CN106459415A - Polysilsesquioxane copolymer and photosensitive resin composition containing same - Google Patents
Polysilsesquioxane copolymer and photosensitive resin composition containing same Download PDFInfo
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- CN106459415A CN106459415A CN201580020253.8A CN201580020253A CN106459415A CN 106459415 A CN106459415 A CN 106459415A CN 201580020253 A CN201580020253 A CN 201580020253A CN 106459415 A CN106459415 A CN 106459415A
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- photosensitive resin
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- oligomeric silsesquioxane
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- silsesquioxane copolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- 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
Abstract
A photosensitive resin containing (A) a polysilsesquioxane copolymer represented by chemical formula 1 is provided.
Description
Technical field
The present invention is with regard to oligomeric silsesquioxane (polysilsesquioxane) copolymer and the sense that includes this copolymer
Photopolymer resin compositionss.More particularly the present invention relate to resolution, insulating properties, flatness, chemical resistance, thermostability, folding
Penetrate rate controllability and tack strength is excellent and especially aobvious for high aperture ratio liquid crystal display and reflective liquid crystal in formation
Can ensure that sensitivity, residual film ratio and UV absorbance apparently higher than traditional Photosensitve resin composition in the organic insulating film showing equipment
Minus and positive photosensitive resin composition.
Background technology
For thin film transistor (TFT) (TFT) liquid crystal display and the dielectric film of organic light emitting apparatus compositionss according to development
When photosensitive part dissolubility be divided into eurymeric and minus.The developed solution of exposed portion of eurymeric photoresist dissolves and forms figure
Case.On the contrary, the unexposed portion of negative light resistance agent developed solution dissolving, and exposed portion keep undissolved to form figure
Case.
The organic insulating film of liquid crystal display needs there is excellent insulating property (properties), and in order to reduce after coating with
The stress of the interface of substrate, should have low thermal coefficient of expansion.Physical toughness is also need.It is desirable to exploitation has
The insulating film material of tunable refractive index is used for the application in various fields.
For these reasons, sizable research effort has been carried out to give adhesive resin sensing optical activity, cohere
The representative photosensitive acrylic tree that agent resin includes novolac resin and is conventionally used to the positive type composition of organic insulating film
Fat.
Although having done these effort, the positive type composition of typically used as Photoactive compounds (PAC) exist low transmissivity and
The problem of extreme difference thermostability, leads to give vent to anger during subsequent treatment and volume contraction.Therefore, these problems compel to be essential
Solve.
Prior art literature
Patent documentation
Japanese Patent Publication the 52-13315th
Japanese Patent Publication the 62-135824th
U.S. Patent No. 4,139,391
Korean Patent Publication No. 2010-0009801
Content of the invention
The present invention specifically addresses problem of the prior art, and it is an object of the invention to provide a kind of be used for organic insulation
Film, include the compositionss of silsesquioxane resin, said composition has high sensitivity, experiences less film thickness after development and subtract
Even if also keep after the high-temperature calcination after film forming less high-transmission rate, heat-resisting enough given vent to anger with preventing and formed there is controlled cone
The pattern at angle and there is tunable refractive index.
It is a further object to provide a kind of photopolymer resin and the tree including this photopolymer resin
Oil/fat composition, the acetal protecting group substitution value of this photopolymer resin is controlled for negative resin composition or eurymeric
Resin combination.
According to a scheme of the present invention, provide a kind of photosensitive resin, this photosensitive resin includes (A) by gathering that formula 1 represents
Silsesquioxane copolymer：
Wherein each R1Stand alone as the C being substituted or being unsubstituted1-C20Stretch alkyl,
R2And R3Each stand alone as(wherein R2aAnd R2bEach stand alone as and be substituted or not
The C being substituted1-C30Alkyl, pi-allyl, aryl, aralkyl or cycloalkyl),
R4For having being substituted or being unsubstituted C of at least one vinylation unsaturated bond2-C10Alkyl,
R5Be selected from i) be substituted or be unsubstituted containing C3-C10Cyclic ether group, ii) C that is substituted or is unsubstituted1-
C10Alkyl, iii) C that is substituted or is unsubstituted6-C20The group that cyclic hydrocarbon radical and combinations of the above are formed,
P stands alone as 1 to 3 integer,
L and z each stands alone as 2 to 100 integer, and
M, n, x and y each stand alone as 0 to 100 integer.
According to the further scheme of the present invention, provide a kind of Photosensitve resin composition including this photosensitive resin.
According to another scheme of the present invention, provide a kind of negative-type photosensitive resin composition, this negative-type photosensitive resin combines
Thing includes (A) this photosensitive resin, and (B) has the polyfunctional compound of vinylation unsaturated bond, (C) photopolymerization initiator, and (D) uses
(methyl) acyclic compound or organic solvent in tackness and viscosity adjustment；And (E) at least one is selected from antioxidation
The additive of the group that agent, light stabilizer, tackifier and surfactant are formed.
According to another scheme of the present invention, provide a kind of positive photosensitive resin composition, this positive photosensitive resin combines
Thing includes (A) this photosensitive resin, (F) light acid producing agent or Photoactive compounds；(G) alkali quencher；(D) it is used for tackness and stick
(methyl) acyclic compound of degree adjustment or organic solvent；And (E) at least one selected from antioxidant, light stabilizer,
The additive of the group that tackifier and surfactant are formed.
According to another scheme of the present invention, provide a kind of organic insulating film being formed using this Photosensitve resin composition.
According to another scheme again of the present invention, provide a kind of inclusion by solidifying what this Photosensitve resin composition was formed
The substrate of resin pattern.
This substrate can be used for semiconductor subassembly, LCD device, OLED device, solar battery apparatus, flexible display device
Or touch-controlled screen device, or the assembly manufacture by nano-imprint lithography art can be applied to.
The photopolymer resin of the present invention and organic insulation film composition are extremely sensitive and after can ensure that development
High residual film ratio.Additionally, the organic insulation film composition of the present invention has enough thermostabilitys to form the figure with controlled cone angle
Case and prevent from giving vent to anger, and to substrate, there is high bonding strength, and also its refractive index is easily controllable.Therefore, the compositionss of the present invention
Photoresist as organic insulating film is highly useful.
Brief description
[Fig. 1] is the image of the sectional hole patterns that display is formed using the Photosensitve resin composition of embodiment 1-2；
[Fig. 2] is the image of the sectional hole patterns that display is formed using the Photosensitve resin composition of comparative example 1-1；
[Fig. 3] is the image of the sectional hole patterns that display is formed using the Photosensitve resin composition of embodiment 2-2；And
[Fig. 2] is the image of the sectional hole patterns that display is formed using the Photosensitve resin composition of comparative example 2-1.
Specific embodiment
Will be described in now the present invention.
Term " alkyl " used herein is intended to including straight chain, side chain and cyclic hydrocarbon group.Term " stretching alkyl " refers to spread out
It is conigenous the divalent group of alkyl.For example, stretch alkyl include methylene, stretch ethyl, stretch isobutyl group, stretch cyclohexyl, cyclopenta stretches second
Base, 2- stretch acrylic and 3- stretches butynyl.
Unless otherwise stated, term " miscellaneous alkyl " itself or finger desirable with another term group are former by the carbon of statement number
Stable straight chain that the hetero atom of the sub and one or more group being formed selected from O, N, P, Si and S is formed, side chain,
Cyclic hydrocarbon group or combinations of the above, and wherein nitrogen, phosphorus and sulphur atom can be alternatively oxidized, and nitrogen heteroatom is permissible
Alternatively quaternized.Similarly, term " miscellaneous stretch alkyl " refers to the divalent group derived from miscellaneous alkyl.
