CN102636955A - Photosensitive resin composition - Google Patents
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- CN102636955A CN102636955A CN2011100376783A CN201110037678A CN102636955A CN 102636955 A CN102636955 A CN 102636955A CN 2011100376783 A CN2011100376783 A CN 2011100376783A CN 201110037678 A CN201110037678 A CN 201110037678A CN 102636955 A CN102636955 A CN 102636955A
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Abstract
The invention provides a photosensitive resin composition which comprises alkali solubility resin with an epoxy structure, a photopolymerizable compound with an ethylene-type unsaturated bond, a photoinitiator and a curing agent. The photosensitive resin composition provided by the invention can provide excellent surface hardness, adhesion force and transmission of light, which meet the industrial utilization requirements.
Description
Technical field
The present invention relates to a kind of resin combination, relate in particular to a kind of negative-type photosensitive resin composition.
Background technology
Photosensitive material is meant light is produced reaction and (Intra-reaction) or intermolecular (Inter-reaction) variation (for example change in polarity, bound rupture or chain are crosslinked) in the molecule takes place behind the absorbing light energy, and causes exposure region and unexposed area developer solution to be produced the material of difference on the rate of dissolution.For example, negative photosensitive material produces cross-linking reaction and becomes and is insoluble in developer solution after exposure; Otherwise the positive type light sensitive material then becomes after exposure and is soluble in developer solution, and therefore, its exposure region can be dissolved in developer solution and be removed.Photoetching technique (photolithography) is utilized the characteristic of photosensitive material, makes the fine pattern in the electronic component through steps such as exposure, developments.In the photo-mask process; Photosensitive material is covered on the substrate; Make light see through light shield and on photosensitive material, carry out selectivity exposure, utilize exposure region and the unexposed area difference on rate of dissolution to develop again, make on the light shield pattern (for example: line pattern) be transferred on the photosensitive material.At present, photosensitive material has been widely used in printed circuit board (PCB) (PCB), integrated circuit (IC), display panels (LCD) and MEMS fields such as (MEMS), is used for making the protective seam or the insulation course of photoresist for example and electronic component.Japanese patent application JP2007-156139 has disclosed a kind of photosensitive resin composition, can be used for making the light interval body in the display panels, and splendid elasticity is provided.
Because development trend microminiaturized and high integration (Integration); To the requirement of photosensitive material also increasingly stringent; Therefore, for meeting high-resolution demand and promoting reliability of products and qualification rate, photosensitive material must have high photosensitivity, high light transmittance, high surface hardness, high-fire resistance, high flat degree, high corrosion stability, low heat expansion; And to the characteristics such as high adhesion force of substrate (for example, the indium tin oxide (ITO) in display panels, the contact panel).U.S. Pat 7374861 discloses and contains the unsaturated ethylene thiazolinyl monomer of polyimide, tool tertiary amine groups and the photosensitive composition of light trigger, can shorten development time through said monomer.Jap.P. JP3994429 discloses a kind of resin combination that can be used for forming the film in display panels, IC apparatus or the solid-state image capturing apparatus (solid state image pickup device), and surface of good smoothness (surface smoothness), thermotolerance (heat resistance), transparency (transparency) and chemical resistance (chemical resistance) can be provided.In addition, U.S. Pat 6432616 imports in the polymkeric substance through containing unsaturated link and/or heteroatomic side chain, reaches the adhesion to copper base with the photonasty that improves photosensitive material.Taiwan patent TW180311 then discloses the photoresist of a kind of short wavelength's of being used for imaging (short wavelength imaging), can provide good resolution to reach the adhesion to copper base.Yet, for meeting industry demand, still need badly and have high adhesion force, and the material of characteristics such as high surface hardness and high light transmittance is provided simultaneously.
Summary of the invention
The present invention provides a kind of photosensitive resin composition; Comprise: the alkali soluble resins that (A) has epoxy construction; Be selected from the polymerizable monomer of acrylic monomer, its acid anhydrides or its potpourri and the multipolymer that (a2) contains the acrylic monomer polymerization of epoxy construction by comprising (a1); It is characterized in that, be benchmark in the gross weight of said photosensitive resin composition, and the content of said alkali soluble resins is 10 to 50wt%; (B) gross weight in said photosensitive resin composition is a benchmark, 1 to 10wt% photopolymerization (photopolymerizable) compound with ethylene type unsaturated link (ethylenicallyunsaturated bond); (C) gross weight in said photosensitive resin composition is a benchmark, 1 to 10wt% light trigger; And (D) be benchmark in the gross weight of said photosensitive resin composition, 1 to 10wt% hardening agent.
