CN106905767B - Photosensitive ink containing hyperbranched UV (ultraviolet) curing WPU (waterborne polyurethane) prepolymer, and preparation method and application thereof - Google Patents
Photosensitive ink containing hyperbranched UV (ultraviolet) curing WPU (waterborne polyurethane) prepolymer, and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
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- 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
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- 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
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
- H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
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- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses photosensitive ink containing hyperbranched UV (ultraviolet) curing WPU (waterborne polyurethane) prepolymer, which comprises the following substances in parts by weight: 100 parts of hyperbranched UV curing WPU prepolymer, 15-45 parts of reactive diluent, 3-8 parts of photoinitiator and 10-100 parts of filler. The photosensitive ink has the advantages of moderate viscosity, good insulation and protection effects, high curing speed, small environmental pollution, low energy consumption and the like, and in addition, the photosensitive ink has high solid content, high crosslinking degree after film forming, excellent comprehensive performance, and good compatibility and adhesive force of a substrate material of a flexible circuit board. The invention also discloses a preparation method of the photosensitive ink, application of the photosensitive ink to printing of a flexible circuit board and the printed flexible circuit board.
Description
Technical Field
The invention relates to the field of UV (ultraviolet) curing high polymer materials, in particular to photosensitive ink containing hyperbranched UV curing WPU prepolymer, a preparation method of the photosensitive ink, application of the photosensitive ink in printing of a flexible circuit board and the flexible circuit board printed with the photosensitive ink.
Background
The flexible circuit board can provide excellent conductive performance, can be freely bent, wound and folded, can bear millions of dynamic bending without damaging the lead, can be randomly arranged according to the space layout requirement, and can be randomly moved and stretched in a three-dimensional space, so that the integration of component assembly and lead connection is achieved, the design requirement of more small and high-density installation can be met, the reduction of assembly procedures and the enhancement of reliability are facilitated, and the flexible circuit board is the only solution for meeting the requirements of miniaturization and movement of electronic products. The flexible circuit board comprises a single-sided flexible board, a double-sided flexible board and a multilayer flexible board, and is prepared by etching to prepare a copper circuit, coating an insulating solder mask layer, wherein the insulating solder mask layer is coated by adopting a silk screen method and a wet film method, and respectively adopting flexible solder mask ink and light imaging solder mask ink. Since flexible wiring boards need to be bent, folded and moved, which requires the flexible solder resist ink to meet such requirements, the main resin of the ink needs to have excellent flexibility to ensure that the cured solder resist film does not show separation, cracking or delamination from the substrate or wires after 25 cycles of bending. Therefore, the flexible circuit board has high requirements on flexible solder resist ink and photo-imaging solder resist ink, and the common ink is difficult to meet the requirements.
The photosensitive ink is ink which is sensitive to ultraviolet rays and can be cured by the ultraviolet rays, and is widely used in the industries of FPC (flexible printed circuit), PCB (printed circuit board), mobile phone, SMT (surface mount technology), IC (integrated circuit) lead wires, VFD (vacuum frequency detector) grids, watches, notebook shells, labels and the like. The main resin of the common photosensitive ink mainly adopts polyurethane acrylate (PUA), and the PUA is a typical waterborne polyurethane resin (WPU), has excellent high tension, waterproof and breathable performance, toughness and ageing resistance, and has excellent biological and blood compatibility and chemical resistance. The photosensitive ink also needs to be added with a reactive diluent, the reactive diluent usually adopts functional acrylate with good flexibility, but the polyurethane acrylate prepolymer is a linear prepolymer with high viscosity, and needs to use more reactive diluent, so that the solid content of the ink is low, the crosslinking degree of the linear prepolymer after film formation is low, and the performance of the ink is far lower than that of a hyperbranched prepolymer.
