NL2032627B1 - Resistance welding dry film photoresist as well as preparation method use thereof - Google Patents
Resistance welding dry film photoresist as well as preparation method use thereof Download PDFInfo
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- NL2032627B1 NL2032627B1 NL2032627A NL2032627A NL2032627B1 NL 2032627 B1 NL2032627 B1 NL 2032627B1 NL 2032627 A NL2032627 A NL 2032627A NL 2032627 A NL2032627 A NL 2032627A NL 2032627 B1 NL2032627 B1 NL 2032627B1
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- photoresist layer
- resistance welding
- photoresist
- dry
- acrylate compound
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- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
-
- 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
-
- 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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- 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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
Abstract
Disclosed is a resistance welding dry film photoresist as well as a preparation method and 5 use thereof, belonging to the technical field of circuit board fabrication. The resistance welding dry film photoresist has a 3 - layer structure including a photoresist layer 1, a photoresist layer 2 and a photoresist layer 3 respectively, wherein the photoresist layer 1 comprises an epoxy acrylate base resin, a photocurable monomer, a thermocuring catalyst and a free radical initiator; the photoresist layer2 comprises a carboxyl - containing acrylate compound, a thermocuring resin 10 having a thermocurable functional group, a photo - polymerization monomer having at least two photocurable unsaturated functional groups, a photo initiator and a thermocuring catalyst; the photoresist layer 3 comprises a carboxyl - containing polymer adhesive, a photo - polymerization monomer, a thermo-polymerization inhibitor and a free radical photo initiator.
Description
RESISTANCE WELDING DRY FILM PHOTORESIST AS WELL AS PREPARATION METHOD
USE THEREOF
The present disclosure belongs to the technical field of circuit board fabrication, and particularly relates to a resistance welding dry film photoresist as well as a preparation method and use thereof.
A dry film photoresist generally comprises the following components: a polymer adhesive, a photo - polymerization monomer, a thermo-polymerization inhibitor and a free radical photo initiator. Developing a dry film with an aqueous solution is because the polymer adhesive is a carboxyl - containing polymer adhesive that can form a film, which can be sold as a dry film coil.
The components are clamped between a flexible support film and a cover film.
Polymerizable components are transported in a form of dry film, and often affected by cold flow, that is to say, the components flow under the action of pressure, namely, a resist can generate local flow to cause uneven thickness. In such the way, the component materials on the edge of the coil are fused together to produce flow glue. The occurring of glue flow is related to the viscosity of the photo - polymerization components. To prevent or reduce the components on the edge from being fused together to produce flow glue, it is conducive to properly increasing the viscosity of the photo - polymerization components.
The dry film photoresist is a polymerizable component, which is used for production of printed circuit boards. Also, it has another advisable advantage of good flexibility. In the polymerization state, the better the flexibility of the film, the less likely the printed board cracks or detaches from the printed board when being bent or slitted.
In addition, the dry film photoresist for resistance welding has welding protection, insulation, corrosion prevention, oxidation resistance, certain pencil hardness, electrical property and others, except for the parts and advantages included above.
At present, regardless of a resistance welding ink or a resistance welding dry film, their functions focus on welding protection, insulation, corrosion prevention and oxidation resistance, but they have poor adhesive force and resolution capability, etc. Therefore, there is currently almost no anti - soldering flux for ultra - high resolution of fine circuits.
In order to solve the above technical problems, the present disclosure provides a resistance welding dry film photoresist with a multilayer structure. The dry film photoresist has a three - layer structure including a photoresist layer 1, a photoresist layer 2 and a photoresist layer 3 respectively, wherein the upper photoresist layer comprises an epoxy acrylate base resin, a photocurable monomer, a thermocuring catalyst and a free radical initiator; the photoresist layer 2 comprises a mixture of photocurable and thermocuring resins, a photo - polymerization monomer having at least two photocurable unsaturated functional groups, a photo initiator, a thermocuring catalyst, dye or pigment; and the lower photoresist layer comprises a carboxyl - containing polymer adhesive, a photo - polymerization monomer, a thermo-polymerization inhibitor and a free radical photo initiator.
