CN1987650A - Negative Photoresist Composition - Google Patents
Negative Photoresist Composition Download PDFInfo
- Publication number
- CN1987650A CN1987650A CN 200510134663 CN200510134663A CN1987650A CN 1987650 A CN1987650 A CN 1987650A CN 200510134663 CN200510134663 CN 200510134663 CN 200510134663 A CN200510134663 A CN 200510134663A CN 1987650 A CN1987650 A CN 1987650A
- Authority
- CN
- China
- Prior art keywords
- composition
- monomer
- methyl
- bis
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 229920002120 photoresistant polymer Polymers 0.000 title abstract 5
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 16
- 125000003368 amide group Chemical group 0.000 claims description 14
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
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- CRXLYZZNDQEWAV-UHFFFAOYSA-N CP(C1=CC=CC=C1)(C1=CC=CC=C1)=O.CC1=CC(=CC(=C1)C)C Chemical compound CP(C1=CC=CC=C1)(C1=CC=CC=C1)=O.CC1=CC(=CC(=C1)C)C CRXLYZZNDQEWAV-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 2
- SUXZDKKETJMFHI-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone;diphenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1.C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 SUXZDKKETJMFHI-UHFFFAOYSA-N 0.000 claims description 2
- LMORUOIFIKITKP-UHFFFAOYSA-N bis[4-(dimethylamino)phenyl]methanone;diphenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1.C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 LMORUOIFIKITKP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 4
- 239000003504 photosensitizing agent Substances 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
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- 125000003277 amino group Chemical group 0.000 abstract 1
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 15
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- BDLWRIAFNYVGTC-UHFFFAOYSA-N 2-[bis(2-chloroethyl)amino]ethyl 3-(acridin-9-ylamino)propanoate Chemical compound C1=CC=C2C(NCCC(=O)OCCN(CCCl)CCCl)=C(C=CC=C3)C3=NC2=C1 BDLWRIAFNYVGTC-UHFFFAOYSA-N 0.000 description 2
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- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Materials For Photolithography (AREA)
Abstract
本发明是关于一种负型光阻剂组合物，尤其一种含有聚亚酰胺的负型光阻剂组合物。本发明的负型光阻剂组合物的一主要成份为(a)聚亚酰胺其具有悬垂的－COOH(羧酸基)且部分的羧酸基与带有环氧基团的(甲基)丙烯酸酯单体(glycidyl(meth)acrylate)反应形成键结，而残留的另一部分羧酸基与另外添加的成份(b)带有第三胺基及C＝C双键的单体形成离子键结。本发明的负型光阻剂组合物的另一成份(c)为光起始剂(photoinitiator)或称光敏感剂(photosensitizer)。以上成份(a)至(c)均溶解于一溶剂中。The present invention relates to a negative photoresist composition, in particular to a negative photoresist composition containing polyimide. A main component of the negative photoresist composition of the present invention is (a) polyimide having pendant -COOH (carboxylic acid group) and part of the carboxylic acid group reacts with (meth) acrylate monomer (glycidyl (meth) acrylate) with epoxy group to form a bond, while the remaining part of the carboxylic acid group forms an ionic bond with the additional component (b) monomer with a third amine group and a C=C double bond. Another component (c) of the negative photoresist composition of the present invention is a photoinitiator or photosensitizer. The above components (a) to (c) are all dissolved in a solvent.
Description
Technical field
The invention relates to a kind of negative light resistance agent composition, especially a kind of negative light resistance agent composition that contains pi.
Background technology
Along with product microminiaturization trend, make that the development of high density flexible base plate is flourishing day by day.Under the prerequisite of high density, graph thinning, the coverlay material behavior of used flexible base plate material must possess better thermotolerance, dimensional stability, electrically reach endurance.Used pre-punched hole (Pre-punching) or its smallest aperture aperture of prebored hole (Pre-drilling) perforate technology of tradition soft board can only reach 800 μ m, and other minimum-value aperture as wire mark boring (Screen Printing Drilling) also can only reach 300 μ m.In addition Laser drill (Laser Drlling) though mode can reach 25 μ m, but its cost is higher, competitiveless.For improving the problem of perforate, therefore import the coverlay material of sensing optical activity, it utilizes the mode of micro-photographing process can obtain meticulous pattern, yet the material of these sensing optical activities mostly is epoxy (epoxy) resin greatly and acrylic acid (acrylic) resin is formed, the physical strength of its thermotolerance and coverlay all is not enough to be applied to the product of high-order, and because of the demand of environmental protection such as following non-halogen non-phosphate, for epoxy resin and acryl resin, the anti-combustion grade of UL-94V0 is a big problem.And sensing optical activity pi (PSPI) material has excellent thermostability and favorable mechanical, electric and chemical property, can be issued to the anti-combustion grade of UL-94V0 not adding flame retardant, not have problems such as non-halogen non-phosphate, be suitable for very much the high-order flexible base plate of high density, graph thinning.
