CN115373223A - Preparation method of water-soluble dry film polyurethane modified acrylic resin polymer for photoetching - Google Patents
Preparation method of water-soluble dry film polyurethane modified acrylic resin polymer for photoetching Download PDFInfo
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- CN115373223A CN115373223A CN202210947557.0A CN202210947557A CN115373223A CN 115373223 A CN115373223 A CN 115373223A CN 202210947557 A CN202210947557 A CN 202210947557A CN 115373223 A CN115373223 A CN 115373223A
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- Prior art keywords
- dry film
- acrylic resin
- water
- preparing
- modified acrylic
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 42
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 31
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 30
- 229920000642 polymer Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000001259 photo etching Methods 0.000 title claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- 239000003292 glue Substances 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 239000011342 resin composition Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 23
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 17
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 17
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000012948 isocyanate Substances 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- 229920001451 polypropylene glycol Polymers 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001459 lithography Methods 0.000 claims description 10
- 230000001502 supplementing effect Effects 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012974 tin catalyst Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- -1 hydroxyalkyl acrylate Chemical compound 0.000 description 5
- PSGCQDPCAWOCSH-BOURZNODSA-N exo-1,7,7-Trimethylbicyclo(2.2.1)hept-2-yl acrylate Chemical compound C1C[C@]2(C)C(OC(=O)C=C)C[C@H]1C2(C)C PSGCQDPCAWOCSH-BOURZNODSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
Abstract
The invention discloses a preparation method of a water-soluble dry film polyurethane modified acrylic resin polymer for photoetching, which comprises the synthesis of a polyurethane acrylic prepolymer; synthesizing a styrene-acrylate copolymer; preparing photosensitive glue; preparation of the resin composition. According to the invention, the thickness of the prepared dry film is about 10 μm, the adhesion to a PCB plate is still good, the thinner the thickness of the dry film is, the higher the resolution of the dry film is, the L/S (10 μm/10 μm) can be reached, the obtained water-soluble dry film polyurethane modified acrylic resin polymer for photoetching has more excellent adhesion, flexibility, temperature resistance and outstanding high elasticity, and the prepared dry film has excellent adhesion and exhaust performance.
Description
Technical Field
The invention belongs to the technical field of photosensitive materials, relates to preparation of a photosensitive dry film, and particularly relates to a preparation method of a water-soluble dry film polyurethane modified acrylic resin polymer for photoetching.
Background
The photosensitive dry film is developed by DuPont company in 1968, and is widely applied to pattern transfer from the beginning, and the photosensitive dry film becomes an important material in the modern electronic field, particularly the field of printed circuit boards. In recent years, with miniaturization and lightness of electronic devices, the requirement of the market on circuit boards is higher, how to realize extremely narrow line width and line pitch becomes the ultimate goal of various large circuit board manufacturers, and the photosensitive dry film is the core electronic material for realizing the goal.
Because a back-end customer needs exposure to transfer the circuit of the negative film to a circuit board, the existing photosensitive film is prepared by adding a photoinitiator, active acrylic resin and other additives to acrylic resin oligomer and a large amount of solvent, drying the solvent by using an oven to form a film and rolling.
The photosensitive dry film is composed of three layers, namely a supporting film layer, a resist layer and a protective film layer. Wherein the main functions of the support film layer and the protective film layer are to carry and protect the resist layer located in the middle. The dry film is a high molecular compound which can generate a polymerization reaction (a reaction process of synthesizing a polymer from a monomer) after being irradiated by ultraviolet rays to form a stable substance to be attached to the surface of the board, thereby achieving the functions of blocking electroplating and etching.
The three-layer photosensitive dry film sold in the market at present is easy to generate bubbles in the film pasting process, and easy to cause residual glue in the developing process, and the basic reason is caused by poor performance of an acrylic resin polymer for forming the dry film.