One specific embodiment according to the present invention, acrylic monomer are acrylic or methacrylic acid, and unsaturated carboxylic acid anhydrides is acrylic anhydride or methacrylic anhydride.
One specific embodiment according to the present invention, the acrylic monomer that contains epoxy construction contains formula (I) structure:
One specific embodiment according to the present invention, the weight-average molecular weight with alkali soluble resins of epoxy construction is 5000 to 15000.
One specific embodiment according to the present invention, the polymerizable monomer, (a2) that are selected from acrylic monomer, its acid anhydrides or its potpourri except that (a1) contain the acrylic monomer of epoxy construction, and the alkali soluble resins with epoxy construction also can comprise (a3) activated monomer unit.(a3) activated monomer is the ethylene type unsaturated monomer of non-acrylic monomer or through the acrylic monomer of modification.
One specific embodiment according to the present invention, hardening agent contain formula (II) structure:
It is characterized in that R is H or CH
3
In one specific embodiment, hardening agent contains formula (III) structure:
One specific embodiment according to the present invention, photosensitive resin composition can be chosen wantonly and comprise solvent.One specific embodiment according to the present invention, photosensitive resin composition can be chosen wantonly and comprise adjuvant.
Alkali soluble resins and the hardening agent of photosensitive resin composition of the present invention because of having the tool epoxy construction can provide good adhesion and light transmission through hardening agent in the effect of cross-linking reaction when promoting skin hardness, thus the demand of accords with industrial utilization.
Embodiment
Below through particular specific embodiment embodiment of the present invention is described, these those skilled in the art can understand other advantages of the present invention and effect by content that this instructions disclosed.The present invention also can implement or use through other different specific embodiments, and each item details in this instructions also can be based on different viewpoints and application, under spirit of the present invention, carries out various modifications and change not being contrary to.
Term as used herein " weight-average molecular weight " is to utilize gel permeation chromatography (GPC) (solvent: the value of tetrahydrofuran (THF)) being measured that is converted into polystyrene weight-average molecular weight (Mw).
Term as used herein " acrylic acid series " comprises acrylic acid series and metha crylic.Term as used herein " (methyl) acrylic acid ... " expression comprises or does not comprise the literal in the parantheses.For example, " (methyl) acrylic acid " comprises acrylic acid and methacrylic acid, and " (methyl) acrylic anhydride " comprises acrylic anhydride and methacrylic anhydride, by that analogy.
The present invention provides a kind of photosensitive resin composition; Demand with accords with industrial utilization; Said photosensitive resin composition comprises: (A) have the alkali soluble resins of epoxy construction, be selected from the polymerizable monomer of acrylic monomer, its acid anhydrides or its potpourri and the multipolymer that (a2) contains the acrylic monomer polymerization of epoxy construction by comprising (a1), it is characterized in that; Gross weight in said photosensitive resin composition is a benchmark, and the content of said alkali soluble resins is 10 to 50wt%; (B) gross weight in said photosensitive resin composition is a benchmark, the photopolymerization compound of 1 to 10wt% tool ethylene type unsaturated link; (C) gross weight in said photosensitive resin composition is a benchmark, 1 to 10wt% light trigger; And (D) be benchmark in the gross weight of said photosensitive resin composition, 1 to 10wt% hardening agent.
One specific embodiment according to the present invention is selected from preferred (methyl) acrylic acid of polymerizable monomer of acrylic monomer, its acid anhydrides or its potpourri.One specific embodiment according to the present invention, preferred (methyl) acrylic anhydride of the acid anhydrides of acrylic monomer.
One specific embodiment according to the present invention is a benchmark in the gross weight of said alkali soluble resins, and the content that (a1) is selected from the polymerizable monomer of acrylic monomer, its acid anhydrides or its potpourri is 1 to 10wt%, and preferred 3 to 5wt%.
The acrylic monomer that contains epoxy construction that is used for photosensitive resin composition of the present invention does not have special restriction, so long as contain epoxide group and can with acrylic monomer and/or its acid anhydrides copolymerization all be suitable for said alkali soluble resins.