Unless otherwise stated, otherwise term " aryl " means polyunsaturated aromatics hydrocarbon substituent, its can be monocyclic or
Multi-ring (1 to 3 ring) being fused together or being covalently attached.Term " heteroaryl " refers to be selected from N, O and S containing one to four
The aryl (or ring) of hetero atom (in the case of multi-ring in each single ring), wherein nitrogen and sulphur atom are alternatively by oxygen
Change, and nitrogen-atoms are alternatively quaternized.Heteroaryl can be connected to the remainder of molecule by carbon or hetero atom.Aryl
Include phenyl, 1- naphthyl, 2- naphthyl, 4- xenyl, 1- pyrrole radicals, 2- pyrrole radicals, 3- pyrrole with the non-limiting examples of heteroaryl
Cough up base, 3- pyrazolyl, 2- imidazole radicals, 4- imidazole radicals, pyrroleBase, 2- oxazolyl, 4- oxazolyl, 2- phenyl -4- oxazolyl, 5-
Oxazolyl, 3- isoxazolyl, 4- isoxazolyl, 5- isoxazolyl, 2- thiazolyl, 4- thiazolyl, 5- thiazolyl, 2- furyl,
3- furyl, 2- thienyl, 3- thienyl, 2- pyridine radicals, 3- pyridine radicals, 4- pyridine radicals, 2- pyrimidine radicals, 4- pyrimidine radicals, 5- benzene
Benzothiazolyl, purine radicals, 2- benzimidazolyl, 5- indyl, 1- isoquinolyl, 5- isoquinolyl, 2- quinolineQuinoline base, 5- quinoline
Quinoline base, 3- quinolyl and 6- quinolyl.The substituent group of each of above-mentioned aryl and heteroaryl is to be subjected to selected from following
The group that substituent group is formed.Term " stretching aryl " and " miscellaneous stretch aryl " refer respectively to the divalent group of aryl and heteroaryl.
In the statement of " be substituted or be unsubstituted " described herein, term " being substituted " mean one of hydrocarbon or
More hydrogen atoms are substituted by identical or different substituent group independently of one another.
Suitable substituent group includes but is not limited to-Ra,-halogen ,-O-,=O ,-ORb、-SRb、-S-,=S ,-NRcRc,=
NRb,=N-ORb, trihalomethyl ,-CF3、-CN、-OCN、-SCN、-NO、-NO2,=N2、-N3、-S(O)2Rb、-S(O)2NRb、-S
(O)2O-、-S(O)2ORb、-OS(O)2Rb、-OS(O)2O-、-OS(O)2ORb、-P(O)(O-)2、-P(O)(ORb)(O-)、-P(O)
(ORb)(ORb)、-C(O)Rb、-C(S)Rb、-C(NRb)Rb、-C(O)O-、-C(O)ORb、-C(S)ORb、-C(O)NRcRc、-C(NRb)
NRcRc、-OC(O)Rb、-OC(S)Rb、-OC(O)O-、-OC(O)ORb、-OC(S)ORb、-NRbC(O)Rb、-NRbC(S)Rb、-NRbC
(O)O-、-NRbC(O)ORb、-NRbC(S)ORb、-NRbC(O)NRcRc、-NRbC(NRb)Rb, and-NRbC(NRb)NRcRc, wherein Ra
It is the group being formed selected from alkyl, cycloalkyl, miscellaneous alkyl, cycloheteroalkyl, aryl, aralkyl, heteroaryl and heteroaryl alkyl
Group；Each RbAll stand alone as hydrogen or Ra；Each RcAll stand alone as Rb, premise is two RcGroup nitrogen-atoms in connection are permissible
Form 4-, 5-, 6- or 7- membered cycloheteroalkyl group together, and can alternatively include 1 to 4 group being formed selected from O, N and S
Identical or different other hetero atoms of group.As instantiation ,-NRcRcMean including-NH2,-NH- alkyl, N- Pyrrolizidine
Base and N- forint base.As another example, the alkyl being substituted mean including-stretch alkyl-O- alkyl ,-stretch alkyl-miscellaneous
Aryl ,-stretch alkyl-cycloheteroalkyl ,-stretch alkyl-C (O) ORb,-stretch alkyl-C (O) NRbRb, and-CH2-CH2-C(O)-CH3.Should
The atom that one or more substituent groups are connected with them can together with optionally form including cycloalkyl and cycloheteroalkyl
Cyclic rings.
According to a specific embodiment of the present invention, Photosensitve resin composition includes the poly- silicon as photopolymer resin
Silsesquioxane copolymer, this oligomeric silsesquioxane copolymer is alkali-soluble in itself and can be used for formation and have improvement etch resistant
The organic insulating film of property.The following is being described in more detail of each composition with regard to Photosensitve resin composition.
1. (A) oligomeric silsesquioxane copolymer
Photosensitive resin includes the oligomeric silsesquioxane copolymer that (A) is represented by formula 1：
Oligomeric silsesquioxane copolymer has silsesquioxane structure in main chain.Oligomeric silsesquioxane copolymer is repeating
Unit (I) includes alkali solubility hydroxy-acid group.The presence of alkali solubility functional group allows in negative photosensitive compositionss using poly- silicon
Silsesquioxane copolymer.In the repetitives (III) of oligomeric silsesquioxane copolymer, hydroxyl is bonded phenyl structure.Repeat
The presence of unit (III) allows to control rate of dissolution in alkali for the oligomeric silsesquioxane copolymer further.
- OH the base of repetitives (I) or (III) can be replaced using acetal protecting group.This replacement can control poly- silicon
The alkali solubility of silsesquioxane copolymer.Some hydroxy-acid groups in repetitives (I) can be by sour unstable acetal protecting group
Replace, or the phenyl structure of repetitives can include sour unstable acetal protecting group (repetitives (II) and (IV)).?
In this case, oligomeric silsesquioxane copolymer can be used for the chemically amplified positive photosensitive composition including light acid producing agent
In.Hydroxyl is introduced into the eurymeric sense making it possible in phenyl structure including Photoactive compounds (PAC) (repetitives (III))
Using oligomeric silsesquioxane copolymer in light compositionss.Oligomeric silsesquioxane copolymer can have sudden and violent in the presence of light initiator
It is exposed to the photosensitive functional group (repetitives (V)) that can participate in curing reaction during light.Additionally, oligomeric silsesquioxane copolymer is permissible
There are the various functional groups (repetitives (VI)) that can give physical property needed for oligomeric silsesquioxane copolymer.
Oligomeric silsesquioxane copolymer has the acid number in 50 to 150, preferably 60 to 130 scope.If acid number is little
In the lower limit defining above, then oligomeric silsesquioxane copolymer is less likely to occur to develop.Meanwhile, if acid number exceedes above defining
The upper limit, then oligomeric silsesquioxane copolymer may excessive dissolution making it difficult to by development formed pattern.
Formula 1 is not intended to represent the interior arrangement of average molecular of repetitives.The oligomeric silsesquioxane copolymer of formula 1 can be taken respectively
The form of kind, for example mixed and disorderly copolymer, graft copolymer and block copolymer.
In formula 1, R1For the C being substituted or be unsubstituted1-C20Stretch alkyl.
In formula 1, R2And R3Each stand alone as(wherein R2aAnd R2bEach stand alone as through
The C replacing or being unsubstituted1-C30Alkyl, pi-allyl, aryl, aralkyl or cycloalkyl, preferably methyl or ethyl).
In repetitives (III), each hydroxyl can be in meta or para position, and p can be 1 to 3 integer.
In formula 1, R4The photosensitive functional group of curing reaction is may participate in when being and being exposed to light in the presence of light initiator, and
Stand alone as and there is being substituted or being unsubstituted C of at least one vinylation unsaturated bond2-C10Alkyl.Photosensitive functional group can be
Alkyl containing end 3- methylacryloyl, 3- acryloyl group, vinyl or pi-allyl, its instantiation includes 3- methyl-prop
Alkene acryloxypropylethoxysilane, 3- acryloxypropyl, 3- methylacryloyl, 3- acryloyl group, vinyl and pi-allyl.