In order to meet the requirements of multilayer and high density of circuit boards, the resolution of dry films is generally 50/50 μm in line width spacing (L/S). However, in semiconductor packages (BGA, CSP), the circuit board is generally designed to have an L/S of 25 to 40 μm, and a dry film with high resolution is required.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a water-soluble dry film polyurethane modified acrylic resin polymer for photoetching, the thickness of the prepared dry film is about 10 mu m, the adhesion to a PCB plate is still good, and the thinner the thickness of the dry film is, the higher the resolution of the dry film is, and the L/S (10 mu m/10 mu m) can be reached.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a water-soluble dry film polyurethane modified acrylic resin polymer for photoetching comprises the following steps:
1) Synthesis of polyurethane acrylic prepolymer: adding isocyanate, an organic solvent and hydroxyethyl acrylate into a reaction vessel, reacting for a period of time, heating, adding a catalyst and polyol, and reacting to obtain a polyurethane acrylic prepolymer;
2) Synthesis of styrene-acrylate copolymer: preparing a mixed solution of MAA, AA, ST, BA, MBA and 2-EHA, adding part of the mixed solution into an organic solvent and AIBN, reacting for a period of time, adding the rest of the mixed solution, continuing to react, and cooling to obtain a styrene-acrylate copolymer;
3) Preparing photosensitive glue: uniformly stirring the polyurethane acrylic prepolymer obtained in the step 1) and the styrene-acrylate copolymer obtained in the step 2) with an active monomer and an organic solvent under a water bath condition to obtain photosensitive glue;
4) Preparation of resin composition: uniformly stirring the photosensitive glue obtained in the step 3), a photoinitiator and a dye to obtain the water-soluble dry film polyurethane modified acrylic resin polymer for preparing the photoetching.
As a preferred embodiment of the present invention, in step 1), the isocyanate is one of TDI, IPDI, HDI or MDI, the polyol comprises PPG, the organic solvent comprises toluene or acetone, and the catalyst is an organotin-based catalyst.
In a preferred embodiment of the present invention, in step 1), the molar ratio of isocyanate, polyol and hydroxyethyl acrylate is 2-2.3.
As a preferable scheme of the present invention, the specific steps of step 1) are: adding IPDI, PPG and HEA into a four-neck flask provided with a condenser, a stirrer, a thermometer and a constant pressure funnel, adding a toluene solvent and IPDI for mixing, introducing dry nitrogen, dropwise adding HEA through the constant pressure funnel, reacting for 3h within 2h at the temperature of 50-65 ℃, heating to 75 ℃, adding an organic tin catalyst accounting for 0.5-2% of the total mass of IPDI, PPG and HEA, dropwise adding PPG polyol through the constant pressure funnel, reacting for 4-6h, and cooling to room temperature to obtain the urethane acrylate prepolymer.
As a preferred embodiment of the present invention, in step 2), the mass ratio of MAA, AA, ST, BA, MBA,2-EHA is 10.
As a preferable scheme of the present invention, the specific steps of step 2) are: preparing a mixed solution from MAA, AA, ST, MAA, BA, MBA, BA and 2-EHA, pouring 1/3 of the mixed solution into a four-neck flask, adding toluene and methanol for mixing, introducing nitrogen, heating to reflux, stabilizing for 10-20min, adding AIBN, reacting for 30 min, dropwise adding the rest 2/3 of the mixed solution through a constant-pressure funnel for 3h, supplementing AIBN every 1h in the dropwise adding process, preserving heat for 3.5-4.5h after the dropwise adding is finished, supplementing AIBN every 2h in the heat preserving process, adding acetone and ethyl acetate after the heat preserving is finished, diluting to a proper viscosity, and cooling to room temperature to obtain the styrene-acrylate copolymer.
As a preferable scheme of the invention, in the step 3), by weight, 15-25 parts of polyurethane acrylic prepolymer, 75-85 parts of styrene-acrylate copolymer and 2-12 parts of active monomer are calculated.
In a preferable scheme of the invention, in the step 3), the temperature of water bath heating is 40-45 ℃, the stirring time is 4-5.5h, and the active monomer comprises one or more of TMPTA, LA and IBOA.
As a preferable scheme of the invention, in the step 4), the photoinitiator comprises one or two of a photoinitiator 1173, a photoinitiator 184 and a photoinitiator 1176, and the addition amount of the photoinitiator is 0.5-2% of the mass of the active monomer; the dye is OP and/or PS, and the addition amount of the dye is 0.1-0.5% of the mass of the active monomer.