The Chinese invention patent with the publication number of CN105254499A discloses a tung oil ester alkylated compound containing phenolic hydroxyl groups and application thereof in producing coatings, photosensitive ink and adhesives, the adopted raw material is tung oil, but the photosensitive ink prepared from the compound has poor compatibility and adhesion with polyimide flexible circuit boards, and cannot be widely applied to printed flexible circuit boards, in particular to polyimide substrates with wide application. The chinese patent publication No. CN103616798A discloses a photosensitive resin with flame retardant property and its application in producing photosensitive ink, the photosensitive resin used is a flame retardant epoxy resin, but the problems of poor compatibility and poor adhesion between the photosensitive ink and the polyimide type flexible circuit board still exist. The Chinese patent publication No. CN105828587A also discloses a preparation method of photosensitive ink, the photosensitive oligomer is selected from traditional photocuring prepolymers such as aromatic amine acrylic ester resin, epoxy acrylate and polyurethane acrylate, and the photosensitive ink has low crosslinking degree after film forming and poor comprehensive performance.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the invention provides a photosensitive ink containing hyperbranched UV-curable WPU prepolymer; the invention also aims to provide a method for preparing the photosensitive ink, application of the photosensitive ink to printing of a flexible circuit board and the flexible circuit board printed with the photosensitive ink.
According to one aspect of the invention, a photosensitive ink containing a hyperbranched UV-curable WPU prepolymer is provided, and the composition of the photosensitive ink comprises the following substances in parts by weight: 100 parts of hyperbranched UV curing WPU prepolymer, 15-45 parts of reactive diluent, 3-8 parts of photoinitiator and 10-100 parts of filler,
wherein the hyperbranched UV curing WPU prepolymer has a structure shown in a formula (I),
in the formula (I), R1Is H, Cl, CH3、OH、OCH3And C (CH)3)3Any one of (a); r2Is CH2CH2、CH2CH2CH2、CH2CH(CH3) And
any one of (a); the R is3Is H or CH3；
Wherein the reactive diluent is at least one of isobornyl acrylate, isobornyl methacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate;
wherein the photoinitiator is at least one of diphenylethanone, α -diethoxyacetophenone, benzoin ethyl ether, benzoin butyl ether, 2,4, 6-trimethylbenzoylphosphine oxide and 1-chloro-4-propoxyl thioxanthone;
wherein, the filler is at least one of barium sulfate, calcium carbonate and aluminum hydroxide.
According to another aspect of the present invention, there is also provided a method of preparing the above photosensitive ink containing a hyperbranched UV-curable WPU prepolymer, comprising the steps of:
(1) adding the raw materials into a reactor at 15-25 ℃ in parts by weight
100 parts, then dropwise adding a mixture of 200-1000 parts of polyisocyanate and 0.05-0.3 part of dibutyltin dilaurate into a reactor, uniformly mixing, heating to 50-80 ℃, and reacting for 1-3 hours to obtain an intermediate product I;
(2) adding 100 parts of the intermediate product I into a reactor, dissolving the intermediate product I with enough castor oil, dropwise adding a mixture of 50-200 parts of hydroxyalkyl acrylate and 0.01-1 part of polymerization inhibitor into the reactor, and controlling the mixed system to react for 1-3.5 hours at 50-90 ℃ to obtain a hyperbranched UV (ultraviolet) curing WPU prepolymer;
(3) mixing the prepared hyperbranched UV-cured WPU prepolymer, an active diluent, a photoinitiator and a filler in proportion to obtain photosensitive ink containing the hyperbranched UV-cured WPU prepolymer;
wherein the polymerization inhibitor is at least one of p-hydroxyanisole and hydroquinone.
Preferably, in step (1)
R in (1)1Is H, Cl, CH3、OH、OCH3And C (CH)3)3Any one of the above.
Preferably, the polyisocyanate in step (1) is at least one of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and dicyclohexylhexane diisocyanate.
Preferably, the polyisocyanate is added in the step (1) in an amount of 400 to 600 parts by weight.
Preferably, the hydroxyalkyl acrylate in step (2) is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and pentaerythritol triacrylate.
According to another aspect of the invention, the application of the photosensitive ink containing the hyperbranched UV-curing WPU prepolymer in printing of flexible circuit boards is also provided.
According to another aspect of the present invention, there is also provided a flexible wiring board made by ink-jetting or printing the above photosensitive ink containing the hyperbranched UV-curable WPU prepolymer on a substrate.
