CN108165095B - Ink for quickly positioning back reference position of substrate and positioning method thereof - Google Patents
Ink for quickly positioning back reference position of substrate and positioning method thereof Download PDFInfo
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- CN108165095B CN108165095B CN201711455488.7A CN201711455488A CN108165095B CN 108165095 B CN108165095 B CN 108165095B CN 201711455488 A CN201711455488 A CN 201711455488A CN 108165095 B CN108165095 B CN 108165095B
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- ink
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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
- C09D11/50—Sympathetic, colour changing or similar inks
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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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- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0266—Marks, test patterns or identification means
- H05K1/0269—Marks, test patterns or identification means for visual or optical inspection
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to ink for quickly positioning a back reference position of an ink pattern layer substrate and a positioning method thereof, wherein the ink comprises a color-changing composition for improving the color difference of the ink before and after UV (ultraviolet) photocuring, the color-changing composition comprises a photoinitiator and a dye, and the weight ratio of the photoinitiator to the dye is 1: (0.1-1), wherein the photoinitiator is hexaarylbisimidazole photoinitiator, and the dye is malachite green dye. After the color-changing composition is applied to ink, a circuit board coated with the ink is changed into light blue to blue purple after being cured by ultraviolet light, and the color-changing composition can be used for an infrared CCD automatic identification system of LDI equipment to identify and align, and the infrared CCD automatic identification rate is 100%.
Description
Technical Field
The invention belongs to the field of circuit board preparation, and particularly relates to a method for quickly positioning the back surface of a circuit board and ink applied to the method, in particular to ink for quickly positioning the back surface reference position of an ink pattern layer substrate and a positioning method of the ink.
Background
At present, the substrate is punched or a film is fixed or other machines are aligned in the traditional way, and the traditional ink can not meet the requirement of LDI (laser direct injection) process color change identification alignment.
Generally, the common photosensitive ink is milky white and light blue, the exposed part is changed into light purple, but the contrast of the exposed part and the unexposed part cannot be obviously distinguished, so that the alignment cannot be identified in the LDI process.
In the prior art, for example, CN201510596317.0 discloses a solder resist photosensitive resin composition, which adopts 12-14 wt% of photoinitiator and 3.5-4.5 wt% of dye as the components, but it solves the problems of making the photosensitive dry film have good mechanical properties, fast curing speed, no air bubbles between the solder resist and the circuit board, and the problem of photosensitive identification is not solved because the type of photoinitiator used is not matched with the dye.
Chinese patent application CN200610165254.4 discloses a photo-curable ink-jet resist for printed circuit boards, wherein a radical type photoinitiator is applied, such as benzoin, benzil, α' -dimethylbenzyl ketal, α -diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl propanone, 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinyl) 1-butanone, 2, 4, 6-trimethylbenzoylethoxyphenyl phosphorus oxide, 2-hydroxy-2-methyl-1-hydroxy-2-morpholinophenyl ketone, 2, 4, 6-trimethylbenzoylethoxyphenyl phosphorus oxide, and, 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 4-p-tolylmercaptobenzophenone, benzophenone, 2, 4, 6-trimethylbenzophenone, 4-methylbenzophenone, 4 ' -bis (dimethylamino) benzophenone, 4 ' -bis (diethylamino) benzophenone, 4 ' -bis (methyl, ethylamino) benzophenone, isopropylthioxanthone, 2-chlorothianthrone, 1-chloro-4-propoxythioxanthone, 2, 4-diethylthioxanthone, 2-ethylanthraquinone; cationic photoinitiators, such as didodecylbenziodonium salts, long-chain alkoxydiphenyliodonium salts, bis (4, 4 '-thiotriphenylsulfonium) hexafluoroantimonate, phenylthiophenyldiphenyldiphenylsulfonium hexafluoroantimonate, bis (4, 4' -thiotriphenylsulfonium) hexafluorophosphate, phenylthiophenyldiphenylsulfonium hexafluorophosphate,. eta.6-cumeneferrocene hexafluorophosphate, blue or green dyes are used, blue dyes such as: acid emerald blue 2G, weak acid blue AS, acid blue 2G, acid blue 78, acid lake blue V, acid brilliant blue R, acid blue G, weak acid brilliant blue 5R, weak acid brilliant blue GR, acid complex blue GGN, direct blue 2B, direct fast blue FRL, disperse blue BGL, disperse dark blue H-3G, disperse blue FFR, disperse turquoise blue HBF, disperse blue 2BLN, disperse brilliant blue G; green dyes such as vat brilliant green 3B, vat brilliant green 2G, vat olive green B, sulphur brilliant green GB, and basic green.