In formula 1, R5Can selected from i) be substituted or be unsubstituted containing C3-C10Cyclic ether group, ii) it is substituted or not
The C being substituted1-C10Alkyl, and iii) C that is substituted or is unsubstituted6-C20The group that cyclic hydrocarbon radical is formed.Including R5Weight
Multiple unit (VI) can be only made up of a kind of repetitives, or can be preferably the repetitives of two or three multi-form
Combination, the physical property of oligomeric silsesquioxane copolymer is controlled to required level.For example, oligomeric silsesquioxane polymerization
Thing can the repetitives containing three kinds of multi-forms (VI)a、(VI)b, and (VI)cCombination as repetitives (VI), wherein
R5Group can be same to each other or different to each other.
Be substituted or be unsubstituted containing C3-C10Cyclic ether group is strong to sticking together of substrate in order to improve Photosensitve resin composition
Degree, and improve thermostability after the solidification of Photosensitve resin composition.Group containing cyclic ethers is (the such as epoxy of oxacycloalkyl containing end
Base or oxetanyl) alkyl.
The C being substituted or being unsubstituted1-C10Alkyl makes oligomeric silsesquioxane polymer have enough flexibility and allow to gather
Silsesquioxane polymer has suitable glass transition temperature.The C being substituted or being unsubstituted3-C18Cyclic hydrocarbon radical improves photosensitive
The thermostability of resin combination and hardness.
Be substituted or be unsubstituted containing C3-C10Cyclic ether group can be containing terminal glycidyl group, 2- (3,4- epoxy
Cyclohexyl) or oxetanes -3- base alkyl, its instantiation include 3- glycidoxypropyl, 3- glycidyl,
2- (3,4- epoxycyclohexyl) ethyl, 3- ethyl -3- [3- propoxy methyl] oxetanyl and oxetanes -3- base
Methyl.Preferably, be substituted or be unsubstituted containing C3-C10Cyclic ether group can include epoxy radicals.
The C being substituted or being unsubstituted1-C10Alkyl can be such as methyl, ethyl, propyl group, butyl, hexyl or octyl group.
The C being substituted or being unsubstituted3-C18Cyclic hydrocarbon radical can be cycloalkyl, bicyclic alkyl, aryl or
Heteroaryl, it can be alternatively by C1-C4Alkyl replaces.Cyclic hydrocarbon radical can include at least one in the structure
Individual hetero atom or double bond.Preferably, it is substituted or the C that is unsubstituted3-C18Cyclic hydrocarbon radical is to be selected from but is not limited toAndInstitute
The group of composition.
In formula 1, l, m, n, o, x, y and z represent the number of corresponding repetitives, and are equal to or whole more than 0
Number.Depending on the expected purpose of oligomeric silsesquioxane copolymer, l and z can be each independently selected from 2 to 100 scope, and m,
N, o, x and y can be each independently selected from 0 to 100 scope.
In the case that oligomeric silsesquioxane copolymer is used for negative-type photosensitive resin composition, repetitives (I),
(II), (III), (IV), (V) and (VI) ratio in this oligomeric silsesquioxane copolymer can be respectively 5 to 40 and rub
That %, 0 to 20 mole of %, 5 to 40 moles of %, 5 to 40 moles of %, 5 to 40 moles of % and 5 to 30 moles of %.
Or, this oligomeric silsesquioxane copolymer can be used for positive photosensitive resin composition.In the case, repeat list
First (I), (II), (III), (IV), (V) and (VI) ratio in this oligomeric silsesquioxane copolymer can be respectively 5 to 20
Mole %, 5 to 20 moles of %, 0 to 20 mole of %, 0 to 30 mole of %, 0 to 5 mole of % and 5 to 30 moles of %.
The weight average molecular weight of oligomeric silsesquioxane copolymer is preferably from 2,000 to 50,000.Mean molecule quantity is less than
2,000 oligomeric silsesquioxane copolymer can carry out rapid development so that being not likely to form pattern, and needed for cannot guaranteeing
Residual film ratio.Meanwhile, the oligomeric silsesquioxane copolymer more than 50,000 for the mean molecule quantity may not use developing liquid developing.Poly- silicon
The dispersion of silsesquioxane copolymer is preferably 1.0 to 5.0.The average oligomeric silsesquioxane copolymer more than 5.0 for the dispersion is just
It is probably unfavorable for resolution aspect.
Oligomeric silsesquioxane copolymer preferably be 5 to 45 weight % based on the gross weight of compositionss amount exist.If
The content of oligomeric silsesquioxane copolymer is less than the lower limit defining above, then might have difficulty on forming thin film.Meanwhile, false
The content of oligomeric silsesquioxane copolymer is made to exceed the above upper limit defining, then the viscosity of compositionss may be required in patterning
Scope outside.
Oligomeric silsesquioxane copolymer as photopolymer resin can be used to form and to have improvement elching resistant
Organic insulating film, there is enough thermostabilitys to form the pattern with controlled cone angle and to prevent from giving vent to anger, and substrate is had
High tack strength.Additionally, the refractive index of oligomeric silsesquioxane copolymer is easily controllable.Oligomeric silsesquioxane copolymer can be employed
In chemically amplified positive photosensitive composition.In this case, common in the partly middle oligomeric silsesquioxane of exposure (such as UV light)
The acid that polymers is produced from light acid producing agent acts on and quickly deprotects in the way of chemistry amplifies, thus producing Gao Rong
Xie Du.Meanwhile, the oligomeric silsesquioxane copolymer in unexposed portion has the ability of antilysis.In exposure and unexposed portion
The different qualities of the oligomeric silsesquioxane copolymer in point can improve the contrast of compositionss and resolution for organic insulating film
Rate, causes fine circuit pattern to be formed.
2. negative-type photosensitive resin composition
According to a specific embodiment of the present invention, (A) oligomeric silsesquioxane copolymer can be applied to negative photosensitive tree
Oil/fat composition.In addition to (A) oligomeric silsesquioxane copolymer, negative-type photosensitive resin composition also includes (B) and has vinylation
The polyfunctional compound of unsaturated bond；(C) photopolymerization initiator；(D) it is used for tackness and (methyl) acrylic acid of viscosity adjustment
Compound or organic solvent；And (E) at least one additive.
(B) there is the polyfunctional compound of vinylation unsaturated bond
The polyfunctional compound with vinylation unsaturated bond typically has the cross-linking of at least two vinylation double bonds
Unit.For example, the polyfunctional compound with vinylation unsaturated bond can be selected from：Multifunctional (methyl) acrylic monomerss and widow
Polymers, such as glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, 2,2'-ethylenedioxybis(ethanol). two propylene
Acid esters, triethylene glycol dimethacrylate, Aronix M 240, TEG dimethylacrylate, butanediol diformazan
Base acrylate, propylene glycol diacrylate, dimethacrylate, trimethylolpropane trimethacrylate, three hydroxyls
Trimethacrylate, tetra methylol tetraacrylate, tetra methylol propane tetramethyl acrylate, new penta
Tetrol triacrylate, new penta tetrol trimethyl acrylic ester, new penta tetra-acrylate, new penta tetrol tetramethyl acrylic acid
Ester, two new penta tetrol five acrylate, two new penta tetrol pentamethacrylates, two new penta tetrol six acrylate, two new penta
Tetrol hexamethacrylate, 1,6 hexanediol diacrylate, 1,6-HD dimethylacrylate and pendency epoxy two
Acrylate (cardoepoxy diacrylate)；React the polyester obtaining by making (methyl) acrylic acid and polyester prepolyer
(methyl) acrylate, this polyester prepolyer is condensed to yield with unitary or polyprotic acid by polyhydric alcohol；Many by making to have
The polyamine that the compound of first alcohol radical and two NCOs reacts and makes product and (methyl) propylene acid reaction and obtains
Ester (methyl) acrylate；And react, by making (methyl) acrylic acid, epoxy (methyl) acrylate obtaining with epoxy resin
Resin, this epoxy resin such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol or cresol
Phenolic resin varnish type epoxy resin, solvable phenol aldehyde type epoxy resin, tris-phenol type epoxy resin, polycarboxylic acids poly epihydric alcohol
Ester, poly glycidyl ester, polyhydric alcohol poly glycidyl ester, aliphatic series or alicyclic epoxy resin, amine epoxy resin or dihydroxy benzenes
Type epoxy resin.When considering the factor of such as exposure sensitive, the use of multifunctional (methyl) acrylic monomerss is probably favourable
's.