Compared with the prior photosensitive ink synthesis technology, the invention has the following advantages and beneficial effects:
(1) the base material of the flexible circuit board is mostly polyimide, the basic film forming substance used by the photosensitive ink of the flexible circuit board prepared by the invention is hyperbranched WPU, aromatic diamine is taken as a core, the components of the basic film forming substance are the same as those of the substrate material of the flexible circuit board, and the basic film forming substance is polyimide material which has excellent compatibility and adhesive force.
(2) The invention firstly provides the idea of using the hyperbranched WPU resin for the photosensitive ink of the flexible circuit board, and the designed and synthesized hyperbranched WPU resin not only avoids the safety and environmental protection problems of the traditional thermosetting ink, but also ensures that the photosensitive ink prepared by the hyperbranched WPU resin has excellent performances in the aspects of flexibility, bending resistance, printability, drying speed, water resistance, color brightness and the like.
(3) The invention improves the traditional method for preparing polyimide by polyimide through thermal or chemical treatment, and the solder resist ink is obtained by directly carrying out UV curing on the photosensitive ink containing the hyperbranched UV curing WPU prepolymer, thereby greatly reducing pollution caused by chemical treatment and a large amount of energy consumption required by thermal treatment.
(4) The photosensitive ink containing the hyperbranched UV curing WPU prepolymer has the advantages of moderate viscosity, good insulation and protection effects, high curing speed and the like, the UV curing photosensitive ink is convenient for printing a flexible circuit board by an ink-jet printing method, the printing steps of the ink are simplified, the sprayed circuit board can be rapidly cured by UV exposure, the production is convenient, and areas which do not need to be cured can also be washed clean by an organic solvent.
(5) The photosensitive ink containing the hyperbranched UV curing WPU prepolymer has moderate viscosity, does not need to use excessive reactive diluent, and therefore, the photosensitive ink containing the hyperbranched UV curing WPU prepolymer can increase the solid content of the ink, has high crosslinking degree after the ink forms a film, and has good comprehensive performance.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
1. Preparation of hyperbranched WPU resin prepolymer core:
sequentially adding dimethylolpropionic acid and aromatic diamine shown in Table 1 into a reaction kettle, dissolving dimethylolpropionic acid and aromatic diamine by using a solvent A, uniformly mixing, carrying out a neutralization reaction for 0.5-2.5 h, and continuously stirring in the reaction process to obtain the hyperbranched WPU resin prepolymer core, wherein the dosage of dimethylolpropionic acid is 100 parts by weight, and the dosage of the aromatic diamine is relative to the weight of dimethylolpropionic acid.
TABLE 1 substrate and conditions for the preparation of hyperbranched WPU resin prepolymer cores
In other embodiments, the aromatic diamine can also be 1,5 naphthalene diamine and naphthalene ring substituents thereof, and the 1,5 naphthalene diamine and naphthalene ring substituents thereof react with dimethylolpropionic acid to also prepare hyperbranched WPU resin prepolymer cores for preparing hyperbranched UV-cured WPU prepolymers and photosensitive inks containing the hyperbranched UV-cured WPU prepolymers.
2. Preparation of hyperbranched hydroxyl resin:
after the preparation reaction of the hyperbranched WPU resin prepolymer core is completed, dimethylolpropionic acid and an esterification catalyst are continuously added into the reaction kettle, the addition amount of the dimethylolpropionic acid in the previous step is 100 parts by weight, the weight parts of the dimethylolpropionic acid and the esterification catalyst in the step are shown in table 2, the mixture is stirred and mixed uniformly, the temperature is increased to 100-180 ℃, the vacuum-pumping dehydration reaction is carried out for 1-3 h, then the temperature is reduced to 65-75 ℃, a sufficient amount of solvent A is added to dissolve the mixed substrate, the mixed substrate is placed in an environment of 5-15 ℃ for cooling, a precipitating agent is added into a reaction mixed system until a product is crystallized and precipitates are separated out, and the crystal is dried in vacuum to obtain the hyperbranched hydroxyl resin.
TABLE 2 preparation of substrates and conditions for hyperbranched hydroxy resins
3. Preparation of modified polyisocyanate:
adding the hyperbranched hydroxyl resin prepared in all the embodiments into a reaction kettle at 15-25 ℃, dropwise adding a mixture of polyisocyanate and dibutyltin dilaurate into the reaction kettle, adjusting the dropwise adding speed and controlling the dropwise adding within 1-2 h, uniformly mixing, wherein the adding amount of the hyperbranched hydroxyl resin is 100 parts by weight, the adding amounts of the polyisocyanate and dibutyltin dilaurate are both relative to the weight of the hyperbranched hydroxyl resin, the specific types and the using amounts of the two substrates are shown in table 3, heating to 50-80 ℃, and stirring for reacting for 1-3 h to obtain an intermediate product I, namely the modified polyisocyanate.