(methyl) acrylic ester and the derivant thereof that contain the optional self-contained epoxide group of acrylic monomer of epoxy construction.Containing (methyl) acrylic ester of epoxide group and the instance of derivant thereof comprises; But be not limited to: (methyl) acrylic ester and the derivant thereof that contain oxirane ring (oxirane ring); For example; (methyl) acrylic acid epoxy ethyl ester (oxiranyl (meth) acrylates), (methyl) acrylic acid epoxy propyl ester ((methyl) glycidyl acrylate), 2-methyl glycidyl (methyl) acrylic ester, (methyl) acrylic acid 2-ethyl epoxy propyl ester, (methyl) acrylic acid 2-epoxy ethyl ethyl ester, (methyl) acrylic acid 2-glycidoxy ethyl ester (2-glycidyloxyethyl (meth) acrylates), (methyl) acrylic acid 3-glycidyl oxygen base propyl ester, (methyl) acrylic acid epoxy propoxyl group phenyl ester (glycidyloxyphenyl (meth) acrylates) etc., and combination; Contain 3, (methyl) acrylic ester and the derivant thereof of 4-7-oxa-bicyclo[4.1.0 ring (3,4-epoxycyclohexane ring); For example, (methyl) acrylic acid 3,4-epoxy cyclohexyl, (methyl) acrylic acid 3; 4-epoxycyclohexyl methyl esters, (methyl) acrylic acid 2-(3, the 4-epoxycyclohexyl) ethyl ester, (methyl) acrylic acid 2-(3,4-epoxycyclohexyl methoxyl) ethyl ester, (methyl) acrylic acid 3-(3; 4-epoxycyclohexyl methoxyl) propyl ester etc., and combination; Contain 5, (methyl) acrylic ester and the derivant thereof of 6-epoxy-2-dicyclo [2.2.1] heptane ring (5,6-epoxy-2-bicyclo [2.2.1] heptane ring), for example, (methyl) acrylic acid 5,6-epoxy-2-dicyclo [2.2.1] heptyl ester etc.; Contain 3,4-epoxy three ring [5.2.1.0
2,6] (methyl) acrylic ester and the derivant thereof of decane; The vinyl ether and the derivant thereof that contain epoxide group; The allyl ether and the derivant thereof that contain epoxide group; And combination.
One specific embodiment according to the present invention, the acrylic monomer that contains epoxy construction are selected from (methyl) acrylic ester and the derivant thereof that contains the oxirane ring, and contain 3, (methyl) acrylic ester and the derivant thereof of 4-7-oxa-bicyclo[4.1.0 ring.
One specific embodiment according to the present invention is a benchmark in the gross weight of the alkali soluble resins of said tool epoxy construction, and the content that (a2) contains the acrylic monomer of epoxy construction is 1 to 15wt%, and preferred 3 to 5wt%.
In one specific embodiment, the acrylic monomer that contains epoxy construction contains the structure of formula (I):
One specific embodiment according to the present invention, the weight-average molecular weight with alkali soluble resins of epoxy construction is 5000 to 15000.One specific embodiment according to the present invention is a benchmark in the gross weight of said photosensitive resin composition, and the content with alkali soluble resins of epoxy construction is 10 to 50wt%, and preferred 20 to 50wt%, and more preferably 20 to 40wt%.
One specific embodiment according to the present invention has in the alkali soluble resins of epoxy construction, and (a1) being selected from the polymerizable monomer of acrylic monomer, its acid anhydrides or its potpourri is 1: 0.8 to 1: 3 with the weight ratio that (a2) contains the acrylic monomer of epoxy construction.
The alkali soluble resins that is used for photosensitive resin composition of the present invention with epoxy construction; Can pass through the whole bag of tricks; Carrying out (a1) is selected from the polymerizable monomer of acrylic monomer, its acid anhydrides or its potpourri and prepares with the copolymerization of the acrylic monomer that (a2) contains epoxy construction; The preparation method includes, but are not limited to the method that this paper embodiment is narrated.
One specific embodiment according to the present invention can randomly add activated monomer and have the characteristic of the alkali soluble resins of epoxy construction with adjustment, for example, but is not limited to skin hardness, flexible, adhesion, viscosity etc.One specific embodiment according to the present invention can randomly add the acrylic monomer that activated monomer with the polymerizable monomer that (a1) is selected from acrylic monomer, its acid anhydrides or its potpourri and (a2) contains epoxy construction and carry out copolymerization, with the preparation alkali soluble resins.In one specific embodiment, polymerizable monomer, (a2) that the alkali soluble resins with epoxy construction is selected from acrylic monomer, its acid anhydrides or its potpourri for (a1) contains the acrylic monomer of epoxy construction and (a3) multipolymer of activated monomer.In the part embodiment of these specific embodiments, activated monomer is selected from the monomer with ethylene type unsaturated link.
Monomer with ethylene type unsaturated link can be, and for example, but is not limited to: esters of unsaturated carboxylic acids; Unsaturated aromatic monomer; The monomer of amide-containing; Propionate, vinyl acetate etc.; And combination.
