or can combine molten below two or more as needed
Agent:Methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve (methyl cellosolve), ethyl cellosolve (ethyl
Cellosolve), toluene, N, N '-dimethyl formamide, propylene glycol monomethyl ether etc..By being mixed to form solid constituent with solvent
For the solution of 0 to 20 quality % or so light curing resin composition, then re-dry formation composition.But, in this situation
Under, for the remaining organic solvent amount in dried light curing resin composition, in order to prevent in process below
The diffusion of organic solvent, preferably below 2 mass %.
Light curing resin composition of the present invention can be prepared from by the way that each component is well mixed.
Then, the manufacturing process of the light curing resin composition of the present invention is illustrated.
With regard to coating for, can for example, by rolling method, comma rubbing method, gravure coating process, air knife coating method, die coating method,
The known methods such as scraper rubbing method, spraying coating method are carried out.After coating, the drying for removing organic solvent etc. can profit
Handle 5-30 minutes to carry out at 70-150 DEG C with hot wind convection type drying machine.
For the dried thickness of light curing resin composition, different because of purposes difference, dried thickness is preferred
For 1-200 μm, more preferably 1-15 μm, particularly preferably 1-10 μm.If the thickness is less than l μm, there is mechanical strength not
The tendency of foot, if it exceeds 200 μm, then exist causes sensitivity to become insufficient because of the reduction that light is passed through, and causes photocuring
The tendency of the mixed photo-curable reduction of resin combination.
For exposure process, light curing resin composition is solidified by irradiating active ray.It is used as active ray
Light source, known light source, such as carbon arc lamp, mercury-vapor arcs, extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, ammonia lamp can be used
Deng the light source of effectively radiation ultraviolet, visible ray etc..In addition, it is possible to use Ar ion lasers, semiconductor laser etc. have
The light source of effect ground radiation ultraviolet, visible ray etc..Photography floodlight bulb (flood light further can also be used
Bulb), Solar lamp (solar lamp) etc. effectively radiates the lamp of visible ray, or can also use by using laser explosure
The method that the directly picture such as method irradiates active ray so as to image shape.
By above-mentioned process, so as to obtain a kind of light curing resin composition for possessing color inhibition.For the present invention
Light curing resin composition manufacturing process for, also can be by light curing resin composition formed thereby（I.e. in development
Afterwards）, heating or 0.2-10J/cm as needed and that carry out 60-250 DEG C or so2The exposure of left and right, so as to further solidify.
So, light curing resin composition of the invention can be easily in base materials such as glass, plastics, ceramics, metals
Upper formation one patterned.
For the light curing resin composition of the present invention, resistance to UV and high temperature xanthochromia result utilize Lab colors after solidification
Model carries out xanthochromia judgement, and Lab color model is by illumination（L）With a about color, tri- key element compositions of b.L represents illumination
（Luminosity）, equivalent to brightness, a represents the scope from carmetta to green, and b represents the scope from yellow to blueness.
Passed through using PBG-325 light curing resin composition<350mJ/cm2Energy-curable after, then again pass through 200 DEG C
After Temperature Treatment 6 hours, yellow value degree (YI) is less than or equal to 4.
Passed through using PBG-325 light curing resin composition<350mJ/cm2Energy-curable after, then again by plus expose
4J/cm2, yellow value degree (YI) is less than or equal to 4.
Advantage and effect：
Test result indicates that, the light curing resin composition of the invention performance in terms of the xanthochromia of resistance to UV with high temperature xanthochromia is excellent
It is different, can be caused unlike the Photoepolymerizationinitiater initiaters such as OXE-01 light curing resin composition solidify after be easier to produce UV xanthochromias with
The problem of high temperature xanthochromia.
Embodiment
Below with reference to embodiment to be described in further detail to the present invention, but it should not be construed as to present invention guarantor
Protect the limitation of scope.
<Make binder polymer, quality % by oneself>
| Binder polymer | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 |
| Methacrylic acid | 27.00% | 27.00% | 20.00% | 24.10% | 27.70% | 27.70% |
| Yue base acrylic acid Yue esters | 36.00% | 30.00% | 30.60% | 32.80% | 35.60% | 40.60% |
| Butyl acrylate | 10.10% | 5.10% | 12.90% | 14.70% | 12.90% | 10.90% |
| Benzyl acrylate | 0.00% | 5.00% | 14.90% | 12.90% | 14.90% | 12.90% |
| Butyl methacrylate | 0.00% | 6.00% | 7.90% | 0.00% | 7.90% | 6.90% |
| Acrylic acid 2- ethylhexyls | 23.60% | 23.60% | 11.7% | 9.60% | 0.00% | 0.00% |
| Styrene | 0.00% | 2.30% | 1% | 0.00% | 0.00% | 0.00% |
| 2,2-- azobis isobutyronitriles | 3.30% | 1.00% | 1.00% | 5.90% | 1.00% | 1.00% |
| Total | 100% | 100% | 100% | 100% | 100% | 100% |
<Photocurable composition>
B1：Three Yue alcohol propane triacrylates of ethyoxyl modification（4155, Cognis)
B2：Aliphatic amine carbamate oligomer
B3：Three Yue alcohol propane triacrylates（231, Changxing chemical industry）
B4：The Yue base acrylate of trihydroxymethyl propane three（331, Changxing chemical industry）
B5：Standard bisphenol-A-epoxy diacrylate（621A-80, Changxing）
C1:Compound shown in PBG-325, i.e. formula (1) (Changzhou potenxin electronic material)
C2:Irgacure OXE01 (Ciba spy's chemical company)
C3:TPO (2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide)
D1:Acetone
According in above-mentioned experiment discovery, binder polymer or the photopolymerizable compound with vinyl unsaturated bond
If benzene ring structure, amido epoxy radicals, Photocurable composition can be easier to xanthochromia, but during using Photoepolymerizationinitiater initiater PGB325
Still possesses excellent color inhibition characteristic.