Traditional PSPI generally is made up of its presoma-polyamic acid or polyesteramide, and it needs 350 ℃ of sclerosis of high temperature to form pi behind micro-photographing process.The problem that 350 ℃ of copper wire is had oxidation produces; Also have thickness to shrink (shrinkage) excessive problem to pi itself, and its thickness can't satisfy the above thickness demand of coverlay 20 μ m mostly less than 10 μ m.
Solvable type sensing optical activity pi material is used for high-order flexible base plate coverlay, disclose as US2003/0176528, US2004/0247908, US2004/0265731, US2004/0235992, though can be 230 ℃ of hardening at subcritical temeratures, but, has the not good problem of flame resistance because the content of its light sensitive molecule (acrylate) is too high.Therefore need add the flame retardant of phosphorous or halogen again, and not meet the trend of following non-halogen non-phosphate.
Though its firmly roasting temperature of the PSPI material of solvable type can be lower, its solvent resistance is all general just relatively poor, and needs can develop with the alkaline-based developer of high concentration, so its practicality is lower.People such as Masao Tomoi are in Reactive﹠amp; Functional Polymers, 2003,56,59～73, JP2002341535, JP2003345007 propose its main chain and have-the solvable type pi of COOH group, utilization has acrylic acid (ester) monomer of the 3rd amido and is somebody's turn to do-COOH group generation ion bond, forms minus PSPI material.The PSPI material of ion of bonding is because therefore its bond intensity poor than covalent bond type be applicable to the PSPI thickness below 10 μ m, if PSPI is that its exposure energy is up to 8000mj/cm under thick film (the 20 μ m) situation
2, do not have a practicality.Also because of the relation of above-mentioned ionic link, this PSPI material has relatively poor solvent resistance and alkali resistance at the formed PSPI film in hard roasting back.
Summary of the invention
A fundamental purpose of the present invention is to propose a kind of negative light resistance agent composition (sensing optical activity pi (PSPI) material) that does not have the shortcoming of Prior Art.
One Main Ingredients and Appearance of negative light resistance agent composition of the present invention for (a) pi its have dangle-carboxylic acid group of COOH (carboxylic acid group) and part forms bond with (methyl) acrylate monomer (glycidyl (meth) acrlate) reaction that has epoxide group, and residual another part carboxylic acid group forms the ion bond with the monomer that the composition (b) that adds in addition has the 3rd amido and the two keys of C=C.Another composition (c) of negative light resistance agent composition of the present invention is light initiator (photoinitiator) or claims photosensitizer (photosensitizer).Above composition (a) to (c) all is dissolved in the solvent.
Its Main Ingredients and Appearance of negative light resistance agent composition proposed by the invention is made up of pi, does not therefore need to carry out roasting (post-curing) firmly with high temperature again, can satisfy the demand of the high-order flexible base plate coverlay that needs high density, graph thinning.Because the main chain bond of this pi has (methyl) acrylate monomer, therefore negative light resistance agent composition of the present invention can be used for forming thick film and has excellent thickness conservation rate.Composition (b) then helps negative light resistance agent composition of the present invention available alkaline solution after exposure to develop at short notice to finish.
Embodiment
The invention provides a kind of negative light resistance agent composition (a sensing optical activity pi material), its coverlay that can be used in the flexible printed wiring board is solder flux shielding (Solder Mask) to protect copper cash fragile on soft board, also can be used as during assembling.