The polyfunctional compound with vinylation unsaturated bond can be by with the gross weight based on compositionss for 5 to 50 weights
Amount %, the amount of preferably 10 to 40 weight % use.If the content with the polyfunctional compound of vinylation unsaturated bond is less than
The lower limit more than defining, then the curing degree of photosensitive resin (i.e. oligomeric silsesquioxane copolymer) may reduce making it difficult to be formed
Pattern.Meanwhile, if the content with the polyfunctional compound of vinylation unsaturated bond exceedes the above upper limit defining, then may
The pattern with soft and resolution can be formed.
(C) photopolymerization initiator
The function of photopolymerization initiator is to cause the polymerization of crosslinkable units by visible ray, ultraviolet light or extreme ultraviolet light.
For example, photopolymerization initiator can be selected from：Acetophenones, such as 1-Phenylethanone., 2,2- diethoxy acetophenone, p- dimethyl benzene
Ethyl ketone, p- dimethyl amido propiophenone, dichloroacetophenone, trichloroacetophenone and p- tert-butyl benzene ethyl ketone；Benzophenone,
Such as benzophenone, 2- chlorobenzophenone and p, the double dimethyl amido benzophenone of p'-；Benzoin ethers, such as hexichol first
Acyl, benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether；Sulphur compound, such as base diformazan
Base ketal, thioxanthene (thioxanthene), 2- diuril ton, 2,4- diethyl thioxanthene, 2- methyl thioxanthene and 2- isopropylthioxanthones；Anthracene
Quinones, such as 2-ethyl-anthraquinone, prestox anthraquinone, 1,2- benzo anthraquinone and 2,3- diphenyl anthraquinone；Organic peroxide, example
As azobis isobutyronitrile, benzoyl peroxide and dicumyl peroxide；Mercaptan compound, such as 2-mercaptobenzimidazole, 2- mercapto
Base benzoxazoles and 2-mercaptobenzothiazole；Imidazole-based compounds, such as 2- (o- chlorphenyl) -4,5- bis- (m- methoxybenzene
Base)-imidazole radicals dimer；Triaizine compounds, for example p- methoxyl group triazine；There are the triaizine compounds of halomethyl, such as 2,4,
6- ginseng (trichloromethyl)-s- triazine, 2- methyl -4,6- double (trichloromethyl)-s- triazine, 2- [2- (5- methylfuran -2- base) second
Thiazolinyl] -4,6- couple of (trichloromethyl)-s- triazine, double (the trichloromethyl)-s- three of 2- [2- (furan -2- base) vinyl] -4,6-
Piperazine, 2- [2- (4- diethyl amido -2- aminomethyl phenyl) vinyl] -4,6- double (trichloromethyl)-s- triazine, 2- [2- (3,4- bis-
Methoxyphenol) vinyl] double (the trichloromethyl)-s- triazine of -4,6-, 2- (4- methoxyphenyl) -4,6- double (trichloromethyl) -
Double (the trichloromethyl)-s- triazine of s- triazine, 2- (4- ethoxystyrene base) -4,6- and 2- (4- n-butoxyphenyl) -4,6-
Double (trichloromethyl)-s- triazine；And amido assimilation compound, such as 2- base -2- dimethyl amido -1- (4- forint benzene
Base)-butyl- 1- ketone.Ketoxime ester and alpha-ketoxime ester compounds can also be used.
Photopolymerization initiator can by with the gross weight based on compositionss be 0.1 to 10 weight %, preferably 0.5 to 7 weight %
Amount use.If the content of photopolymerization initiator is less than the lower limit defining above, then it is less likely to occur to solidify.Meanwhile, if
The content of photopolymerization initiator exceedes the above upper limit defining, then due to the low solubility after solidification it may happen that precipitating.
(D) (methyl) acyclic compound for tackness and viscosity adjustment or organic solvent
(methyl) acyclic compound adjusting for tackness and viscosity can provide and Photosensitve resin composition is sticked
Degree or the control of tackness.In this case, using Photosensitve resin composition under not using any solvent.
As for (methyl) acyclic compound for tackness and viscosity adjustment, it is possible to use such as methacrylic acid
Ester, phenyl maleimide, cyclohexyl methacrylate, acrylic acid tetrahydrofuran ester, THFMA, methyl
Acrylic acid tetrahydropyrans ester, N- pyrrole pyridine ketone, isobornyl methacrylate, ethylhexylacrylate, acrylic acid
Different monooctyl ester, n-butyl acrylate, ethyl acrylate, acrylic acid methyl ester., vinyl acrylate, 2- hydroxy acrylate, β-propylene
Propionic or acrylic acid.
(methyl) acyclic compound for tackness and viscosity adjustment is preferably with the gross weight 10 based on compositionss
Amount to 50 weight % exists.If (methyl) acyclic compound for tackness and viscosity adjustment is less than and defines above
Lower limit, then the viscosity of compositionss may be too high.Meanwhile, if being used for tackness and (methyl) acrylic acid chemical combination of viscosity adjustment
Thing exceedes the above upper limit defining, then the physical property of the film being formed may be degenerated.
Organic solvent has no particular limits, as long as it can dissolve polymer.Organic solvent can be general
Any organic solvent used in photopolymerizable composition, the example includes acetate used in general photopolymerizable composition
Class, ethers, glycolss, ketone, alcohols and carbonate based organic solvent.For example, organic solvent can match road selected from ethyl
Soviet Union, butyl Sai Lusu, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, acetate of butyl carbitol, ethylene glycol,
Ketohexamethylene, Ketocyclopentane, 3- ethoxy-propionic acid, DMAC N,N' dimethyl acetamide, N- methylpyrrole pyridine ketone, N- methyl caprolactam and
The group that above-mentioned mixture is formed.
Organic solvent can be 20 to 75 weight % based on the gross weight of compositionss, the amount of preferably 30 to 70 weight % deposits
?.If the content of organic solvent is less than the lower limit defining above, then it is likely difficult to form thin film by traditional coating technique.
Meanwhile, if the content of organic solvent exceedes the above upper limit defining, then possibly cannot obtain with desired thickness after coating
Thin film.
(E) additive
According to the present invention a specific embodiment, additive be selected from antioxidant, light stabilizer, tackifier and
The group that surfactant is formed.
Tackifier is the composition with the function of improving the tackness to substrate.It is anti-that tackifier preferably has at least one
Answer the silane coupling agent of functional group, this reactive functional group base is selected from carboxyl, methylacryloyl, vinyl, isocyanates and ring
Epoxide.Specifically, tackifier can be selected from trimethoxy silicon substrate benzoic acid, γ-methacryloxypropyl trimethoxy
Base silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanates propyl-triethoxysilicane,
γ-glycidoxypropyltrime,hoxysilane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane and above-mentioned mixing
The group that thing is formed.
Surfactant is the function of the coating homogeneity with the coating improving on substrate, compositionss and from combination
The composition of the ability of spot is removed in thing.Surfactant can be selected from fluorinated surfactant, silica-based surfactant, non-
The group that ionic surface active agent and above-mentioned mixture are formed.
Be applied to the antioxidant of said composition representative example include Irganox 1010, Irganox 1035,
Irganox 1076 and Irganox 1222 (Ciba-Geigy, Japan).The example of suitable light stabilizer includes：Tinuvin
292nd, Tinuvin 144 and Tinuvin 622LD (Ciba-Geigy, Japan)；And sanol LS-770, sanol LS-
765th, sanol LS-292 and sanol LS-744 (Sankyo, Japan).
Additive generally can by be 0.01 to 5 weight % based on the gross weight of compositionss, preferably 0.05 to 3 weight %
Amount uses.The amount of additive can change according to the selection of user, as long as the physical property needing in Photosensitve resin composition
Matter does not change.