TABLE 3 substrates and conditions for the preparation of modified polyisocyanates
4. Preparation of hyperbranched UV-curable WPU prepolymer:
adding the modified polyisocyanate prepared by the reaction into a reaction kettle, dissolving the modified polyisocyanate by using enough castor oil, dropwise adding a certain amount of hydroxyalkyl acrylate and a polymerization inhibitor into the reaction kettle, wherein the addition amount of the hydroxyalkyl acrylate and the polymerization inhibitor is 100 parts by weight of the modified polyisocyanate, the addition amounts of the hydroxyalkyl acrylate and the polymerization inhibitor are both relative to the weight of the modified polyisocyanate, and the specific types and addition amounts of the hydroxyalkyl acrylate and the polymerization inhibitor are shown in Table 4. And controlling the temperature of the mixed system to react for 1-3.5 h at 50-90 ℃ to obtain the hyperbranched UV curing WPU prepolymer.
Table 4 substrates and conditions for preparation of hyperbranched UV-curing WPU prepolymers
5. Preparing photosensitive ink containing hyperbranched UV curing WPU prepolymer:
and mixing the hyperbranched UV-cured WPU prepolymer prepared by the reaction with an active diluent, a photoinitiator and a filler in parts by weight to obtain the photosensitive ink containing the hyperbranched UV-cured WPU prepolymer. The added amounts of the reactive diluent, the photoinitiator and the filler are all relative to the weight of the hyperbranched UV-cured WPU prepolymer, and are shown in Table 5, taking the added amount of the hyperbranched UV-cured WPU prepolymer as 100 parts by weight.
TABLE 5 composition of photosensitive inks
In other embodiments, when preparing the ink containing the hyperbranched UV-curable WPU prepolymer, common additives, such as antiskinning agents (hydroquinone, methyl ethyl ketone oxime, etc.), dispersants (anionic dispersants, nonionic dispersants, etc.), wetting agents (ethoxylated nonionic surfactants, ethylene glycol, etc.), stabilizers (pH stabilizers), etc., may be added to the photosensitive ink mixture obtained in the above embodiments according to actual needs. When preparing the ink, the components are weighed according to the components listed in the table 5 and the corresponding weight parts, and the photosensitive ink containing the hyperbranched polyurethane acrylate prepolymer is obtained by uniformly stirring and mixing the components. When the ink is used, the prepared photosensitive ink containing the hyperbranched UV-cured WPU prepolymer is filled into an ink-jet printing device, and the printing work is completed by ink-jet printing of the polyimide flexible circuit board, namely UV curing is performed by a 30W ultraviolet lamp after ink-jet of the polyimide flexible circuit board is completed.
Printing an electric circuit board:
(1) substrate treatment: cleaning the surface of the substrate with detergent, removing oil stain, soaking in the waste etching solution, brushing with a toothbrush for 10s, drying with a paper towel, and air drying.
(2) Filling the prepared photosensitive ink containing the hyperbranched UV curing WPU prepolymer into an ink jet printing device, and carrying out ink jet printing on a polyimide flexible substrate, and placing the sprayed flexible substrate under sunlight for drying.
(3) And after the ink jet of the polyimide flexible circuit board is finished, carrying out UV curing for 5min by 2 parallel 30W ultraviolet lamp lamps, and carrying out crosslinking reaction hardening on the hyperbranched UV curing WPU prepolymer under the catalysis of ultraviolet light to finish the UV curing.
(4) Shadow making: after the substrate is washed and cured for 2min by the developer, the hyperbranched UV-cured WPU prepolymer which is subjected to the crosslinking reaction cannot be washed away, and the photosensitive ink part which is not catalyzed by ultraviolet rays is not subjected to the crosslinking reaction, so that the photosensitive ink part is washed away by the developer.