Negative light resistance agent composition of the present invention is contained in the pi that a) has formula (I) in the solvent; B) contain the unsaturated ethylene thiazolinyl monomer of the 3rd amido; And c) the light initiator, wherein the amount of light initiator is 0.1～30% of this pi (I) solid weight, the amount of this monomer be the contained carboxylic acid group of pi (I) molal quantity 70～130%, preferable, 90～110%,
In the formula (I)
Ar
1Be the tetravalence base;
Ar
2Be bivalent radical;
Ar
3For containing carboxylic acid group's bivalent radical;
Ar
4For containing-CH
2-C (OH) H-CH
2The bivalent radical of-O-C (O)-C (R)=CH base, wherein R is H or methyl;
M+n+o=1,0.1≤n+o≤0.6, and n: o=9: 1～4: 6, preferable, n: o=3: 1～1: 1.
Preferable, m=0.3～0.7.
Preferable, Ar
3For
Or
Preferable, Ar
4For
Or
R wherein
*For-CH
2-C (OH) H-CH
2-O-C (O)-C (R)=CH, wherein R is H or methyl.
Preferable, this monomer is the 3rd amido C1～C4 Arrcostab of acrylic or methacrylic acid, or N-(the 3rd amido C1-C4 alkyl) acrylamide or Methacrylamide.
Preferable, Ar
1Be to be selected from
Preferable, Ar
2Be to be selected from
Wherein m is 1～20 integer, and X
1For
-O-，-S-，-C(CF
3)
2-，-C(CH
3)
2-
-CH
2，-SO
2-，-NHCO-，
Wherein m is 1～20 integer, and Z is H or methyl.
A kind of method that is suitable for preparing the pi (a) of negative light resistance agent composition of the present invention comprises the following step:
Dicarboxylic anhydride, first kind of diamines and second kind of diamines are reacted, to form polyamic acid (polyamic acid), wherein this second kind of diamines contains the carboxylic acid group, and wherein this dicarboxylic anhydride and first kind of diamines can be the dicarboxylic anhydride that the preparation method used always and the diamines of present pi;
Add a high boiling solvent and in the reaction mixture that contains polyamic acid, carry out the chemical cyclization of polyamic acid, to form pi, wherein the temperature of this high boiling solvent and chemical cyclization can be at present and is equipped with the inferior acid amides dust head of institute of hot polymerization with chemical cyclisation legal system; And
Add acrylic or methacrylic acid glycidyl ester (glycidyl (meth) acrylate) in the reaction mixture that contains pi and the contained temperature of part carboxylic acid group between 60～130 ℃ of this glycidyl and pi reacted, so on the main chain of pi, form
-CH
2-C (OH) H-CH
2-O-C (O)-C (R)=CH side chain, wherein R is H or methyl, wherein if temperature of reaction too Gao Zehui the two keys of C=C are opened and are formed crosslinked (Crosslinking), can add an inhibitor in case of necessity and suppress this crosslinked generation.
The COOH base and the acrylic or methacrylic acid glycidyl ester of 10～60% in the COOH group on the pi main chain side group form covalency bond-COOR
*, if surpass COOH base formation covalency bond-COOR of 60%
*, then the development time of negative light resistance agent composition of the present invention can be long; If be lower than 10% not anti-developer solution, (residual film thickness) is not good for sensitivity variation and thickness conservation rate.
In the pi of above-mentioned preparation, further add and have the 3rd amido and the monomer (b) of the two keys of C=C and the preparation that light initiator (c) can be finished negative light resistance agent composition of the present invention, can add in case of necessity solvent for example N-methyl-2-than pyrrolidone (N-methyl-2-pyrrolidone; NMP), N,N-dimethylacetamide (N, N-dimethylacetamide; DMAc), gamma-butyrolacton (γ-butyrolactone; GBL), dimethylbenzene (Xylene), toluene (Toluene) are adjusted the stickiness of composition to degree that is fit to coating or required concentration.
The monomer (b) that has the two keys of the 3rd amido and C=C is because the 3rd amido can form " salt bridge (salt bridge) " with COOH and help to shorten development time and can increase sensitivity, and it can be array structure person under the tool or its mixing, but is not limited thereto:
The mol ratio (mole ratio) that has COOH base residual on the main chain of its adding proportions of monomer of the two keys of the 3rd amido and C=C and pi is 1: 1.