Instance with monomer of ethylene type unsaturated link comprises; But be not limited to: (methyl) acrylic ester and derivant thereof; For example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) allyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid oxa-ring butyl ester (oxetanyl (meth) acrylates), (methyl) acrylic acid 3-methyl-3-oxa-ring butyl ester, (methyl) acrylic acid 3-ethyl-3-oxa-ring butyl ester, (methyl) acrylic acid (3-methyl-3-oxa-cyclobutyl) methyl esters ((3-methyl-3-oxetanyl) methyl (meth) acrylates), (methyl) acrylic acid (3-ethyl-3-oxa-cyclobutyl) methyl esters, (methyl) acrylic acid 2-(3-methyl-3-oxa-cyclobutyl) ethyl ester, (methyl) acrylic acid 2-(3-ethyl-3-oxa-cyclobutyl) ethyl ester, (methyl) acrylic acid 2-[(3-methyl-3-oxa-cyclobutyl) methoxyl] ethyl ester (2-[(3-methyl-3-oxetanyl) methyloxy] ethyl (meth) acrylates), (methyl) acrylic acid 2-[(3-ethyl-3-oxa-cyclobutyl) methoxyl] ethyl ester, (methyl) acrylic acid 3-[(3-methyl-3-oxa-cyclobutyl) methoxyl] propyl ester, (methyl) acrylic acid 3-[(3-ethyl-3-oxa-cyclobutyl) methoxyl] propyl ester, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid tetrahydrofuran methyl esters, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-(three ring [5.2.1.0
2,6] last of the ten Heavenly stems oxygen base) ethyl ester (2-(tricyclo [5.2.1.0
2,6] decyloxy) ethyl (meth) acrylates) etc., and combination; Styrene, vinyltoluene (for example: adjacent Ethenylbenzene, an Ethenylbenzene, to Ethenylbenzene), α-vinyltoluene, chlorostyrene etc., and combination; Acrylamide derivative; For example, (methyl) acrylic amide, N methacrylamide, N-ethyl-methyl acrylic amide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N-methoxy acrylic amide, N-ethoxyl methyl acrylic amide, N-butoxymethyl acrylic amide, vinyl cyanide etc. and combination thereof; Maleimide derivatives; Propionate, vinyl acetate, vinyl acetate, vinyl benzoate etc. and combination thereof; Isobutylene; And combination.
One specific embodiment according to the present invention is a benchmark in the gross weight of said alkali soluble resins, and (a3) content of activated monomer is 5 to 70wt%, and preferred 40 to 50wt%.
Alkali soluble resins with epoxy construction can pass through the whole bag of tricks; Carrying out (a1) is selected from the copolymerization of the polymerizable monomer of acrylic monomer, its acid anhydrides or its potpourri, acrylic monomer that (a2) contains epoxy construction and optional (a3) activated monomer and prepares; The preparation method includes, but are not limited to the method that this paper embodiment is narrated.
Preparation polyreaction capable of using with alkali soluble resins of epoxy construction is carried out, and polyreaction is carried out in the presence of radical initiator usually.Radical initiator does not have special restriction, can use general employed radical initiator in this technical field.Can use one or more radical initiator.When using the potpourri of two kinds or more kinds of radical initiator, blending ratio does not have special qualification.Gross weight in said alkali soluble resins is a benchmark, and the consumption of radical initiator preferred 2 is to 4wt%.The temperature of polymerization is generally 50 to 90 ℃, preferred 60 to 70 ℃.
Polyreaction is carried out in the presence of solvent usually, the preferred solvent that is enough to dissolve each composition, radical initiator and obtained resin in the alkali soluble resins with epoxy construction that uses.Solvent does not have special restriction, can use general employed solvent in this technical field.Can use one or more solvents.When using the potpourri of two kinds or more kinds of solvents, blending ratio does not have special qualification.
One specific embodiment according to the present invention, the alkali soluble resins that preparation is accomplished with epoxy construction, with (B) have the photopolymerization compound, (C) light trigger of ethylene type unsaturated link and (D) hardening agent mixes acquisition photosensitive resin composition.
The photopolymerization compound with ethylene type unsaturated link that is used for photosensitive resin composition of the present invention can carry out polymerized/cross-linked with the alkali soluble resins with epoxy construction behind the absorbing light energy.Be used for the photopolymerization compound that the present invention has the ethylene type unsaturated link and do not have special restriction, as long as can behind the absorbing light energy, carry out polymerization with alkali soluble resins with epoxy construction.One specific embodiment according to the present invention, the photopolymerization compound with ethylene type unsaturated link is selected from monomer and/or the oligomer with ethylene type unsaturated link.