3. positive photosensitive resin composition
According to a specific embodiment of the present invention, (A) oligomeric silsesquioxane copolymer can be applied to positive type light sensitive tree
Oil/fat composition.In addition to photosensitive resin (A), positive photosensitive resin composition includes (F) light acid producing agent or photolytic activity chemical combination
Thing, (G) alkali quencher, (D) be used for tackness and viscosity adjustment (methyl) acyclic compound or organic solvent and (E)
At least one additive.
(F) light acid producing agent or Photoactive compounds
Light acid producing agent is in the compound producing acid with photochemical roentgenization or when being exposed to radiation.For example, light acid is produced
Raw agent can be selected from diazenium compound, salt compound, sulfonium salt compound, iodine salt compound, acid imide sulphonic acid ester chemical combination
Thing, oxime sulfonate compounds, diazonium two sulphones, two sulphones, o- nitro base sulfonate compound, triazine chemical combination
Thing and above-mentioned mixture.Use can not adversely affect any other smooth acid producing agent that film is formed.250 to
There is under the wavelength of 400nm suitable suction brightness and organic insulating film material can be kept in visible region (>=400nm)
The material of the transparency of material is preferred.The light acid preferably being represented by formula 2 or 3：
According to a specific embodiment of the present invention, light acid producing agent is with the gross weight based on compositionss for 0.1 to 10
Weight %, the amount of preferably 0.5 to 5 weight % exist.If the content of light acid producing agent is less than the lower limit defining above, then it is difficult to
Produce the acid of q.s.Meanwhile, if the content of light acid producing agent exceedes the above upper limit defining, then light acid producing agent is in combination
Dissolubility in thing is deteriorated, thus having the risk it may happen that precipitating.
Used in traditional positive type composition, any two Azide quinones Photoactive compounds are all used as photolytic activity
Compound, the example includes but is not limited to diazo naphthoquinone (DNQ), 1,2- naphthoquinone -2- two nitrine -5- sulfonic acid or 1,2- naphthoquinone -2-
The esterification products of two nitrine-sulfonic acid and low-molecular weight aromatic hydroxy compound, such as 2,3,4- trihydroxybenzophenones, 1,3,5-
Trihydroxy benzene, 2,3,4,4'- tetrahydroxybenzophenone, 2- and 4- methylphenol and 4,4'- hydroxy propane.As for two Azides
Quinone photosensitizer, two Azide naphthoquinone derivatives are especially preferred.Above-claimed cpd may be utilized independently or as wherein both
Or the mixture of more person uses.
The content of Photoactive compounds can change depending on the species of solvent.If the amount of Photoactive compounds is very little, then
Difficult to form photoresist pattern.Meanwhile, if the amount of Photoactive compounds is too many, then the physical property having resist film may become
The risk of difference.Therefore, the gross weight based on compositionss, the amount of Photoactive compounds is preferably restricted to 1 to 30 weight %, more excellent
Choosing is restricted to 5 to 25 weight %.
(G) alkali quencher
According to a specific embodiment of the present invention, alkali quencher can be included in Photosensitve resin composition to improve
The shape of resist pattern and post exposure stability.Alkali quencher is preferably nitrogen-containing compound, and can alternatively contain organic
Carboxylic acid or phosphorus oxyacid or derivatives thereof.
The example of this nitrogen-containing compound include trimethylamine, diethylamine, triethylamine, di-n-propylamine, Tri-n-Propylamine, three
Amine, diethanolamine, triethanolamine, n-hexylamine, positive heptyl amice, 1-Aminooctane, positive nonyl amine, ethylenediamine, N, N, N', N'- tetramethyl second two
Amine, tetra-methylenedimine, hexamethylene diamine, 4,4'- two aminodiphenylmethane, 4,4'- bis- amido diphenyl ether, 4,4'-
Two aminobenzophenones, 4,4'- bis- amido diphenylamine, Methanamide, N-METHYLFORMAMIDE, N,N-dimethylformamide, acetyl
Amine, N- methylacetamide, DMAC N,N' dimethyl acetamide, propionic acid amide., Benzoylamide, Pyrrolizidine ketone, N- methylpyrrole pyridine ketone, methyl
Urea, 1,1- dimethyl urea, 1,3- dimethyl urea, 1,1,3,3- tetramethylurea, 1,3- diphenyl urea, imidazoles, benzimidazole, 4- first
Base imidazoles, 8- oxygen quinoline, acridine, purine, Pyrrolizidine, piperidines, 2,4,6- tri- (2- pyridine radicals)-S- triazine, forint, 4- methyl
Forint, piperazine, 1,4- lupetazin and 1,4- diazabicyclo [2.2.2] octane.Wherein, alkanolamine, such as three ethanol
Amine is especially preferred.These nitrogen-containing compounds may be utilized independently or being applied in combination with wherein both or more person.Nitrogenous
Compound preferably by with the gross weight scope based on compositionss from 0.1 to 3 weight %, particularly make from the amount of 0.5 to 2 weight %
With.
(D) (methyl) acyclic compound for tackness and viscosity adjustment or organic solvent
In (methyl) acyclic compound for tackness and viscosity adjustment or organic solvent and negative photosensitive compositionss
Describe is identical.
(E) additive
According to the present invention a specific embodiment, additive be selected from antioxidant, light stabilizer, tackifier and
The group that surfactant is formed.Additive with identical described in negative photosensitive compositionss.
4. film build method
According to a specific embodiment of the present invention, minus or eurymeric resin combination can be used to form thick photoresist
Film.Can under not limiting using art in known any technology form thick film, and example bag
Include spin coating, dip-coating, roller coat, net painting, flow coat, wire mark and droplet casting.In subsequent pre-bake step, solvent passes through under vacuo
Evaporated using Infrared irradiation or by heating.Then, compositionss are made to be exposed selectively to excimer laser, far ultraviolet
Light, ultraviolet light, visible ray, electron beam, X-ray, g line (wavelength 436nm), i line (wavelength 365nm), h line (wavelength 405nm) or
Above-mentioned mixed light.For example, it is possible to using contact, neighbouring or projection exposure.
After exposure, it is possible to use photoresist is developed by alkaline aqueous solution as developer solution.As for alkaline-based developer, permissible
Using quaternary ammonium water-soluble liquid, such as Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide, or the aqueous solution of amine, for example ammonia, ethamine,
Diethylamine or triethylamine.The aqueous solution of Tetramethylammonium hydroxide (TMAH) is preferred.
The present invention will be explained in greater detail with reference to above example.The purpose that these embodiments illustrate that is provided,
And the scope of the present invention is not limited to this.In the embodiment above, unless otherwise specified, otherwise number is by weight.
Embodiment
1. the synthesis of oligomeric silsesquioxane copolymer (photosensitive resin)
[synthesis example 1]
The photosensitive resin being represented by following procedure formula 4.
To be placed in the flask equipped with agitator and thermometer as the oxolane (40g) of solvent and ultra-pure water (20g),
It is subsequently adding potassium carbonate (0.2g) as catalyst in flask.Mixture is stirred at room temperature dissolving 20 minutes.To solution
Add MTMS (0.2 mole).Allow gained mixture reaction 2 hours.The periods of 30 minutes to reaction solution
It is slowly added dropwise 4- (triethoxy silicon substrate) butanoic acid (0.3 mole), trimethoxy (phenyl) silane (0.2 mole) and 3- (three ethoxies
Base silicon substrate) propyl methacrylate (0.3 mole) mixture.After being added dropwise to complete, reaction carries out 8 hours.Use dichloromethane
Alkane extractive reaction mixture.Dichloromethane is evaporated off under reduced pressure, obtains the subject copolymers of formula 4.
Measure molecular weight and the polydispersity index of product by gpc analysis on the basis of polystyrene.Find polymer
Resin has the acid number of the weight average molecular weight of 12,000-15,000, the polydispersity index of 2.2-2.4 and 110.
[synthesis example 2]
The photosensitive resin being represented by following procedure formula 5.