Negative light resistance agent composition of the present invention is for increasing the acrylate (multi-functional acrylate) that its cross-linking density can additionally add multiple functional radical again, Ethylene glycol dimethacrylate (ethyleneglycoldimethacrylate) for example, the EO of bisphenol-A modifies diacrylate (bisphenol A EO-modifieddiacrylate) (n=2～50), and (EO is oxirane (ethyleneoxide), n is the molal quantity of the oxirane that added), the EO of Bisphenol F modifies diacrylate (bisphenol F EO-modified diacrylate), three acrylic acid, three methanol-based propane esters (trimethylolpropane triacrylate), pentaerythritol triacrylate (pentaerythritol triacrylate), three (2-hydroxyethyl) isocyanates triacrylate (tris (2-hydroxyethyl) isocyanurate triacrylate) etc., but be not limited to above-described acrylate.Its addition is no more than 30% of pi solid weight, can make its flame resistance and mechanical property variation if surpass 30%.Preferable, its addition is higher than 10%, if be lower than 10% lifting of failing to help cross-linking density, and more not anti-developer solution.
Light initiator (c) can produce free radical after exposure, and impels the monomer crosslinked of the two keys of tool C=C.The exposure wavelength of light initiator is preferably 350nm～450nm.If exposure wavelength is outside this scope, then its optical efficiency is bad easily causes monomer crosslinked deficiency.Smooth initiator of the present invention (c) comprises (but being not limited to) the following stated:
Two (2,4,6-trimethylbenzene methyl)-phenylphosphine oxide
(bis (2,4,6-trimethylbenzoyl)-phenylphosphineoxide), 2-benzyl-2-dimethylamino-1-1 (4-good fortune quinoline phenyl)-butanone
(2-benzyl-2-dimethylamino-1-1 (4-morpholinophenyl)-butanone), (2,4,6-trimethylbenzene methyl) diphenyl phosphine oxide ((2,4,6-trimethyl benzoyl) two (.eta.5-2 diphenyl phosphine oxide),, 4-encircles penta 2-1-thiazolinyl)-two (2,6-two fluoro-3-(1H-pyrroles-1-yl) phenyl titanium
(bis (.eta.5-2,4-cyclopentadien-1-yl)-bis (2,6-dufluoro-3-(1H-pyrrol-1-yl)-phenyltitanium), 4,4 '-two (dimethylamino) diphenylketone (4,4 '-bis (dimethylamino) benzophenone), 4,4 '-two (diethylin) diphenylketone (4,4 '-bis (diethylamino) benzophenone), N-diethylamino phenyl alcohol radical amine (N-phenyldiethanolamine).The addition of light initiator (c) is 0.1～30% of a pi solid weight, then can destroy its thermostability too much if add, sensitivity deficiency then very little, and it is 3～10% more in right amount.
One is fit to use the micro-photographing process of negative light resistance agent composition of the present invention as follows: (i) negative light resistance agent composition is utilized rotary coating or alternate manner coat on the suitable base material; (ii) roasting in advance; (iii) exposure; (iv) develop; And (the pi pattern of the v) hard roasting back gained that develops.For example a copper clad laminate, flexible printed wiring board (FCCL), silicon substrate, glass or ito glass on the suitable base material in above-mentioned step (i); And above-mentioned alternate manner is coated with for example roller rubbing method (roller coating), half tone rubbing method (screencoating), a pouring curtain rubbing method (curtain coating), immersion plating (dip coating) and spray coating method (spraycoating), but is not limited to above-mentioned coating process.This step pre-roasting (prebake) (ii) is included in 70～120 ℃ and bakes several minutes down in advance to steam the solvent that removes wherein.The exposure (iii) of this step comprise will be in advance roasting base material under a light shield with by the actinic ray exposure, above-mentioned actinic ray for example can be used as photoactinic light source etc. for x-ray, electron beam ray, ultraviolet light ray, visible light ray or other.
Being added by an alkaline water developer through substrates coated after the exposure given development (iv), can obtain a photoresistance figure.Above-mentioned alkaline water developer comprises an alkaline solution, for example be inorganic base (potassium hydroxide, NaOH), primary amine (ethamine), secondary amine (diethylamine), tertiary amine (triethylamine), quarternary ammonium salt (Tetramethylammonium hydroxide (tetramethylammonium hydroxide, be called for short TMAH), wherein be preferably the developer that contains the Tetramethylammonium hydroxide composition.Development can be by soaking, spraying or cover liquid or use other method to finish.After the photoresistance figure after the development is subsequently via washed with de-ionized water, (v) remaining solvent is driven away and get final product at 180～300 ℃ of carry out down hard roasting.
The present invention will add by following preferred embodiment to give and further specify, and it as illustrative purposes only but not be used to limit the scope of the invention.