The patent applies the photoinitiator and the dye to solve the problems that the ink resist has good stripping performance, short curing time and high resolution, the ink resist can be sprayed on a specific area of a copper-clad plate by utilizing an ink-jet technology, and an anti-etching pattern is formed after photocuring. The prepared cured film has high hardness, good flexibility and good corrosion resistance.
At present, in the field of photosensitive ink, particularly ink for preparing a circuit board by an LDI (laser direct immersion) process, ink and a color-changing composition which can well solve the problems of high recognition rate and rapid positioning of a back reference position of a substrate do not exist.
In order to solve the problem that the reverse side can be accurately positioned and photosensitive and aligned in the process of preparing the circuit board by adopting the LDI process, the technical scheme of the invention solves the problem by adjusting the formula of the photosensitive ink and the applied color-changing composition.
Disclosure of Invention
In order to solve the technical problems, the invention provides a color-changing composition for improving the color difference degree of ink before and after UV (ultraviolet) photocuring, which comprises a photoinitiator and a dye, wherein the weight ratio of the photoinitiator to the dye is 1: (0.1-1), wherein the photoinitiator is hexaarylbisimidazole photoinitiator, and the dye is malachite green dye.
Preferably, in the color-changing composition, the hexaarylbisimidazole photoinitiator is a hexaarylbisimidazole photoinitiator, and the hexaarylbisimidazole photoinitiator is one or two of o-chlorohexaarylbisimidazole (BCIM) and 2,2 '-bis-o-methoxyphenyl-4, 4' -5,5 '-tetraphenyl-1, 2' -Bisimidazole (BMOIM).
Preferably, in the color-changing composition, the weight ratio of the photoinitiator to the dye is 1: (0.1-0.5), it is particularly preferred that the weight ratio of photoinitiator to dye is 1: 0.4.
the ink is prepared from the composition obtained by combining the photoinitiator and the dye, so that the obvious color difference of the ink before and after UV light curing is solved, and the obvious difference can realize the alignment problem of the ink used for the LDI process photosensitive operation procedure after coating a circuit board.
After the back surface of the circuit board passes through the UV light color development calibration area, the color of the calibration area after color development can be accurately and quickly identified by LDI equipment, so that the back surface of the circuit board can accurately and quickly determine the reference position before UV light curing, and the photosensitive action of the second surface of the circuit board is smoothly completed.
The LDI device identifies the color-developed calibration area on the premise that the color of the calibration area after color development is recognized, which requires that the color satisfies a certain requirement. Then, for a long time, the problems have not been solved well by the photosensitive ink circuit boards, which have been solved by the above-mentioned solutions using specific photoinitiators and specific dyes.
The invention also provides ink with obvious color difference before and after UV light curing, and the preparation raw material of the ink comprises the color-changing composition, and the color-changing composition accounts for 5-15% of the preparation raw material by weight, and preferably 6-9% of the preparation raw material by weight.
Preferably, the raw materials for preparing the ink further comprise one or more of an ultraviolet light curing resin, a polymerization initiator, a diluent, a filler, a dispersion stabilizer, a colorant, a thixotropic agent, an antifoaming agent, an anti-halation agent, a leveling agent, an adhesive, a polymerization inhibitor, a flame retardant, a polymeric dispersant and an anti-oxidant. The added components are determined according to actual conditions.
Preferably, in the raw materials for preparing the ink, the ultraviolet curing resin is a mixture of acrylic copolymer and epoxy acrylic acid, wherein the weight ratio of the acrylic copolymer to the epoxy acrylic acid is 1: (0.2-5), the ultraviolet curing resin accounts for 30-60% of the total weight of the ink.