To be placed in the flask equipped with agitator and thermometer as the oxolane (40g) of solvent and ultra-pure water (20g),
It is subsequently adding potassium carbonate (0.2g) as catalyst in flask.Mixture is stirred at room temperature dissolving 20 minutes.To solution
Add trimethoxy (3- (oxirane -2- ylmethoxy) propyl group) silane (0.2 mole).Allow gained mixture reaction 2 hours.
The periods of 30 minutes, reaction solution is slowly added dropwise with 4- (triethoxy silicon substrate) butanoic acid (0.3 mole), trimethoxy (phenyl)
Silane (0.2 mole) and the mixture of 3- (triethoxy silicon substrate) propyl methacrylate (0.3 mole).It is added dropwise to complete it
Afterwards, reaction carries out 8 hours.With dichloromethane extractive reaction mixture.Dichloromethane is evaporated off under reduced pressure, obtains the target of formula 5
Copolymer.
Measure molecular weight and the polydispersity index of product by gpc analysis on the basis of polystyrene.Find polymer
Resin has the acid number of the weight average molecular weight of 16,000-17,000, the polydispersity index of 2.3-2.4 and 102.
[synthesis example 3]
The photosensitive resin being represented by following procedure formula 6.
Put into the dichloromethane of 100mL as solvent under nitrogen stream in the flask equipped with agitator and thermometer,
It is subsequently adding 4- (triethoxy silicon substrate) phenol (0.3 mole).Add while internal temperature is held in room temperature (25 DEG C)
The p- pyridinium p-toluenesulfonic acid of 0.4g.At room temperature solution is slowly added dropwise with ethyl vinyl ether (0.3 mole) in 15g solvent
In dilute solution.Mixture is allowed to react 4 hours at room temperature.Confirm that ethyl vinyl ether disappears it by thin layer chromatography art
Afterwards, the distilled water of 150mL is added so that reaction is quenched to reaction solution.Solution is moved on to separatory funnel.Afterwards, separate the two of lower section
Chloromethanes layer and with distilled water wash three times so that pH to be adjusted to neutrality.Retort solution is to obtain triethoxy (4- under reduced pressure
(1- ethoxy ethoxy) phenyl) silane (0.3 mole) is transparency liquid.
To be placed in another as the oxolane (40g) of solvent and ultra-pure water (40g) equipped with agitator and thermometer
In flask, it is subsequently adding potassium carbonate (0.2g) as catalyst in flask.Mixture is stirred at room temperature dissolving 20 minutes.
MTMS (0.3 mole) is added to solution.Allow gained mixture reaction 2 hours.The periods of 30 minutes to anti-
Solution is answered to be slowly added dropwise triethoxy (4- (1- ethoxy ethoxy) phenyl) silane (0.3 mole), 4- (triethoxy silicon substrate)
Butanoic acid (0.1 mole) and the mixture of trimethoxy (phenyl) silane (0.3 mole).After being added dropwise to complete, it is little that reaction carries out 8
When.With dichloromethane extractive reaction mixture.Dichloromethane is evaporated off under reduced pressure, obtains the subject copolymers of formula 6.
Measure molecular weight and the polydispersity index of product by gpc analysis on the basis of polystyrene.Find polymer
Resin has the acid number of the weight average molecular weight of 9,000-10,000, the polydispersity index of 1.8-2.0 and 38.
[synthesis example 4]
The photosensitive resin being represented by following procedure formula 7.
Put into the dichloromethane of 100mL as solvent under nitrogen stream in the flask equipped with agitator and thermometer,
It is subsequently adding 4- (triethoxy silicon substrate) phenol (0.3 mole).Add while internal temperature is held in room temperature (25 DEG C)
The p- pyridinium p-toluenesulfonic acid of 0.4g.At room temperature solution is slowly added dropwise with ethyl vinyl ether (0.3 mole) in 15g solvent
In dilute solution.Mixture is allowed to react 4 hours at room temperature.Confirm that ethyl vinyl ether disappears it by thin layer chromatography art
Afterwards, the distilled water of 150mL is added so that reaction is quenched to reaction solution.Solution is moved on to separatory funnel.Afterwards, separate the two of lower section
Chloromethanes layer and with distilled water wash three times so that pH to be adjusted to neutrality.Retort solution is to obtain triethoxy (4- under reduced pressure
(1- ethoxy ethoxy) phenyl) silane (0.3 mole) is transparency liquid.
To be placed in another as the oxolane (40g) of solvent and ultra-pure water (40g) equipped with agitator and thermometer
In flask, it is subsequently adding potassium carbonate (0.2g) as catalyst in flask.Mixture is stirred at room temperature dissolving 20 minutes.
MTMS (0.3 mole) is added to solution.Allow gained mixture reaction 2 hours.The periods of 30 minutes to anti-
Solution is answered to be slowly added dropwise triethoxy (4- (1- ethoxy ethoxy) phenyl) silane (0.3 mole), 4- (triethoxy silicon substrate)
Butanoic acid (0.1 mole) and the mixture of trimethoxy (3- (oxirane -2- ylmethoxy) propyl group) silane (0.3 mole).Drip
After adding into, reaction carries out 8 hours.With dichloromethane extractive reaction mixture.Dichloromethane is evaporated off under reduced pressure, obtains formula
7 subject copolymers.
Measure molecular weight and the polydispersity index of product by gpc analysis on the basis of polystyrene.Find polymer
Resin has the acid number of the weight average molecular weight of 9,500-10,500, the polydispersity index of 1.8-2.2 and 37.
[synthesis example 5]
The photosensitive resin being represented by following procedure formula 8.
To be placed in the flask equipped with agitator and thermometer as the oxolane (40g) of solvent and ultra-pure water (40g),
It is subsequently adding potassium carbonate (0.2g) as catalyst in flask.Mixture is stirred at room temperature dissolving 20 minutes.To solution
Add MTMS (0.3 mole).Allow gained mixture reaction 2 hours.The periods of 30 minutes to reaction solution
It is slowly added dropwise 4- (triethoxy silicon substrate) butanoic acid (0.4 mole) and trimethoxy (3- (oxirane -2- ylmethoxy) propyl group)
The mixture of silane (0.3 mole).
After being added dropwise to complete, reaction carries out 8 hours.Dichloromethane extractive reaction mixture with 150mL.Nitrogen stream it
Under put into dichloromethane solution in another flask equipped with agitator and thermometer, then internal temperature is being held in room
The p- pyridinium p-toluenesulfonic acid of 0.4g is added while warm (25 DEG C).At room temperature ethyl vinyl ether is slowly added dropwise to solution
(0.3 mole) dilute solution in 15g solvent.Mixture is allowed to react 4 hours at room temperature.Second is confirmed by thin layer chromatography art
After base vinyl ethers disappear, reaction solution is added with the distilled water of 150mL so that reaction is quenched.Solution is moved on to separatory funnel.
Afterwards, separate the dichloromethane layer of lower section, be then distilled to yield the subject copolymers of formula 8 under vacuo.
Measure molecular weight and the polydispersity index of product by gpc analysis on the basis of polystyrene.Find polymer
Resin has the acid number of the weight average molecular weight of 8,000-8,500, the polydispersity index of 1.8-2.1 and 32.
[synthesis example 6]
The photosensitive resin being represented by following procedure formula 9.
To be placed in the flask equipped with agitator and thermometer as the oxolane (40g) of solvent and ultra-pure water (40g),
It is subsequently adding potassium carbonate (0.2g) as catalyst in flask.Mixture is stirred at room temperature dissolving 20 minutes.To solution
Add MTMS (0.3 mole).Allow gained mixture reaction 2 hours.The periods of 30 minutes to reaction solution
It is slowly added dropwise 4- (triethoxy silicon substrate) butanoic acid (0.4 mole) and trimethoxy (3- (oxirane -2- ylmethoxy) propyl group)
The mixture of silane (0.3 mole).