The formula that is calculated as follows of thickness conservation rate (film residual rate):
Thickness conservation rate (%)=[(thickness after hard the baking)/(thickness after pre-the baking)] * 100%
Medicine:
Dicyclo [2,2,2] suffering-7-thiazolinyl-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride
(bicyclo[2，2，2]oct-7-ene-2，3，5，6-tetracarboxylic dianhydride)(B1317)
Two (3,4-two carboxy phenyls) ether dianhydride (bis (3,4-dicarboxyphenyl) ether dianhydride (ODPA))
3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride (3,3 ', 4,4 '-benzophenone tetracarboxylicdianhydride (BTDA))
3,3 ', 4,4 '-two benzene tertacarbonic acid's dicarboxylic anhydrides (3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA))
3,5-diamines yl benzoic acid (3,5-diaminobenzoic acid (DABZ))
4,4 '-oxygen diphenylamine (4,4 '-Oxydianiline (ODA))
4,4 '-two (3-amido phenoxy group) diphenyl sulfone (4,4 '-bis (3-aminophenoxy) diphenyl sulfone (m-BAPS))
2,2-two (4-(4-amido phenoxy group) phenyl) propane (2,2-bis (4-(4-aminophenoxyl) phenyl) propane (BAPP))
Diamine propyl group tetramethyl disiloxane (bisaminopropyltetramethyldisiloxane (Siloxane248))
Glycidyl methacrylate (glycidyl methacrylate (GMA))
N-N-methyl-2-2-pyrrolidone N-(N-methyl-2-pyrrolidone; NMP)
Embodiment
Embodiment 1
Use is equipped with 500 milliliters three neck round-bottomed flasks of a mechanical stirrer and nitrogen inlet, and the NMP that add the BAPP of the DABZ of 11.41 g (75 mMs), 30.79 g (75 mMs) and add 330 grams add and give dissolving.Solution after the dissolving is added into the B1317 of 24.5708 grams (99 mM) under 0 ℃ of ice bath, stir add again after 2 hours 15.95 the gram (50 mM) BTDA and under room temperature, stirred again 4 hours, heat up after adding 70 dimethylbenzene that restrain, the azeotropic that has water and dimethylbenzene in the time of 160 ℃ produces.Treat to stir 5 hours down in 180 ℃ after wherein dimethylbenzene is run out of fully, cooling subsequently can obtain sticky unmodified PI solution V-1 again.Get V-1 solution 80 grams, the quinhydrones (Hydroquinone) that adds 1.09 gram GMA, 0.08 gram is used as inhibitor (inhibitor), under 100 ℃, stir the companion and can get sticky PI solution PI-1 in 12 hours, with the pentaerythritol triacrylate (pentaerythritol triacrylate) of 3.2 grams, the monomer N-[3-dimethylamine that contains the 3rd amido of 1.31 grams] propyl group] Methacrylamide
(N-[3-(dimethylamino) propyl] methacrylamide) and the 1.6 light initiators that restrain two (2,4,6-trimethylbenzene methyl)-(bis (2 for phenylphosphine oxide, 4,6-trimethylbenzoyl)-phenylphosphineoxide) make it evenly mixed, can get a sensing optical activity pi PSPI-1, utilize scraper PSPI-1 evenly to be coated on the Copper Foil of 1 OZ then, and via hot-air oven under 120 ℃, 5 minutes soft roasting program
(pre-bake) after, just can obtain the sensitization pi film that a thickness is about 20 μ m.(its measured wavelength is thrown about 1000mJ/cm between 250～400nm) then above-mentioned Copper Foil through coating PSPI-1 to be utilized the mercury-arc lamp of a filtered
2Energy exposed, again with tetramethyl ammonium hydroxide (the tetramethylammonium hydroxide of 3% (percentage by weight); TMAH) ethanolic solution that is made into is a developer, under 35 ℃, developed with the ultrasonic oscillator, development time is 120 seconds, cleaned 30 seconds with ethanol again, dry up with air cannon, carry out under 230 ℃ subsequently baking (post-curing) 30 minutes firmly in heated-air circulation oven, just can obtain a pi pattern, thickness is 18um.And this figure is compared with the thickness of its original coating in the hard roasting back of developing, and has 90% thickness conservation rate, can be observed live width and the pitch pattern that resolution is 30 μ m by optical microscope.