Preferably, in the raw material for preparing the ink, the epoxy acrylic acid is an epoxy compound having 2 or more epoxy groups.
Preferably, in the raw materials for preparing the ink, the polymerization initiator is one or more of tert-butyl hydroperoxide, 2-tert-butyl peroxide, lauryl peroxide, benzoyl peroxide, diisopropyl peroxide dicarbonate, azobisisobutyronitrile, methyl 2, 2' -azobisisobutyrate, azobiscyanovaleronitrile and triphenylphosphine.
Preferably, in the raw material for preparing the ink, the diluent is an organic solvent, and the organic solvent is preferably one or more of methyl ethyl ketone, cyclohexanone, toluene, xylene, ethyl acetate, butyl acetate, ethylene glycol ethyl ether acetate, butyl ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, and dialkyl glycol ether.
The invention also provides a circuit board which is characterized in that the front and back surfaces of the circuit board are coated with the ink.
The invention also provides a method for quickly positioning the back reference position of the substrate, which comprises the steps of coating the ink on the front side and the back side of a circuit board, changing the color of the ink on the back side of the circuit board by using ultraviolet light, and identifying and positioning by using an infrared CCD automatic identification system.
The invention has the advantages of
After the color-changing composition is applied to ink, a circuit board coated with the ink is changed into light blue to blue-violet after being cured by ultraviolet light, and an infrared CCD automatic identification system is used for identifying alignment on equipment, wherein the infrared CCD automatic identification rate is 100%.
The ink disclosed by the invention contains the color-changing composition, so that the circuit board coated with the ink can be quickly positioned in the processing process of adopting the LDI (laser direct immersion) process, and the positioning is accurate.
The color-changing composition adopts hexaarylbisimidazole photoinitiator or aryl sulfonium salt photoinitiator and malachite green dye or crystal violet dye, and can change into the best identification color after being irradiated by ultraviolet after being applied to ink, so that the accuracy of identifying the back surface of a circuit board is improved.
Detailed Description
The materials in the following examples are all commercially available.
Example 1: preparation of color-changing composition
A color-changing composition comprising a hexaarylbisimidazole-based photoinitiator and a dye and a composition comprising an arylthionium salt photoinitiator and a dye were prepared, respectively.
The specific formulation of each color-changing composition is as follows in table 1:
TABLE 1 color-changing composition formula table
Wherein the photoinitiator ITX is 2-isopropyl thioxanthone, and the photoinitiator 907 is 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-acetone.
Example 2: preparation of UV inks using color-changing compositions
Mixing acrylic copolymer and epoxy acrylic acid in a weight ratio of 1: 2, taking 50g, adding 0.03g of tert-butyl hydroquinone compound, adding 10g of methyl ethyl ketone, respectively adding 7g of the color-changing composition, then adding a proper amount of BYK-333 leveling agent, a proper amount of KS-66 defoaming agent and a proper amount of talcum powder to achieve that the total weight of the ink is 100g, and grinding and dispersing to obtain the ink containing different color-changing compositions.
In the preparation of the ink, in the process of preparing the ink by using different color-changing compositions, the formula of each ink only changes the variety of the color-changing composition in the ink, and other components are not changed.
The color-changing composition and the method are applied to respectively prepare the ink, then the ink is respectively coated on the front side and the back side of the circuit board, then ultraviolet light curing is carried out, an infrared CCD automatic identification system is used for identifying contraposition, and the identification accuracy is calculated.
The applied color-changing compositions and the achieved recognition effect of each ink are seen in table 2 below.
TABLE 2 ink prepared using the color-changing composition and the recognition accuracy of the ink
| Ink number | Number of color-changing composition | Rate of identification accuracy |
| Y01 | B01 | 100％ |
| Y02 | B02 | 87％ |
| Y03 | B03 | 91％ |
| Y04 | B04 | 100％ |
| Y05 | B05 | 84％ |
| Y06 | B06 | 88％ |
| Y07 | B07 | 83％ |
| Y08 | B08 | 81％ |
| Y09 | B09 | 38％ |
| Y10 | B10 | 43％ |
| Y11 | B11 | 55％ |
Through experiments, the recognition rate of the ink containing the color-changing compositions B01 and B04 is the highest and reaches 100%, while the recognition rate of the ink containing other color-changing compositions cannot reach 100%.