After being added dropwise to complete, reaction carries out 8 hours.Dichloromethane extractive reaction mixture with 150mL.Nitrogen stream it
Under put into dichloromethane solution in another flask equipped with agitator and thermometer, then internal temperature is being held in room
The p- pyridinium p-toluenesulfonic acid of 0.4g is added while warm (25 DEG C).At room temperature solution is slowly added dropwise with 3,4- dihydro -2H-
Piperazine is muttered (0.3 mole) dilute solution in 15g solvent.Mixture is allowed to react 4 hours at room temperature.True by thin layer chromatography art
Recognize 3,4- dihydro -2H- piperazine mutter disappearance after, to reaction solution add 150mL distilled water so that reaction is quenched.Solution is moved on to point
Liquid funnel.Afterwards, separate the dichloromethane layer of lower section, be then distilled to yield the subject copolymers of formula 9 under vacuo.
Measure molecular weight and the polydispersity index of product by gpc analysis on the basis of polystyrene.Find polymer
Resin has the acid number of the weight average molecular weight of 9,000-9,500, the polydispersity index of 1.9-2.1 and 35.
The structure of the oligomeric silsesquioxane copolymer of synthesis is summarized in Table 1.
Table 1
2. the preparation of negative resin composition
Embodiment 1
Fluoropolymer resin using synthesis in synthesis example 1 and 2 prepares negative-tone composition (embodiment 1-1 to 1-4).By 40
Part various fluoropolymer resins, 25 parts of vinylation unsaturated compound (M500, MIWON spy uses Chemical Co., Ltd.), 7 parts
Irgacure TPO (BASF) or TPM-P07 (TAKOMA Technology Co., Ltd.) is as photopolymerization initiator, 3- ethoxy-propionic acid
Ethyl ester mixes at room temperature as the tackifier (KBM 403, SHIN-ETSU) of organic solvent and 3 parts.Stirring 6 hours
Afterwards, the negative-tone composition that solids content is adjusted to 35% is obtained by 5.5 μm of filter filtering mixt.To combine
The composition of thing (embodiment 1-1 to 1-4) and its content are shown in table 2.
Table 2
3. the preparation of eurymeric resin combination
Embodiment 2
Fluoropolymer resin preparation positive type composition (embodiment 2-1 to 2-8) using synthesis in synthesis example 3 to 6.By 45
The various fluoropolymer resins of part, 2 parts of the light acid producing agents being represented by formula 2 or 3, organic solvent, 0.1 part of surfactants
And 0.1 part of adhesion promoters mix (BYK333).It is stirred at room temperature 1 hour afterwards, by 0.2 μm of filter
Filtering mixt is to obtain the positive type composition that solids content is adjusted to 35%.One-tenth by compositionss (embodiment 2-1 to 2-8)
Divide and its content is shown in table 3.
Table 3
[comparative example 1]
Prepare negative-type photosensitive resin composition (comparative example 1-1 and 1-2), difference in the same manner as example 1
It is only that the fluoropolymer resin replacing synthesis in synthesis example 1 and 2 using acroleic acid polymerization resin.By as the two of solvent
The methacrylic acid of the methacrylate of 0 part of polyase 13,10 parts of methyl methacrylate and 10 parts in glycol list ether
To prepare acroleic acid polymerization resin.Acroleic acid polymerization resin has 50% solids content and 13,000 weight average divides
Son amount.
[comparative example 2]
Light acid producing agent that the acrylic resin of 45 weight portions, 2 weight portions are represented by formula 2 or 3, organic solvent, 0.1 weight
The surfactant (BYK333) of amount part, the adhesion promoters (KBM303) of 0.1 weight portion and the diethylene glycol monoethyl ether as solvent
Mix and to prepare compositionss (comparative example 2-1 and 2-2).Acrylic resin is replaced with 30 parts of acetal protecting group, and has 15,
000 weight average molecular weight.
[physical property assessment]
By in embodiment 1-1 to 1-4, embodiment 2-1 to 2-8 and comparative example 1 and 2 preparation every kind of photosensitive composition with
800-900rpm is applied on spin coater and carries out 15 seconds, and is dried 100 seconds on 90 DEG C of hot plate.Film is made to shield by patterning
It is exposed to the ultrahigh pressure mercury lamp as light source, the TMAH solution rotation using 2.38% at 25 DEG C is developed 60 seconds, washes with water,
And toast 40 minutes at 230 DEG C to obtain pattern.Following parameter is assessed to pattern.
(1) sensitivity
Using spin coater, various Photosensitve resin compositions are coated on glass substrate (Eagle2000, SAMSUNG
CORNING on), and it is dried 1 minute on 90 DEG C of hot plate to form organic insulating film.Using contact pilotage contourograph (α-step
500, KLA-Tencor) measure the thickness of film.Then, sample is made to be exposed to high voltage mercury lamp by shielding, and with 2.38%
TMAH solution spray development is to form resist pattern.Sensitivity table is shown as forming size and 20 microns of shielding pattern identical resistances
The optimum exposure dosage (mJ/sqcm) of agent pattern.That is, needing the resist of less exposure dose can use less luminous energy
Form image, represent that sensitivity is higher.
(2) residual film ratio after developing
The pattern thickness recording after development calculates residual film ratio.
(3) absorbance
By every kind of compositionss spin coating on the glass substrate to form 3 microns of thick films.The whole surface of film is made to be exposed to
100mJ, subsequently rear baking 40 minutes at 240 DEG C.Measure absorbance using UV spectrogrph under 400-800nm simultaneously average.
(4) cone angle
Make to carry out after bake at 240 DEG C including size after development and the substrate of 20 microns of shielding pattern identical resist patterns
Roasting 40 minutes.Afterwards, the cone angle of pattern is measured using ultramicroscope.
(5) tackness
According to JIS D 0202 method of testing, make various compositionss exposures, development, and heat 40 minutes at 240 DEG C.?
After cross-cut line being marked with the shape of crossbanding on film, carry out peel test using adhesive tape.Observe interdigitating cuts
The tackness to assess film for the exfoliated state.When not having interdigitating cuts to be stripped, tackness is judged as " good (zero) ".When
When one or more interdigitating cuts are stripped, tackness is judged as " poor (×) ".
Result is shown in table 4-7.
The physical property assessment result of negative-tone composition
The result of table 4 display sensitivity, residual film ratio and tackness aspect.
Table 4
Table 5 shows the result of cone angle and absorbance aspect.
Table 5
The physical property assessment result of positive type composition
The result of table 6 display sensitivity, residual film ratio and tackness aspect.
Table 6
Table 7 shows the result of cone angle and absorbance aspect.
Table 7
The minus organic insulation film composition that can be seen that the present invention from the result of table 4 and table 5 has enough thermostabilitys
To control the cone angle of pattern and to prevent from giving vent to anger, and the negative light resistance agent with high tack strength can be provided to dielectric film.From
The eurymeric organic insulation film composition that the result of table 6 and 7 can be seen that the present invention has enough thermostabilitys to control pattern
Cone angle simultaneously prevents from giving vent to anger, and can provide the high sensitivity eurymeric photoresist of chemistry amplification.
Fig. 1 is the image of the sectional hole patterns of dielectric film that display is formed using the Photosensitve resin composition of embodiment 1-2, Fig. 2
The image of the sectional hole patterns of the dielectric film being formed using the Photosensitve resin composition of comparative example 1-1 for display, Fig. 3 is display using real
Apply the image of the sectional hole patterns of dielectric film of Photosensitve resin composition formation of a 2-2, and Fig. 4 is display using comparative example 2-1
The image of the sectional hole patterns of dielectric film that Photosensitve resin composition is formed.These images show, using the group of embodiment 1-2 and 2-2
Compound formed sectional hole patterns cone angle substantially close to 90 °, different from using comparative example 1-1 and 2-1 compositionss formed hole
The cone angle of pattern.