Embodiment 2
Get the unmodified PI solution V-1 among 80 embodiment 1 that restrain, the quinhydrones that adds 0.55 gram GMA, 0.08 gram again is used as inhibitor, stirs the companion and can get sticky PI solution PI-2 in 12 hours under 100 ℃.Pentaerythritol triacrylate with 3.2 grams, 1.97 the monomer N-[3-dimethylamine that contains the 3rd amido of gram] propyl group] Methacrylamide and the 1.6 light initiators that restrain two (2,4,6-trimethylbenzene methyl)-phenylphosphine oxide and PI solution PI-2 are evenly mixed, can get a sensing optical activity pi PSPI-2.Utilize scraper that PSPI-2 is evenly coated on the Copper Foil of 1 OZ then, and via hot-air oven under 120 ℃, after 5 minutes the soft roasting program, just can obtain the sensitization pi film that a thickness is about 20 μ m.(its measured wavelength is thrown about 1000mJ/cm between 250～400nm) then above-mentioned Copper Foil through coating PSPI to be utilized the mercury-arc lamp of a filtered
2Energy exposed, and be developer with the ethanolic solution of the TMAH of 3 weight %, under 35 ℃, developed with the ultrasonic oscillator, development time is 90 seconds.Cleaned 30 seconds with ethanol, dry up with air cannon, carried out under 230 ℃ in heated-air circulation oven subsequently roasting 30 minutes firmly, just can obtain a pi pattern, thickness is 17um.And this figure is compared with the thickness of its original coating in the hard roasting back of developing, and has 85% thickness conservation rate, can be observed live width and the pitch pattern that resolution is 30 μ m by optical microscope.
Embodiment 3
Sensing optical activity pi PSPI-1 solution among the embodiment 1 is evenly coated on the release PET film, under 120 ℃, after 4 minutes the soft roasting program, just can be obtained the sensitization pi film that a thickness is about 20 μ m via hot-air oven.With above-mentioned PET film, utilize the pressing machine then at 120 ℃ of temperature, pressure 50Kgf/mm through coating PSPI
2Down, it is pressed on the Copper Foil of 1 OZ, the PET film is torn off, obtain having the Copper Foil of PSPI film, then (its measured wavelength is thrown about 1000mJ/cm between 250～400nm) with the mercury-arc lamp of a filtered
2Energy exposed, and be developer with the ethanolic solution of the TMAH of 3 weight %, under 35 ℃, developed with the ultrasonic oscillator, development time is 120 seconds.Cleaned 30 seconds with ethanol again, dry up, in heated-air circulation oven, carried out under 230 ℃ subsequently roasting 30 minutes firmly, just can obtain a pi pattern with air cannon.Resulting pattern has live width and the spacing that resolution is 30 μ m, and thickness is 18 μ m.And this figure is compared with the thickness of its original coating in the hard roasting back of developing, and has 90% thickness conservation rate.
Comparative example 1
Get the unmodified PI solution V-1 among 80 embodiment 1 that restrain, the quinhydrones that add 2.19 gram GMA, 0.08 gram are used as inhibitor, stir the companion and can get sticky PI solution PIC-1 in 12 hours under 100 ℃.The pentaerythritol triacrylate of 3.2 grams and two (2,4,6-trimethylbenzene the methyl)-phenylphosphine oxide of light initiator and the PIC-1 of 1.6 grams are mixed evenly, can get a sensing optical activity pi PSPIC-1.Utilize scraper that PSPIC-1 is evenly coated on the Copper Foil of 1 OZ then, and via hot-air oven under 120 ℃, after 5 minutes the soft roasting program, just can obtain the sensitization pi film that a thickness is about 20 μ m.(its measured wavelength is thrown about 1000mJ/cm between 250～400nm) then above-mentioned Copper Foil through coating PSPI to be utilized the mercury-arc lamp of a filtered
2Energy exposed, and be developer with the ethanolic solution of the TMAH of 3 weight %, under 35 ℃, developed with the ultrasonic oscillator.Surpass 200 seconds at development time, (can not form clean pattern) still can't develop successfully.