The polyurethane modified acrylic resin is prepared by reacting isocyanate, hydroxyalkyl acrylate and aliphatic alcohol to synthesize a carbamate monomer containing unsaturated bonds, and then polymerizing the carbamate monomer and an acrylate monomer, wherein the polyurethane modified acrylic resin contains the result of the alkyl carbamate and has the performances of polyurethane and acrylate, wherein a-NHCOO-group contains a large number of hydrogen bonds (a special coordination bond), according to the coordination bond theory of the bonding theory, the strong adhesion effect is derived from the coordination bond generated on the interface between an adhesive molecule and an adherend, and in the polyurethane group, a wide range of hydrogen bonds are beneficial to forming a strong coordination bond with the metal surface, so that the polyurethane modified acrylic resin has strong adhesion to a PCB (printed circuit board), and a dry film cannot generate bubbles in the pressing process.
Meanwhile, the-NHCOO-bond is unstable and easy to hydrolyze under alkaline conditions, and is favorable for solving the problem of residual gum in the developing process.
The thickness of the dry film prepared by using the polyurethane modified acrylic resin is about 10 mu m, the adhesion force to a PCB (printed circuit board) is still good, and the thinner the thickness of the dry film is, the higher the resolution of the dry film is, and the L/S (10 mu m/10 mu m) can be reached.
Compared with the prior art, the invention has the following beneficial effects:
1) The water-soluble dry film polyurethane modified acrylic resin polymer for lithography, which is obtained by the preparation method, solves the problem of bubbles in the use process of a PCB dry film;
2) The water-soluble dry film polyurethane modified acrylic resin polymer for photoetching, which is prepared by the preparation method, solves the problem of developing residual glue and improves the yield of products.
3) The water-soluble dry film polyurethane modified acrylic resin polymer for lithography obtained by the invention can be used for preparing circuits with high resolution.
4) The water-soluble dry film polyurethane modified acrylic resin polymer for photoetching, which is obtained by the invention, has more excellent adhesive force, flexibility, temperature resistance and outstanding high elasticity, and the prepared dry film has excellent adhesive force and air exhaust performance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the present invention are all commercially available.
Example 1
The embodiment provides a preparation method of a water-soluble dry film polyurethane modified acrylic resin polymer for photoetching, which comprises the following steps:
1) Polyurethane acrylate prepolymer synthesis:
raw materials: isocyanate (isocyanate such as TDI, IPDI, HDI, MDI) and the like), polyol, hydroxyethyl acrylate, organotin catalyst, toluene, acetone and the like.
Feeding IPDI (PPG (700): HEA into a four-neck flask provided with a condenser, a stirrer, a thermometer and a constant pressure funnel according to the molar ratio of 2.
2) Synthesis of styrene-acrylate copolymer:
raw materials: methacrylic acid/acrylic acid, methyl methacrylate/ethyl methacrylate/acrylonitrile/styrene, butyl acrylate/butyl methacrylate/isooctyl acrylate/hydroxyethyl acrylate, ethyl acetate/toluene/acetone/butanone/methanol, azobisisobutyronitrile/azobisisoheptonitrile/BPO/HTP, and the like.
Preparing a 1/3 mixed solution into a four-neck flask, adding solvents of toluene and methanol, mixing, introducing nitrogen, heating to reflux, stabilizing for 15min, adding AIBN, reacting for 30 min, dropwise adding the rest 2/3 monomers through a constant-pressure funnel for 3h, supplementing AIBN every 1h in the dropwise adding process, preserving heat for 4h after the dropwise adding is finished, supplementing AIBN every 2h in the heat preservation process, adding acetone and ethyl acetate after the heat preservation is finished, diluting to a proper viscosity, and cooling to room temperature to obtain the styrene-acrylate copolymer, wherein the mass ratio of MAA, AA, ST, BA, MBA,2-EHA is 10.
3) Preparing photosensitive glue:
raw materials: urethane acrylate prepolymer, styrene-acrylate prepolymer, reactive monomer, methanol, acetone and other solvents.
Weighing 20 parts of urethane acrylate prepolymer and 80 parts of styrene-acrylate copolymer, adding TMPTA, LA and IBOA which account for 10% of the total mass of the prepolymer, methanol and acetone solvents, heating in a water bath, and uniformly stirring at 40 ℃ for 5 hours to obtain the photosensitive glue.