Claims (13)
1. a kind of photosensitive resin, comprises (A) the oligomeric silsesquioxane copolymer being represented by formula 1：
Wherein each R1Stand alone as the C being substituted or being unsubstituted1-C20Stretch alkyl,
R2And R3Each stand alone as(wherein R2aAnd R2bEach stand alone as and be substituted or without taking
The C in generation1-C30Alkyl, C3-C30Pi-allyl, C6-C30Aryl, C7-C30Aralkyl or C3-C30Cycloalkyl),
R4For having being substituted or being unsubstituted C of at least one vinylation unsaturated bond2-C10Alkyl,
R5Be selected from i) be substituted or be unsubstituted containing C3-C10Cyclic ether group, ii) C that is substituted or is unsubstituted1-C10Alkane
Base, iii) C that is substituted or is unsubstituted6-C20The group that cyclic hydrocarbon radical and combinations of the above are formed,
P is 1 to 3 integer,
L and z each stands alone as 2 to 100 integer, and
M, n, x and y each stand alone as 0 to 100 integer.
2. photosensitive resin as claimed in claim 1, wherein said oligomeric silsesquioxane copolymer has 2,000 to 50,000
Weight average molecular weight.
3. photosensitive resin as claimed in claim 2, wherein said oligomeric silsesquioxane copolymer has 1.0 to 5.0 dispersion
Degree.
4. photosensitive resin as claimed in claim 1, wherein said oligomeric silsesquioxane copolymer has 50 to 150 acid number.
5. photosensitive resin as claimed in claim 1, wherein when described oligomeric silsesquioxane copolymer is used for negative photosensitive tree
During oil/fat composition, repetitives (I), (II), (III), (IV), (V) and (VI) are in described oligomeric silsesquioxane copolymer
Ratio is respectively 5 to 40 moles of %, 0 to 20 mole of %, 5 to 40 moles of %, 5 to 40 moles of %, 5 to 40 moles of % and 5 to 30
Mole %.
6. photosensitive resin as claimed in claim 1, wherein when described oligomeric silsesquioxane copolymer is used for positive type light sensitive tree
During oil/fat composition, repetitives (I), (II), (III), (IV), (V) and (VI) are in described oligomeric silsesquioxane copolymer
Ratio is respectively 5 to 20 moles of %, 5 to 20 moles of %, 0 to 20 mole of %, 0 to 30 mole of %, 0 to 5 mole of % and 5 to 30
Mole %.
7. a kind of Photosensitve resin composition, comprises the photosensitive resin as any one of claim 1 to 6.
8. a kind of negative-type photosensitive resin composition, comprises：
(A) photosensitive resin as claimed in claim 1；
(B) there is the polyfunctional compound of vinylation unsaturated bond；
(C) photopolymerization initiator；
(D) (methyl) acyclic compound for tackness and viscosity adjustment or organic solvent；And
(E) interpolation of at least one group being formed selected from antioxidant, light stabilizer, tackifier and surfactant
Agent.
9. negative-type photosensitive resin composition as claimed in claim 8, wherein said photosensitive resin, described has vinylation insatiable hunger
With the polyfunctional compound of key, described photopolymerization initiator, described (methyl) acrylated for tackness and viscosity adjustment
Compound, described organic solvent and described additive are respectively with gross weight 5 to 45 weight % based on described compositionss, 5 to 50 weights
Amount %, 0.1 to 10 weight %, the amount of 10 to 50 weight %, 20 to 75 weight % and 0.01 to 5 weight % exist.
10. a kind of positive photosensitive resin composition, comprises：
(A) photosensitive resin as claimed in claim 1；
(F) light acid producing agent or Photoactive compounds；
(G) alkali quencher；
(D) (methyl) acyclic compound for tackness and viscosity adjustment or organic solvent；And
(E) interpolation of at least one group being formed selected from antioxidant, light stabilizer, tackifier and surfactant
Agent.
11. positive photosensitive resin compositions as claimed in claim 10, wherein said photosensitive resin, described smooth acid producing agent,
Described Photoactive compounds, described alkali quencher, described for tackness and viscosity adjustment (methyl) acyclic compound, institute
State organic solvent and described additive respectively with gross weight 5 to 45 weight % based on described compositionss, 0.1 to 10 weight %,
1 to 30 weight %, 0.1 to 3 weight %, the amount of 10 to 50 weight %, 20 to 75 weight % and 0.01 to 5 weight % exist.
A kind of 12. organic insulating films being formed using Photosensitve resin composition as claimed in claim 7.
A kind of 13. substrates, comprise by solidifying the resin pattern that Photosensitve resin composition as claimed in claim 7 is formed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20140046944 | 2014-04-18 | ||
| KR10-2014-0046944 | 2014-04-18 | ||
| PCT/KR2015/003902 WO2015160229A1 (en) | 2014-04-18 | 2015-04-18 | Polysilsesquioxane copolymer and photosensitive resin composition containing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106459415A true CN106459415A (en) | 2017-02-22 |
| CN106459415B CN106459415B (en) | 2019-09-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201580020253.8A Active CN106459415B (en) | 2014-04-18 | 2015-04-18 | Oligomeric silsesquioxane copolymer and Photosensitve resin composition including the oligomeric silsesquioxane copolymer |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR101580898B1 (en) |
| CN (1) | CN106459415B (en) |
| TW (1) | TWI534182B (en) |
| WO (1) | WO2015160229A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021168949A1 (en) * | 2020-02-24 | 2021-09-02 | Tcl华星光电技术有限公司 | Display panel and negative photoresist material |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102612640B1 (en) * | 2016-01-21 | 2023-12-11 | 도오꾜오까고오교 가부시끼가이샤 | Resist composition, polymer compound, and method of forming resist pattern |
| KR101906281B1 (en) * | 2016-03-30 | 2018-10-10 | 삼성에스디아이 주식회사 | Photo-sensitive Composition, Cured Film Prepared Therefrom, and Device Incoporating the Cured Film |
| KR20180065185A (en) * | 2016-12-07 | 2018-06-18 | 한국과학기술연구원 | Self-healing polysilsesquioxanes and hybrid film using the same |
| KR101996262B1 (en) * | 2017-09-01 | 2019-10-01 | (주)휴넷플러스 | Barrier resin composition, method for uv curable barrier layer and electronic device |
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| US20120003437A1 (en) * | 2010-07-01 | 2012-01-05 | Fujifilm Corporation | Photosensitive composition, pattern forming material and photosensitive film using the same, pattern forming method, pattern film, antireflection film, insulating film, optical device, and electronic device |
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| EP0224680B1 (en) | 1985-12-05 | 1992-01-15 | International Business Machines Corporation | Diazoquinone sensitized polyamic acid based photoresist compositions having reduced dissolution rates in alkaline developers |
| KR20000076531A (en) * | 1999-01-28 | 2000-12-26 | 무네유키 가코우 | Positive silicone-containing photosensitive composition |
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2015
- 2015-04-17 KR KR1020150054397A patent/KR101580898B1/en active IP Right Grant
- 2015-04-17 TW TW104112409A patent/TWI534182B/en active
- 2015-04-18 CN CN201580020253.8A patent/CN106459415B/en active Active
- 2015-04-18 WO PCT/KR2015/003902 patent/WO2015160229A1/en active Application Filing
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| CN102549736A (en) * | 2009-09-29 | 2012-07-04 | 国际商业机器公司 | Patternable low-k dielectric interconnect structure with a graded cap layer and method of fabrication |
| US20120003437A1 (en) * | 2010-07-01 | 2012-01-05 | Fujifilm Corporation | Photosensitive composition, pattern forming material and photosensitive film using the same, pattern forming method, pattern film, antireflection film, insulating film, optical device, and electronic device |
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| WO2021168949A1 (en) * | 2020-02-24 | 2021-09-02 | Tcl华星光电技术有限公司 | Display panel and negative photoresist material |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015160229A1 (en) | 2015-10-22 |
| TW201602173A (en) | 2016-01-16 |
| TWI534182B (en) | 2016-05-21 |
| CN106459415B (en) | 2019-09-24 |
| KR20150121666A (en) | 2015-10-29 |
| KR101580898B1 (en) | 2015-12-31 |
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