Comparative example 2
Get PI-1 solution 80 grams among the embodiment 1, add the pentaerythritol triacrylate of 3.2 grams and two (2,4,6-trimethylbenzene the methyl)-phenylphosphine oxide of light initiator of 1.6 grams again and make it evenly mixed, can get a sensing optical activity pi PSPIC-1.Utilize scraper that PSPIC-1 is evenly coated on the Copper Foil of 1 OZ then, and via hot-air oven under 120 ℃, after 5 minutes the soft roasting program, just can obtain the sensitization pi film that a thickness is about 20 μ m.(its measured wavelength is thrown about 1000mJ/cm between 250～400nm) then resulting Copper Foil through coating PSPI to be utilized the mercury-arc lamp of a filtered
2Energy exposed, and be developer with the ethanolic solution of the TMAH of 3 weight %, under 35 ℃, developed with the ultrasonic oscillator.After development time surpasses 200 seconds, the success of still can't developing.
Comparative example 3
Get the unmodified PI solution V-180 gram among the embodiment 1, the pentaerythritol triacrylate that adds 3.2 grams again, 2.63 the monomer N-[3-dimethylamine that contains the 3rd amido of gram] propyl group] Methacrylamide and the 1.6 light initiators that restrain two (2,4,6-trimethylbenzene methyl)-phenylphosphine oxide makes it mixed evenly, can get a sensing optical activity pi PSPIC-3.Utilize scraper that PSPIC-3 is evenly coated on the Copper Foil of 1 OZ then, and via hot-air oven under 120 ℃, after 5 minutes the soft roasting program, just can obtain the sensitization pi film that a thickness is about 20 μ m.(its measured wavelength is thrown about 1000mJ/cm between 250～400nm) then resulting Copper Foil through coating PSPI to be utilized the mercury-arc lamp of a filtered
2Energy exposed, and be developer with the ethanolic solution of the TMAH of 3 weight %, under 35 ℃, developed with the ultrasonic oscillator, development time is 90 seconds, cleaned 30 seconds with ethanol again, dry up with air cannon, in heated-air circulation oven, carried out under 230 ℃ subsequently roasting 30 minutes firmly, just can obtain a pi pattern.The pattern that is obtained has live width and the spacing that resolution is 30 μ m, and thickness is 10 μ m.And this figure is compared with the thickness of its original coating in the hard roasting back of developing, and has 50% thickness conservation rate.
Following table 1 is listed the result of embodiment 1 to comparative example 3.
Table 1
| Embodiment 1 and 3 | Embodiment 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| GMA/ unmodified PI-the COOH mol ratio | 0.5 | 0.25 | 1 | 0.5 | 0 |
| The 3rd amido/unmodified PI-the COOH mol ratio | 0.5 | 0.75 | 0 | 0 | 1 |
| Development time (sec) | 120 | 90 | ＞200 | ＞200 | ＜90 |
| Remaining thickness % | 90 | 85 | Can't develop | Can't develop | 50 |
Following table 2 is listed the character of embodiment 1 formed pi pattern.
Table 2
| Character | Embodiment 1 | Method of testing |
| Exposure energy | 1000mJ/cm 2 | |
| Pulling strengrth | 10kgf/mm 2 | ASTM D882 |
| Elongation | 4.9％ | ASTM D882 |
| Resolution | ＜30μm | Electron microscope |
| Deflection degree (MIT, R=0.8) | 485，631，670 | IPC-TM-650(2.4.3) |
| Cohesiveness | 5lb/in | 180 °, uneven surface (F2-WS) |
| Thickness | 20μm | |
| 5% thermogravimetric loss/Tg thermal expansivity CTE (ppm, 30～200 ℃) | 319.6℃/224.6℃ 68.6 | TGA/TMA |
| DK/Df | 3.7/0.023 | |
| Anti-weldering (300 ℃ * 10 seconds) | By |
Claims (10)
1. a negative light resistance agent composition is contained in the pi that a) has formula (I) in the solvent; B) contain the unsaturated ethylene thiazolinyl monomer of the 3rd amido; And c) the light initiator, wherein the amount of light initiator is 0.1～30% of this pi (I) solid weight, the amount of this monomer be the contained carboxylic acid group of pi (I) molal quantity 70～130%,
In the formula (I)
Ar
1Be the tetravalence base;
Ar
2Be bivalent radical;
Ar
3For containing carboxylic acid group's bivalent radical;
Ar
4For containing-CH
2-C (OH) H-CH
2The bivalent radical of-O-C (O)-C (R)=CH base, wherein R is H or methyl;
M+n+o=1,0.1≤n+o≤0.6, and n: o=9: 1～4: 6.
2. composition as claimed in claim 1, wherein n: o=3: 1～1: 1.