4) Preparation of resin composition:
pouring the photosensitive glue into a four-neck flask, weighing a photoinitiator 1173 accounting for 0.5 percent of the total mass of the active monomers, a photoinitiator 184 accounting for 0.5 percent of the total mass of the active monomers, a photoinitiator 1176 accounting for 1 percent of the total mass of the active monomers, OP powder accounting for 0.1 percent of the total mass of the photoreactive monomers and PS powder accounting for 0.1 percent of the total mass of the photoreactive monomers, and uniformly stirring for 2 hours to obtain the resin composition for preparing the dry film.
Example 2
The embodiment provides a preparation method of a water-soluble dry film polyurethane modified acrylic resin polymer for photoetching, which comprises the following steps:
1) Polyurethane acrylate prepolymer synthesis:
raw materials: isocyanate (isocyanate such as TDI, IPDI, HDI, MDI) and the like), polyol, hydroxyethyl acrylate, organotin catalyst, toluene, acetone and the like.
Feeding IPDI (PPG (700): HEA into a four-neck flask provided with a condenser, a stirrer, a thermometer and a constant pressure funnel according to the molar ratio of 2.1.
2) Synthesis of styrene-acrylate copolymer:
raw materials: methacrylic acid/acrylic acid, methyl methacrylate/ethyl methacrylate/acrylonitrile/styrene, butyl acrylate/butyl methacrylate/isooctyl acrylate/hydroxyethyl acrylate, ethyl acetate/toluene/acetone/butanone/methanol, azobisisobutyronitrile/azobisisoheptonitrile/BPO/HTP, and the like.
Preparing a 1/3 mixed solution into a four-neck flask, adding solvents of toluene and methanol, mixing, introducing nitrogen, heating to reflux, stabilizing for 15min, adding AIBN, reacting for 30 min, dropwise adding the rest 2/3 monomers through a constant-pressure funnel for 3h, supplementing AIBN every 1h in the dropwise adding process, preserving heat for 4h after the dropwise adding is finished, supplementing AIBN every 2h in the heat preservation process, adding acetone and ethyl acetate after the heat preservation is finished, diluting to a proper viscosity, and cooling to room temperature to obtain the styrene-acrylate copolymer, wherein the mass ratio of MAA, AA, ST, BA, MBA,2-EHA is 10.
3) Preparing photosensitive glue:
raw materials: urethane acrylate prepolymer, styrene-acrylate prepolymer, reactive monomer, methanol, acetone and other solvents.
Weighing 20 parts of urethane acrylate prepolymer and 80 parts of styrene-acrylate copolymer, adding TMPTA, LA and IBOA which account for 30% of the total mass of the prepolymer, methanol and acetone solvents, heating in a water bath, and uniformly stirring at 40 ℃ for 5 hours to obtain the photosensitive glue.
4) Preparation of resin composition:
pouring the photosensitive glue into a four-neck flask, weighing a photoinitiator 1173 accounting for 1 percent of the total mass of the active monomers and dye OP powder accounting for 0.3 percent of the total mass of the active monomers, and uniformly stirring for 2 hours to obtain the resin composition for preparing the dry film.
Example 3
The embodiment provides a preparation method of a water-soluble dry film polyurethane modified acrylic resin polymer for lithography, which comprises the following steps:
1) Polyurethane acrylate prepolymer synthesis:
raw materials: isocyanate (isocyanate such as TDI, IPDI, HDI, MDI) and the like), polyol, hydroxyethyl acrylate, organotin catalyst, toluene, acetone and the like.
Feeding IPDI (PPG (700): HEA in a molar ratio of 2.3: 1.4 into a four-neck flask provided with a condenser, a stirrer, a thermometer and a constant pressure funnel, adding a toluene solvent and IPDI (isophorone diisocyanate) for mixing, introducing dry nitrogen, dropwise adding HEA through the constant pressure funnel, completing the addition within 2h, reacting for 3h at 65 ℃, heating to 75 ℃, adding an organic tin catalyst accounting for 2% of the total mass of the IPDI, PPG and HEA, dropwise adding PPG polyhydric alcohol through the constant pressure funnel, completing the addition within 1.5h, reacting for 6h, and cooling to room temperature to obtain the polyurethane acrylate prepolymer.