Particularly; Photopolymerization compound with ethylene type unsaturated link; Can be to have the compound (hereafter is a polyfunctional compound) of a plurality of carbon-carbon double bond functional group for cross-linking reaction; The instance of polyfunctional compound includes, but are not limited to commercially available Nikalac MX-302 (by Sanwa ChemicalCo., Ltd. makes); Aronix M-400, M-402, M-403, M-404, M-408, M-450, M-305, M-309, M-310, M-313, M-315, M-320, M-325, M-326, M-327, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-1382, TO-902, TO-904, TO-905, TO-1330 (by Toagosei Co., Ltd. makes); Kayarad D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, R-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-368, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA (by Nippon Kayaku Co., Ltd. makes); Light Acrylate PE-4A, DPE-6A, DTMP-4A (by Kyoeisha Chemical Co., Ltd. makes) etc., and combination.
One specific embodiment according to the present invention is a benchmark in the gross weight of said photosensitive resin composition, and the content with photopolymerization compound of ethylene type unsaturated link is 1 to 10wt%, and preferred 5 to 9wt%, and more preferably 5 to 8wt%.
The light trigger that is used for photosensitive resin composition of the present invention does not have special restriction, can use the light trigger that can cause Raolical polymerizable behind the absorbing light energy.
The instance of light trigger includes, but are not limited to: benzoin and alkyl ether thereof, for example, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin phenyl ether (benzoin phenylether), acetyl benzoin; Acetophenone, for example, acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone; The amido acetophenone, for example, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-1-ketone; Anthraquinone, for example, 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone (2-amylanthraquinone); Thioxanthones (thioxanthone) and xanthone (xanthone), for example, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2,4-diisopropyl thioxanthones; Ketal, for example, acetophenone dimethyl ketal, benzyl dimethyl ketone; Benzophenone, for example, benzophenone, 4,4 '-two (N, N '-two-methyl-amido) benzophenone (4,4 '-bis (N, the benzophenone of N '-di-methyl-amino)), 4,4 '-two (N, N '-two-ethyl-amido) benzophenone; Acridine derivatives (acridine derivative); Azophenlyene derivant (phenazine derivative); Quinoxaline derivatices (quinoxaline derivative); Triphenylphosphine; Phosphine oxide, for example, (2,6-dimethoxy benzoyl)-2,4; 4-amyl group phosphine oxide ((2,6-dimethoxybenzoyl)-2,4,4-pentylphosphine oxide), two (2; 4,6-trimethylbenzoyl) phenyl phosphine oxide (bis (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide), 2; 4,6-trimethylbenzoyl-diphenyl phosphine oxide (2,4,6-trimethylbenzoyl-diphenyl phosphine oxide), ethyl-2; 4, and 6-trimethylbenzoyl-phenyl-phosphonite ester (ethyl-2,4,6-trimethylbenzoyl-phenylphosphinate); 1-phenyl-1,2-propanedione-2-O-benzoyl oxime (1-phenyl-1,2-propanedione2-O-benzoyl oxime); 4-(2-hydroxyl-oxethyl) phenyl-(2-propyl group)-ketone (4-(2-hydroxyethoxy) Phenyl-(2-propyl) ketone); 1-aminocarbonyl phenyl ketone (1-aminophenylketone) and 1-hydroxy phenyl ketone (1-hydroxy phenyl ketone); For example, 1-hydroxycyclohexylphenylketone, 2-hydroxyl isopropyl phenyl ketone, phenyl 1-hydroxyl nezukone (phenyl1-hydroxyisopropyl ketone), 4-isopropyl phenyl 1-hydroxyl nezukone (4-isopropylphenyl1-hydroxyisopropyl ketone); Various superoxide (peroxide); And combination.
One specific embodiment according to the present invention is a benchmark in the gross weight of said photosensitive resin composition, and the content of light trigger is 1 to 10wt%, and preferred 3 to 8wt%, and more preferably 3 to 7wt%.
The hardening agent that is used for photosensitive resin composition of the present invention, preferably contain the hardening agent of formula (II) structure:
It is characterized in that R is H or CH
3
In one specific embodiment, hardening agent is for containing the hardening agent of formula (III) structure:
One specific embodiment according to the present invention is a benchmark in the gross weight of said photosensitive resin composition, and the content of hardening agent is 1 to 10wt%, and preferred 2 to 8wt%, and more preferably 3 to 5wt%.
One specific embodiment according to the present invention, the photosensitive resin composition can randomly comprise solvent.The employed solvent of photosensitive resin composition does not have special qualification; As long as can the composition of photosensitive resin composition be dispersed or dissolved, and do not react with these compositions, and; Have appropriate volatility and suitable rate of drying, and can provide even and level and smooth filming to get final product after the volatilization.Can use general employed solvent in this technical field.
The instance of solvent includes, but are not limited to: cyclohexanone, ethyl lactate, glycol monomethyl methyl ether, monoethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and 3-ethoxyethyl propionic ester.Can use one or more solvent.When using the potpourri of two kinds or more kinds of solvents, blending ratio does not have special qualification.