3. composition as claimed in claim 2, wherein m=0.3～0.7.
4. composition as claimed in claim 3, wherein the amount of this monomer be the contained carboxylic acid group of pi (I) molal quantity 90～110%.
5. composition as claimed in claim 1, wherein Ar
3For
Or
6. composition as claimed in claim 1, wherein Ar
4For
R wherein
*For-CH
2-C (OH) H-CH
2-O-C (O)-C (R)=CH, wherein R is H or methyl.
7. composition as claimed in claim 1, wherein this monomer is the 3rd an amido C1-C4 Arrcostab of acrylic or methacrylic acid, or N-(the 3rd amido C1-C4 alkyl) acrylamide or Methacrylamide.
8. composition as claimed in claim 7, wherein this monomer is
9. composition as claimed in claim 1, wherein this solvent is N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, gamma-butyrolacton, dimethylbenzene or toluene.
10. composition as claimed in claim 1, wherein this light initiator is that two (2,4,6-trimethylbenzene methyl)-(bis (2 for phenylphosphine oxide, 4,6-trimethylbenzoyl)-phenylphosphineoxide), 2-benzyl-2-dimethylamino-1-1 (4-good fortune quinoline phenyl)-butanone
(2-benzyl-2-dimethylamino-1-1 (4-morpholinophenyl)-butanone), (2,4,6-trimethylbenzene methyl) diphenyl phosphine oxide ((2,4,6-trimethyl benzoyl) diphenyl phosphine oxide), two (.eta.5-2,4-encircles penta 2-1-thiazolinyl)-two (2,6-two fluoro-3-(1H-pyrroles-1-yl) phenyl titanium (bis (.eta.5-2,4-cyclopentadien-1-yl)-bis (2,6-dufluoro-3-(1H-pyrrol-1-yl)-phenyltitanium), 4,4 '-two (dimethylamino) diphenylketone (4,4 '-bis (dimethylamino) benzophenone), 4,4 '-two (diethylin) diphenylketone (4,4 '-bis (diethylamino) benzophenone) or N-diethylamino phenyl alcohol radical amine (N-phenyldiethanolamine).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111149058A (en) * | 2017-09-22 | 2020-05-12 | 东丽株式会社 | Transparent photosensitive resin composition, photo spacer, liquid crystal display device, method for manufacturing photo spacer, method for manufacturing liquid crystal display device, and use of transparent photosensitive resin composition in lens scanning exposure |
| CN111176070A (en) * | 2018-11-12 | 2020-05-19 | 台湾永光化学工业股份有限公司 | Negative photoresist composition and use thereof |
| CN113448164A (en) * | 2020-03-26 | 2021-09-28 | 台湾永光化学工业股份有限公司 | Negative photosensitive resin composition and use thereof |
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| JP4390028B2 (en) * | 2000-10-04 | 2009-12-24 | 日産化学工業株式会社 | Positive photosensitive polyimide resin composition |
| KR100529577B1 (en) * | 2001-11-22 | 2005-11-17 | 미쓰이 가가쿠 가부시키가이샤 | Photosensitive resin compositions, dry film, and a product using the same |
| JP2003345007A (en) * | 2002-03-19 | 2003-12-03 | Hitachi Cable Ltd | Photosensitive polyimide composition |
| EP1630605B1 (en) * | 2003-06-02 | 2017-10-11 | Toray Industries, Inc. | Photosensitive resin composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111149058A (en) * | 2017-09-22 | 2020-05-12 | 东丽株式会社 | Transparent photosensitive resin composition, photo spacer, liquid crystal display device, method for manufacturing photo spacer, method for manufacturing liquid crystal display device, and use of transparent photosensitive resin composition in lens scanning exposure |
| CN111149058B (en) * | 2017-09-22 | 2024-03-08 | 东丽株式会社 | Transparent photosensitive resin composition and application thereof, photoetching spacer, liquid crystal display device and manufacturing method thereof |
| CN111176070A (en) * | 2018-11-12 | 2020-05-19 | 台湾永光化学工业股份有限公司 | Negative photoresist composition and use thereof |
| CN111176070B (en) * | 2018-11-12 | 2023-09-01 | 台湾永光化学工业股份有限公司 | Negative photoresist composition and use thereof |
| CN113448164A (en) * | 2020-03-26 | 2021-09-28 | 台湾永光化学工业股份有限公司 | Negative photosensitive resin composition and use thereof |
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