2) Synthesis of styrene-acrylate copolymer:
raw materials: methacrylic acid/acrylic acid, methyl methacrylate/ethyl methacrylate/acrylonitrile/styrene, butyl acrylate/butyl methacrylate/isooctyl acrylate/hydroxyethyl acrylate, ethyl acetate/toluene/acetone/butanone/methanol, azobisisobutyronitrile/azobisisoheptonitrile/BPO/HTP, and the like.
Preparing a 1/3 mixed solution into a four-neck flask, adding solvents of toluene and methanol, mixing, introducing nitrogen, heating to reflux, stabilizing for 15min, adding AIBN, reacting for 30 min, dropwise adding the rest 2/3 monomers through a constant-pressure funnel for 3h, supplementing AIBN every 1h in the dropwise adding process, preserving heat for 4h after the dropwise adding is finished, supplementing AIBN every 2h in the heat preservation process, adding acetone and ethyl acetate after the heat preservation is finished, diluting to a proper viscosity, and cooling to room temperature to obtain the styrene-acrylate copolymer, wherein the mass ratio of MAA, AA, ST, BA, MBA,2-EHA is 10.
3) Preparing photosensitive glue:
raw materials: urethane acrylate prepolymer, styrene-acrylate prepolymer, reactive monomer, methanol, acetone and other solvents.
Weighing 20 parts of urethane acrylate prepolymer and 80 parts of styrene-acrylate copolymer, adding TMPTA, LA, IBOA, methanol and acetone solvent accounting for 60% of the total mass of the prepolymer, heating in water bath, and uniformly stirring at 40 ℃ for about 5 hours to obtain the photosensitive glue.
4) Preparation of resin composition:
pouring the photosensitive glue into a four-neck flask, weighing a photoinitiator 1173 accounting for 0.2 percent of the total mass of the active monomers, a photoinitiator 184 accounting for 0.2 percent of the total mass of the active monomers and dye PS powder accounting for 0.5 percent of the total mass of the photoreactive monomers, and uniformly stirring for 2 hours to obtain the resin composition for preparing the dry film.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any equivalent changes, modifications and evolutions of the above embodiments according to the essential technology of the present invention are still within the scope of the technical solution of the present invention.
Claims (9)
1. The preparation method of the water-soluble dry film polyurethane modified acrylic resin polymer for photoetching is characterized by comprising the following steps of:
1) Synthesis of polyurethane acrylic prepolymer: adding isocyanate, an organic solvent and hydroxyethyl acrylate into a reaction vessel, reacting for a period of time, heating, adding a catalyst and polyol, and reacting to obtain a polyurethane acrylic prepolymer;
2) Synthesis of styrene-acrylate copolymer: preparing a mixed solution of MAA, AA, ST, BA, MBA and 2-EHA, adding an organic solvent into a part of the mixed solution to react with AIBN for a period of time, adding the rest of the mixed solution, continuing to react, and cooling to obtain a styrene-acrylate copolymer;
3) Preparing photosensitive glue: uniformly stirring the polyurethane acrylic prepolymer obtained in the step 1) and the styrene-acrylate copolymer obtained in the step 2) with an active monomer and an organic solvent under a water bath condition to obtain photosensitive glue;
4) Preparation of resin composition: uniformly stirring the photosensitive glue obtained in the step 3), a photoinitiator and a dye to obtain the water-soluble dry film polyurethane modified acrylic resin polymer for preparing the photoetching.
2. The method of claim 1, wherein in step 1), the isocyanate is one of TDI, IPDI, HDI or MDI, the polyol comprises PPG, the organic solvent comprises toluene or acetone, and the catalyst is an organotin-based catalyst.
3. The method for preparing a water soluble dry film polyurethane modified acrylic resin polymer for lithography according to claim 1 or 2, wherein in step 1), the molar ratio of isocyanate, polyol and hydroxyethyl acrylate is 2-2.3.