In one specific embodiment, be benchmark in the gross weight of said photosensitive resin composition, the content of solvent is 30 to 80wt%, and preferred 40 to 70wt%, and more preferably 60 to 70wt%.
One specific embodiment according to the present invention, the photosensitive resin composition can randomly comprise adjuvant.The instance of adjuvant comprises; But be not limited to: modifier (modifier), toughner (toughener), stabilizing agent (stabilizer), foam-breaking agent, spreading agent (dispersant), levelling agent (leveling agent), thickening agent (thickening agent), reinforcing agent (reinforcing agent), coupling agent (coupling agent), increase and scratch agent (flexibility-imparting agent), plastifier (plasticizer), sensitizer (sensitizers), water, fire retardant, anti-oxidant, pigment, dyestuff, filler, antisettling agent etc., and combination.
In one specific embodiment, be benchmark in the gross weight of said photosensitive resin composition, content of additive is no more than 3wt% usually.
One specific embodiment according to the present invention, the photosensitive resin composition can be used for making photoresist, especially the minus photoresist.In the part embodiment of these specific embodiments, the photosensitive resin composition is applied to substrate after, through dry, exposure, develop with patterning.In the part embodiment of these specific embodiments, behind the photosensitive resin composition patterning that is applied on the substrate, can further carry out etching or plating to substrate.
One specific embodiment according to the present invention, the photosensitive resin composition can be as protective seam or the insulation course made in the electronic component.
Photosensitive resin composition of the present invention can provide suitable skin hardness and high light transmittance, high etch-resistance, high adhesion force, and meets high-resolution demand and promote reliability of products and yield.
The present invention will more specifically explain through embodiment, but said embodiment is used to limit category of the present invention.Only if specialize, it is benchmark with weight that " % " that is used to represent content and any amount of substance of any composition in the following example and the comparing embodiment reaches " weight portion ".
Embodiment
The preparation of resin
Preparation example 1: the preparation of resin 1
In the flask that condenser pipe, stirring machine are housed; Drop into the thermal free radical initiator 2 of 4 weight portions; The solvent MEDG of 2 '-azobis isobutyronitrile (AIBN), 282 weight portions (Methyl Ethyl Di Glycol) then drops into the methacrylic acid (MAA) of 46 weight portion TCDMA (tricyclodecanyl methacrylate), 21 weight portions, the styrene (Styrene) of 3 weight portions, CYCLOMER M-100 (Methacrylic acid, 7-oxabicyclo [4.1.0] the hept-3-ylmethyl ester of 40 weight portions; By Daicel ChemicalIndustries; Ltd makes), the methacrylic acid tetrahydrofuran methyl esters of 12 weight portions (Tetrahydrofurfurylmethacrylate, THFMA), behind nitrogen replacement; Beginning is stirred fast; Temperature was kept under 65 ℃ 3.5 hours, then be warmed up to 75 ℃ following 2.5 hours, obtain resin 1.
Preparation example 2: the preparation of resin 2
In the flask that condenser pipe, stirring machine are housed, drop into the thermal free radical initiator 2 of 4 weight portions, the solvent MEDG of 2 '-azobis isobutyronitrile (AIBN), 282 weight portions; Then drop into the TCDMA of 33 weight portions, the methacrylic acid of 21 weight portions, the styrene of 3 weight portions, the GMA (GMA) of 45.5 weight portions; Behind nitrogen replacement, beginning is stirred fast, and temperature was kept under 65 ℃ 3.5 hours; Then be warmed up to 75 ℃ following 2.5 hours, obtain resin 2.
Preparation example 3: the preparation of resin 3
In the flask that condenser pipe, stirring machine are housed, drop into the thermal free radical initiator 2 of 4 weight portions, the solvent MEDG of 2 '-azobis isobutyronitrile, 282 weight portions; Then drop into the TCDMA of 11 weight portions, the methacrylic acid of 20 weight portions, the styrene of 3 weight portions, the CYCLOMER M-100 of 98 weight portions; Behind nitrogen replacement, beginning is stirred fast, and temperature was kept under 65 ℃ 3.5 hours; Then be warmed up to 75 ℃ following 2.5 hours, obtain resin 3.
Preparation example 4: the preparation of resin 4
In the flask that condenser pipe, stirring machine are housed, drop into the thermal free radical initiator 2 of 4 weight portions, the solvent MEDG of 2 '-azobis isobutyronitrile, 282 weight portions; Then drop into the TCDMA of 42 weight portions, the methacrylic acid of 14 weight portions, the CYCLOMER M-100 of 90 weight portions; Behind nitrogen replacement, beginning is stirred fast, and temperature was kept under 65 ℃ 3.5 hours; Then be warmed up to 75 ℃ following 2.5 hours, obtain resin 4.