By adjusting the ratio of the photoinitiator to the dye in the color-changing compositions B01 and B04, the weight ratio of the photoinitiator to the dye is found to be 1: (0.2-5) the efficiency of 100% recognition rate, and the recognition rate of the color-changing compositions B01 and B04 can reach 100% within the range of 5-15% by weight percent.
Claims (4)
1. The method for quickly positioning the back reference position of the substrate comprises the steps of coating ink on the front side and the back side of a circuit board, changing color of the ink on the back side of the circuit board by using ultraviolet light, and identifying and positioning by using an infrared CCD automatic identification system, wherein a preparation raw material of the ink comprises a color-changing composition, the color-changing composition accounts for 5-15% of the preparation raw material by weight, the color-changing composition comprises a photoinitiator and a dye, and the weight ratio of the photoinitiator to the dye is 1: (0.1-1), wherein the photoinitiator is hexaarylbisimidazole photoinitiator, the dye is malachite green dye, the hexaarylimidazole photoinitiator is hexaarylbisimidazole photoinitiator, and the hexaarylbisimidazole photoinitiator is one or two of o-chloro-hexaarylbisimidazole, 2 '-di-o-methoxyphenyl-4, 4' -5,5 '-tetraphenyl-1, 2' -bisimidazole.
2. The method of claim 1, wherein the weight ratio of photoinitiator to dye is 1: (0.1-0.5).
3. The method according to claim 1, wherein the ink is prepared from one or more of a uv curable resin, a polymerization initiator and a diluent, a filler, a dispersion stabilizer, a colorant, a thixotropic agent, an antifoaming agent, an antihalation agent, a leveling agent, an adhesive, a polymerization inhibitor, a flame retardant, a polymeric dispersant, and an antioxidant.
4. The method according to claim 3, wherein the UV-curable resin is a mixture of acrylic copolymer and epoxy acrylic acid, wherein the weight ratio of acrylic copolymer to epoxy acrylic acid is 1: (0.2-5), the ultraviolet curing resin accounts for 30-60% of the total weight of the ink.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711455488.7A CN108165095B (en) | 2017-12-28 | 2017-12-28 | Ink for quickly positioning back reference position of substrate and positioning method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711455488.7A CN108165095B (en) | 2017-12-28 | 2017-12-28 | Ink for quickly positioning back reference position of substrate and positioning method thereof |
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| CN108165095A CN108165095A (en) | 2018-06-15 |
| CN108165095B true CN108165095B (en) | 2020-12-18 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102186643A (en) * | 2008-08-21 | 2011-09-14 | 因诺瓦动力学股份有限公司 | Enhanced surfaces, coatings, and related methods |
| CN101386599B (en) * | 2008-10-31 | 2012-05-23 | 王宝湖 | Hexaarylbisimidazoles compounds, preparation method and application thereof and composition containing thereof |
| CN103543608A (en) * | 2009-02-26 | 2014-01-29 | 日立化成工业株式会社 | Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same |
| CN107501442A (en) * | 2017-08-15 | 2017-12-22 | 宁波七诺新材料科技有限公司 | For 3D printing technique by visible light-initiated photoinitiator composite and application |
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2017
- 2017-12-28 CN CN201711455488.7A patent/CN108165095B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102186643A (en) * | 2008-08-21 | 2011-09-14 | 因诺瓦动力学股份有限公司 | Enhanced surfaces, coatings, and related methods |
| CN101386599B (en) * | 2008-10-31 | 2012-05-23 | 王宝湖 | Hexaarylbisimidazoles compounds, preparation method and application thereof and composition containing thereof |
| CN103543608A (en) * | 2009-02-26 | 2014-01-29 | 日立化成工业株式会社 | Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same |
| CN107501442A (en) * | 2017-08-15 | 2017-12-22 | 宁波七诺新材料科技有限公司 | For 3D printing technique by visible light-initiated photoinitiator composite and application |
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| CN108165095A (en) | 2018-06-15 |
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