4. The method for preparing the water-soluble dry film polyurethane modified acrylic resin polymer for lithography according to claim 1, wherein the specific steps of step 1) are as follows: adding IPDI, PPG and HEA into a four-neck flask provided with a condenser, a stirrer, a thermometer and a constant pressure funnel, adding a toluene solvent and IPDI for mixing, introducing dry nitrogen, dropwise adding HEA through the constant pressure funnel within 2 hours, reacting for 3 hours at the temperature of 50-65 ℃, heating to 75 ℃, adding an organic tin catalyst accounting for 0.5-2% of the total mass of the IPDI, PPG and HEA, dropwise adding PPG polyol through the constant pressure funnel, reacting for 4-6 hours, and cooling to room temperature to obtain the urethane acrylate prepolymer.
5. The method for preparing a water-soluble dry film polyurethane-modified acrylic resin polymer for lithography according to claim 1, wherein in step 2), the mass ratio of MAA, AA, ST, BA, MBA,2-EHA is 10.
6. The method for preparing the water-soluble dry film polyurethane modified acrylic resin polymer for lithography according to claim 1, wherein the step 2) comprises the following specific steps: preparing a mixed solution from MAA, AA, ST, BA, MBA and 2-EHA, pouring 1/3 of the mixed solution into a four-neck flask, adding toluene and methanol for mixing, introducing nitrogen, heating to reflux, stabilizing for 10-20min, adding AIBN, reacting for 30 min, dropwise adding the rest 2/3 of the mixed solution through a constant-pressure funnel for 3h, supplementing AIBN every 1h in the dropwise adding process, preserving heat for 3.5-4.5h after the dropwise adding is finished, supplementing AIBN every 2h in the heat preserving process, adding acetone and ethyl acetate after the heat preserving process is finished, diluting to a proper viscosity, and cooling to room temperature to obtain the styrene-acrylate copolymer.
7. The method for preparing the water-soluble dry film polyurethane modified acrylic resin polymer for lithography according to claim 1, wherein in the step 3), 15-25 parts by weight of polyurethane acrylic prepolymer, 75-85 parts by weight of styrene-acrylate copolymer and 2-12 parts by weight of reactive monomer are used.
8. The method for preparing the water-soluble dry film polyurethane modified acrylic resin polymer for lithography according to claim 1, wherein in the step 3), the temperature of water bath heating is 40-45 ℃ and the stirring time is 4-5.5h, and the active monomer comprises one or more of TMPTA, LA and IBOA.
9. The method for preparing the water-soluble dry film polyurethane modified acrylic resin polymer for lithography according to claim 1, wherein in the step 4), the photoinitiator comprises one or a combination of two of a photoinitiator 1173, a photoinitiator 184 and a photoinitiator 1176, and the addition amount of the photoinitiator is 0.5-2% of the mass of the active monomer; the dye is OP and/or PS, and the addition amount of the dye is 0.1-0.5% of the mass of the active monomer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117320297A (en) * | 2023-10-23 | 2023-12-29 | 浙江晶引电子科技有限公司 | Preparation method of ultrathin flexible film packaging substrate combining photoetching and die cutting |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120142871A1 (en) * | 2009-06-01 | 2012-06-07 | Wenjun Zhong | Polyurethane-modified acrylic resin and preparing method thereof |
| CN106752864A (en) * | 2016-12-08 | 2017-05-31 | 陕西高新实业有限公司 | The preparation method of urethane acrylate cured film |
| 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 |
| CN113583212A (en) * | 2021-08-05 | 2021-11-02 | 明光科迪新材料有限公司 | Polyurethane modified epoxy acrylate UV resin containing double-type photo-initiation group |
-
2022
- 2022-08-09 CN CN202210947557.0A patent/CN115373223A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120142871A1 (en) * | 2009-06-01 | 2012-06-07 | Wenjun Zhong | Polyurethane-modified acrylic resin and preparing method thereof |
| CN106752864A (en) * | 2016-12-08 | 2017-05-31 | 陕西高新实业有限公司 | The preparation method of urethane acrylate cured film |
| 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 |
| CN113583212A (en) * | 2021-08-05 | 2021-11-02 | 明光科迪新材料有限公司 | Polyurethane modified epoxy acrylate UV resin containing double-type photo-initiation group |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117320297A (en) * | 2023-10-23 | 2023-12-29 | 浙江晶引电子科技有限公司 | Preparation method of ultrathin flexible film packaging substrate combining photoetching and die cutting |
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