Preparation example 5: the preparation of resin 5
In the flask that condenser pipe, stirring machine are housed, drop into the thermal free radical initiator 2 of 4 weight portions, the solvent MEDG of 2 '-azobis isobutyronitrile, 282 weight portions; Then drop into the TCDMA of 94 weight portions, the methacrylic acid of 11 weight portions, the CYCLOMER M-100 of 40 weight portions; Behind nitrogen replacement, beginning is stirred fast, and temperature was kept under 65 ℃ 3.5 hours; Then be warmed up to 75 ℃ following 2.5 hours, obtain resin 5.
The photosensitive resin preparation of compositions
Embodiment 1
Evenly be mixed with example 1 resulting resin 1 solution 47.47 weight portions, light trigger IRGACURE
907 (making) 3.08 weight portions, polyfunctional monomer Aronix M 400 (by Toagosei Co. by Ciba Inc.; Ltd. manufacturing) 7.02 weight portions, hardening agent CYMEL 303 (being made by CytecIndustries Inc.) 2 weight portions and solvent propylene glycol monomethyl ether (PGMEA) 40.43 weight portions filter with 10 microns (μ m) filtrators then.
Embodiment 2
To prepare the resin 1 in example 2 resulting resin 2 alternate embodiments 1, according to the step of embodiment 1, preparation photosensitive resin composition.
Embodiment 3
To prepare the resin 1 in example 3 resulting resin 3 alternate embodiments 1, according to the step of embodiment 1, preparation photosensitive resin composition.
Embodiment 4
To prepare the resin 1 in example 4 resulting resin 4 alternate embodiments 1, according to the step of embodiment 1, preparation photosensitive resin composition.
Embodiment 5
To prepare the resin 1 in example 5 resulting resin 5 alternate embodiments 1, according to the step of embodiment 1, preparation photosensitive resin composition.
Comparative example 1
With the resin 1 in commercially available resin B L-100 (by the upright big chemical industry manufacturing) alternate embodiment 1, according to the step of embodiment 1, preparation photosensitive resin composition.
Comparative example 2
With the resin 1 in commercially available resin 295 (making) alternate embodiment 1 by DIC, according to the step of embodiment 1, preparation photosensitive resin composition.
Comparative example 3
Repeat the step of embodiment 1, but do not add hardening agent CYMEL 303.
Comparative example 4
Repeat the step of embodiment 3, but do not add hardening agent CYMEL 303.
Comparative example 5
Repeat the step of comparative example 1, but do not add hardening agent CYMEL 303.
Comparative example 6
Repeat the step of comparative example 2, but do not add hardening agent CYMEL 303.
The composition of the resin combination of embodiment 1 to 5 and comparative example 1 to 6 is as shown in table 1 below.
Table 1
Test
The resin combination of the foregoing description and comparative example gained is carried out the test of adhesion (adhesion), skin hardness (surface hardness) and light transmission (transmittance) etc.
Respectively with the resin combination of the foregoing description and comparative example gained, be uniformly coated on the conducting glass substrate that is coated with ITO (tin indium oxide) with the mode of rotary coating (rotating speed 1000rpm, 7 seconds).In baking oven with 100 ℃ of preliminary dryings (Pre-bake) 10 minutes.See through light shield, and with 150mJ/cm
2Exposure energy to resin combination make public (Exposure).After 30 seconds, in baking oven, carry out back baking (Post-bake) 30 minutes with mobile washed with de-ionized water (Rinse) with 230 ℃.According to following method, the film that resin combination forms on substrate is tested, with the characteristic of assessment resin combination.
(1) adhesion after the etching
To be formed with substrate immersion (HCl:215ml, 37wt% in the iron chloride acid etching liquid of resin combination film; H
2O:69.2ml; FeCl
3: 16.8ml, 15wt%), kept under 40 ℃ 3 minutes.Then, according to the gluing property chessboard eye band method that JIS K-5400-1990 8.5.3 is put down in writing, assessment etching rear film is to the adhesion of substrate, and in evaluation score, the adhesion of 5B is best, and 4B takes second place, and 0B is the poorest.
Can know that by table 2 result displayed photosensitive resin composition of the present invention has good resistance to etching solution after exposure, and after etching, substrate showed outstanding adhesion.
(2) skin hardness
To the film that forms by resin combination, carry out pencil cut test (Pencil Scratch HardnessTest), with the skin hardness of assessment film.The result is shown in the following table 2, and wherein, 6B representes that hardness is the poorest, and 6H representes hardness optimal, and for example: if use the no scratch in H pencil surface, use 2H pencil surface also not have scratch, but use 3H pencil surface that scratch is arranged, the hardness of then judging test film is 2H.