(5) Etching: and cleaning the surface of the substrate by using tap water until the surface of the substrate is cleaned, naturally drying the substrate, soaking the dried substrate in the environment-friendly etching solution for 15-30 min, and shaking a container containing the environment-friendly etching solution every 2 min.
(6) Demoulding: preparing a stripping solution, soaking the etched substrate in the stripping solution for 5min, and removing the blue oil on the electric circuit to obtain the printed flexible polyimide electric circuit board.
The photosensitive ink containing the hyperbranched UV-curable WPU prepolymer prepared in the above examples is used for comprehensive performance tests, that is, various performance tests are performed under the same conditions, and the test results are shown in Table 6.
Testing of surface drying time: and uniformly coating the photosensitive ink on the surface of the polytetrafluoroethylene plate, and carrying out UV curing under the set light source and exposure time. According to GB1728-79, a piece of filter paper is pressed on a curing film by a dry weight of 200g, the weight is removed after a certain time, the curing film is turned over, the filter paper can freely fall off, namely the curing film is considered to be surface-dried, and the curing and surface-drying time of the ink is measured.
The ink fineness analysis is characterized by adopting particle size analysis: the inks were tested using a Malvern ZS Nano S Malvern nanosize Analyzer.
And (3) viscosity analysis and characterization: the test temperature is 25 ℃ by adopting an NDJ-8S rotational viscometer of Shanghai precision instruments and meters Limited.
And (3) stability testing: respectively adopting thermal stability and mechanical stability analysis for characterization and thermal stability analysis, placing the printing ink in a constant-temperature oven at 50 ℃, observing the change of the appearance along with time, and recording the time required for layering. And (4) analyzing mechanical stability, namely putting the ink into a centrifugal tube, centrifuging for 20min at 8000r/min by using a centrifugal machine, and observing whether layering occurs or not.
Ink leveling test: the ability of the wet film to flow after ink application to eliminate smearing. In the method for testing leveling property in this embodiment, the time required for the film to recover or reach a uniform and smooth surface is taken as a reference, the leveling property of the film which is leveled within 5min is excellent, and the leveling property of the film which is leveled within 10min is good.
Determination of mechanical properties of ink cured film: the mechanical properties of the photocurable films were measured by a precision mechanical testing machine (Japan) model AG-I-50 in accordance with GB 13022-91.
The water resistance is characterized by water absorption and is tested according to the method of GB/T1733-93.
The adhesion was measured according to the method of GB/T9286-1998.
TABLE 6 comprehensive Property test results
The good UV curing printing ink generally has the characteristics of high curing rate, moderate hardness, excellent mechanical property after film forming and the like, for sensitization, the shorter the surface drying time of the resin is required, the higher the tensile strength is, the better the flexibility is, namely the higher the elongation at break is, the better the comprehensive performance of the resin is, the surface drying time of the prepared photosensitive printing ink containing the hyperbranched UV curing WPU prepolymer is less than 30 seconds, the fineness is less than 250nm, the viscosity is intensively distributed between 1000-2200 pas, the thermal stability and mechanical stability analysis is not layered, the leveling property is excellent, the elongation at break is more than 7%, the water absorption rate is low, the printing ink adhesion of a cutting edge is good, and only part of the coating falls off, so the comprehensive performances of the curing rate, the film mechanical property and the like completely meet the requirements of practical application.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (7)
1. The photosensitive ink containing the hyperbranched UV-curable WPU prepolymer is characterized by comprising the following substances in parts by weight: 100 parts of hyperbranched UV curing WPU prepolymer, 15-45 parts of reactive diluent, 3-8 parts of photoinitiator and 10-100 parts of filler,
wherein the hyperbranched UV-curing WPU prepolymer has a structure shown in a formula (I),
in the formula (I), R is1Is H, Cl, CH3、OH、OCH3And C (CH)3)3Any one of (a); the R is2Is CH2CH2、CH2CH2CH2、CH2CH(CH3) And
any one of (a); the R is3Is H or CH3；
Wherein the reactive diluent is at least one of isobornyl acrylate, isobornyl methacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate;
wherein the photoinitiator is at least one of diphenylethanone, α -diethoxyacetophenone, benzoin ethyl ether, benzoin butyl ether, 2,4, 6-trimethylbenzoylphosphine oxide and 1-chloro-4-propoxythioanthrone;
wherein, the filler is at least one of barium sulfate, calcium carbonate and aluminum hydroxide.