Found according to above-mentioned experiment, by the use of PGB-325 as Photoepolymerizationinitiater initiater, the resistance to Huang of Photocurable composition can be lifted
The characteristic of change simultaneously can have high photosensitivity concurrently.
Utilization possibility in industry
The invention provides a kind of new light curing resin composition, with the more excellent xanthochromia of resistance to UV, resisting high-temperature yellowing
With the property of high photosensitivity.
Claims (2)
1. a kind of light curing resin composition, it is characterised in that including at least following components：
(a) 20 to 90 quality % acrylic resin, the acrylic resin contains from (methyl) acrylic acid and (methyl) third
The monomeric building blocks of olefin(e) acid alkyl ester；
(b) what 5 to 60 quality % one or more can be compatible with component (a) acrylic resin has ethene unsaturated
The photopolymerizable compound of key, selected from trimethylolpropane ethyoxyl three (methyl) acrylate, trimethylolpropane diethoxy
Base three (methyl) acrylate, trimethylolpropane tris ethyoxyl three (methyl) acrylate, trimethylolpropane tetraethoxy
Double (4- ((methyl) acryloyls of three (methyl) acrylate, trimethylolpropane five ethyoxyl three (methyl) acrylate, 2,2-
Epoxide polyethoxy) phenyl) propane, double (the poly- propoxyl group of 4- (methyl) acryloxy) phenyl of 2,2-) propane, the double (4- of 2,2-
(the poly- propoxyl group of (methyl) acryloxy polyethoxy) phenyl) propane；
(c) 0 to 20 quality % additive and/or adjuvant；
(d) 0.01 to 20 quality % Photoepolymerizationinitiater initiater, the Photoepolymerizationinitiater initiater includes compound shown in following formula (1)：
Also, when exposure energy is less than 350mJ/cm2Time, described light curing resin composition has the yellow value degree less than 4.
2. light curing resin composition according to claim 1, it is characterised in that relative to component (a) and the total amount of (b)
100 mass parts, Photoepolymerizationinitiater initiater is 0.01-10 mass parts.
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| WO2017115755A1 (en) * | 2015-12-28 | 2017-07-06 | 積水化学工業株式会社 | Photocurable composition and method for producing electronic component |
| CN110221520B (en) * | 2018-03-02 | 2021-10-08 | 常州强力电子新材料股份有限公司 | Graphene modified dry film photoresist and application thereof in printed circuit board |
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| JP2003226718A (en) * | 2002-02-07 | 2003-08-12 | Mitsubishi Gas Chem Co Inc | Photo-curing composition of high refractive index and its cured substance |
| US20050158659A1 (en) * | 2004-01-19 | 2005-07-21 | Chun-Hsien Lee | Photosensitive resin composition for black matrix |
| CN101960380A (en) * | 2008-03-10 | 2011-01-26 | 富士胶片株式会社 | Colored curable composition, color filter and solid-state imaging device |
| CN102667531A (en) * | 2010-01-20 | 2012-09-12 | 富士胶片株式会社 | Black curable composition for wafer-level lens, and wafer-level lens |
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| JP2012067226A (en) * | 2010-09-24 | 2012-04-05 | Fujifilm Corp | Ink composition, inkjet recording method, and printed matter |
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| JP2003226718A (en) * | 2002-02-07 | 2003-08-12 | Mitsubishi Gas Chem Co Inc | Photo-curing composition of high refractive index and its cured substance |
| US20050158659A1 (en) * | 2004-01-19 | 2005-07-21 | Chun-Hsien Lee | Photosensitive resin composition for black matrix |
| CN101960380A (en) * | 2008-03-10 | 2011-01-26 | 富士胶片株式会社 | Colored curable composition, color filter and solid-state imaging device |
| CN102667531A (en) * | 2010-01-20 | 2012-09-12 | 富士胶片株式会社 | Black curable composition for wafer-level lens, and wafer-level lens |
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