Can know that by table 2 the photosensitive resin composition of the embodiment of the invention provides surface of good hardness.
(3) 230 ℃ of light transmissions
Utilize microspectrophotometer (MX-50; The OLYMPUS corporate system), respectively with the wavelength of 390nm, 400nm and 450nm, measure the light light transmission of the film that forms by resin combination.The result is shown in the following table 2, can be known that by table 2 the photosensitive resin composition of the embodiment of the invention when good adhesion and skin hardness are provided, also can be kept high light transmittance.
Table 2
Annotate: atomizing refers to said film after baking finishes later, and the surface has appeared opaque vaporific in vain.
The photosensitive resin composition of the embodiment of the invention can provide good adhesion, skin hardness and light transmission, the demand of accords with industrial utilization simultaneously.
The foregoing description is illustrative composition of the present invention and preparation method only, but not is used to limit the present invention.Any these those skilled in the art all can be under spirit of the present invention and category, and the foregoing description is modified and changed.Therefore, rights protection scope of the present invention, should such as claims record.
Claims (10)
1. photosensitive resin composition comprises:
(A) has the alkali soluble resins of epoxy construction; Be selected from the polymerizable monomer of acrylic monomer, its acid anhydrides or its potpourri and the multipolymer that (a2) contains the acrylic monomer polymerization of epoxy construction by comprising (a1); Wherein, Gross weight in said photosensitive resin composition is a benchmark, and the content of said alkali soluble resins is 10 to 50wt%;
(B) gross weight in said photosensitive resin composition is a benchmark, 1 to 10wt% the photopolymerization compound with ethylene type unsaturated link;
(C) gross weight in said photosensitive resin composition is a benchmark, 1 to 10wt% light trigger; And
(D) gross weight in said photosensitive resin composition is a benchmark, 1 to 10wt% hardening agent.
2. photosensitive resin composition as claimed in claim 1 is characterized in that, said acrylic monomer is acrylic or methacrylic acid.
3. photosensitive resin composition as claimed in claim 1 is characterized in that, the said acrylic monomer that contains epoxy construction contains formula (I) structure:
4. photosensitive resin composition as claimed in claim 1 is characterized in that, said weight-average molecular weight with alkali soluble resins of epoxy construction is 5000 to 15000.
5. photosensitive resin composition as claimed in claim 1; It is characterized in that; In the said alkali soluble resins with epoxy construction, (a1) being selected from the polymerizable monomer of acrylic monomer, its acid anhydrides or its potpourri is 1: 0.8 to 1: 3 with the weight ratio that (a2) contains the acrylic monomer of epoxy construction.
6. photosensitive resin composition as claimed in claim 1 is characterized in that, said hardening agent has formula (II) structure:
It is characterized in that R is H or CH
3
7. photosensitive resin composition as claimed in claim 6 is characterized in that, is benchmark in the gross weight of said photosensitive resin composition, and the content of said hardening agent is 3 to 5wt%.
8. photosensitive resin composition as claimed in claim 1 also comprises solvent.
9. photosensitive resin composition as claimed in claim 8 is characterized in that, is benchmark in the gross weight of said photosensitive resin composition, and the content of said solvent is 60 to 70wt%.
10. photosensitive resin composition as claimed in claim 1 also comprises adjuvant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100376783A CN102636955A (en) | 2011-02-10 | 2011-02-10 | Photosensitive resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100376783A CN102636955A (en) | 2011-02-10 | 2011-02-10 | Photosensitive resin composition |
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|---|---|
| CN102636955A true CN102636955A (en) | 2012-08-15 |
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|---|---|---|---|
| CN2011100376783A Pending CN102636955A (en) | 2011-02-10 | 2011-02-10 | Photosensitive resin composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104007618A (en) * | 2014-06-18 | 2014-08-27 | 杭州福斯特光伏材料股份有限公司 | High-adhesive-force sensitive dry film used for PCB |
| CN107219726A (en) * | 2017-06-27 | 2017-09-29 | 浙江福斯特新材料研究院有限公司 | A kind of resin combination and purposes |
| CN109575342A (en) * | 2018-12-03 | 2019-04-05 | 湖南鸿瑞新材料股份有限公司 | A kind of synthetic method of novel photoactive dry film acrylic resin |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104007618A (en) * | 2014-06-18 | 2014-08-27 | 杭州福斯特光伏材料股份有限公司 | High-adhesive-force sensitive dry film used for PCB |
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| CN109575342B (en) * | 2018-12-03 | 2021-06-04 | 湖南五江高科技材料有限公司 | Synthetic method of acrylic resin for photosensitive dry film |
| 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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Application publication date: 20120815 |