2. The method of making a photosensitive ink comprising a hyperbranched UV curable WPU prepolymer of claim 1, comprising the steps of:
(1) adding the raw materials into a reactor at 15-25 ℃ in parts by weight
100 parts, then dropwise adding a mixture of 200-1000 parts of polyisocyanate and 0.05-0.3 part of dibutyltin dilaurate into a reactor, uniformly mixing, heating to 50-80 ℃, and reacting for 1-3 hours to obtain an intermediate product I;
(2) adding 100 parts of the intermediate product I into a reactor, dissolving the intermediate product I with enough castor oil, dropwise adding a mixture of 50-200 parts of hydroxyalkyl acrylate and 0.01-1 part of polymerization inhibitor into the reactor, and controlling the mixed system to react for 1-3.5 hours at 50-90 ℃ to obtain a hyperbranched UV (ultraviolet) curing WPU prepolymer;
(3) mixing the prepared hyperbranched UV-cured WPU prepolymer, an active diluent, a photoinitiator and a filler in proportion to obtain photosensitive ink containing the hyperbranched UV-cured WPU prepolymer;
wherein the polymerization inhibitor is at least one of p-hydroxyanisole and hydroquinone.
3. The method for preparing photosensitive ink containing hyperbranched UV-curable WPU prepolymer as claimed in claim 2, wherein the polyisocyanate in the step (1) is at least one of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and dicyclohexyl hexane diisocyanate.
4. The preparation method of the photosensitive ink containing the hyperbranched UV-curable WPU prepolymer, according to claim 3, wherein the polyisocyanate is added in the step (1) in an amount of 400 to 600 parts by weight.
5. The method for preparing photosensitive ink containing hyperbranched UV-curable WPU prepolymer as claimed in claim 2, 3 or 4, wherein the hydroxyalkyl acrylate in the step (2) is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and pentaerythritol triacrylate.
6. Use of the photosensitive ink containing a hyperbranched UV-curable WPU prepolymer according to claim 1 for printing flexible wiring boards.
7. A flexible wiring board made by printing the photosensitive ink containing a hyperbranched UV-curable WPU prepolymer of claim 1 on a substrate.
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| CN201710178294.0A CN106905767B (en) | 2017-03-23 | 2017-03-23 | Photosensitive ink containing hyperbranched UV (ultraviolet) curing WPU (waterborne polyurethane) prepolymer, and preparation method and application thereof |
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| CN108055792A (en) * | 2017-11-09 | 2018-05-18 | 建业科技电子（惠州）有限公司 | A kind of segmentation gold finger plate wet film production method |
| CN108676189B (en) * | 2018-06-08 | 2020-10-02 | 东南大学 | Preparation method of ultraviolet-curing fluorosilicone release film for optical display |
| CN113419402B (en) * | 2021-06-10 | 2023-12-22 | 安徽强邦新材料股份有限公司 | Positive thermosensitive photosensitive composition and preparation method thereof |
| CN114716878A (en) * | 2022-02-21 | 2022-07-08 | 张家港保税区康得菲尔实业有限公司 | Solvent-free UV gloss oil and preparation and use methods thereof |
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| US6177523B1 (en) * | 1999-07-14 | 2001-01-23 | Cardiotech International, Inc. | Functionalized polyurethanes |
| JP2014519528A (en) * | 2011-04-15 | 2014-08-14 | ビーエーエスエフ ソシエタス・ヨーロピア | Hyperbranched polyester in printing ink |
| CN102585158B (en) * | 2011-12-23 | 2013-02-13 | 江苏飞翔化工股份有限公司 | Water-based double-component light-cured polyurethane resin and preparation method thereof |
| CN104311783B (en) * | 2014-11-11 | 2017-01-11 | 合肥思敬齐化工材料有限责任公司 | Unsaturated hyperbranched polyurethane prepolymer as well as preparation method and application thereof |
| JP6635711B2 (en) * | 2015-08-20 | 2020-01-29 | 株式会社ポリシス | Flexible polyurethane foam with excellent compression set, vibration damping and compression creep |
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