The photoresist layer 1 has a thickness of 5 - 15 um, the photoresist layer 2 has a thickness of 10 - 50 um, and the photoresist layer 3 has a thickness of 5 - 15 um. Meanwhile, a polythene (PE) film is arranged outside the photoresist layer 1 and has a thickness of 10 - 50 um, a polyethylene terephthalate (PET) film is arranged outside the photoresist layer 3 and has a thickness of 10 - 30 um. The specific structure is as shown in FIG.1. The main functions of the
PE and PET films are to protect and bear the photoresist layers.
In the photoresist layers with multilayer structures provided by the present disclosure, from bottom to top, the solid acid values of the acrylate base resins are gradually increased, namely, the solid acid value of the photoresist layer 1 > the solid acid value of the photoresist layer 2 > the solid acid value of the photoresist layer 3. When the photoresist layer with the multilayer structure is attached to a base material, the PE film must be tore, and then the photoresist layer 1 contacts with the base material to be pressed. The specific structure is as shown in FIG.2.
Therefore, the photoresist layer 1 is the bottom layer of the dry film photoresist when being applied. Accordingly, a higher acid value is needed to ensure the efficiency and resolution of development.
Meanwhile, to ensure that the deep photocuring effect of the bottom, the photoresist layer 3 is mainly designed to be transparent and highly glossy, and its light crosslinking degree is slightly lower than the light crosslinking degrees of other photoresist layers. This is to allow light to more easily penetrate into the bottom so that the bottom is better cured, thereby facilitating the promotion of adhesion. The photoresist layer 2 is a main anti-welding layer which is mainly designed to have bright colour, electrical performance, anti-welding property and the like. The photoresist layer 1 mainly takes the effects of improving the bonding force and resolution ability between the anti-welding layer and the surface of the base material.
The multifunctional photo - polymerization monomers (containing two or more vinyl double bonds) can improve the crosslinking density and strength in a cured film, etc. Common multifunctional monomers include: trimethylolpropane triacrylate (TMPTA), dipenta-erythritol penta-acrylate (DPPA), trimethylolpropane tetra-acrylate (DTMPTA), hexafunctional polyester acrylate (PEA), tetrafunctional polyester acrylate (PEA) and triethylene glycol diacrylate (TEGDA).
The free radical photo initiators are traditional photo initiators which generate free radicals excited by photochemical radiation and are stable to heat below 185°C. The photo initiators include one or more of the following compounds: benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, a-aminoacetophenone compounds, acyl phosphine oxides, oxime ester compounds, bisimidazole compounds, and triazine compounds.
The thermocuring catalysts include one or more of the following compounds: imidazole derivatives, amine compounds, hydrazine compounds and phosphine compounds.
The carboxyl - containing polymer adhesive that can form a film is obtained by synthesizing one or more vinyl monomers and one or more 0,8 - vinyl unsaturated carboxyl - containing monomers with 3 - 15 carbon atoms. The resulting adhesive is water - soluble. Examples of vinyl monomers are alkanes, hydroxyalkyl acrylate and methacrylate which contain 3 - 15 carbon atoms, as well as styrene and alkyl substituted styrene. Acrylate and methacrylate are preferred. Examples of carboxyl - containing monomers are phenylacrylic acid, butenoic acid, fumaric acid, sorbic acid, acrylic acid, methacrylic acid, itaconic acid, propargylic acid, maleic acid and their anhydrides. Among them, acrylic acid and methacrylic acid are preferred.
The thermocuring resins having the thermocurable functional groups comprise one or more amino compounds selected from a urea - formaldehyde resin, a melamine - formaldehyde resin, an alkyl melamine-formaldehyde resin and a co - polycondensation resin
The thermo-polymerization inhibitor matched with the present disclosure is intended to prevent the thermo-polymerization of the photoresist during the drying and storage. The thermo- polymerization inhibitors include p-methoxyphenol, hydrobenzoquinone, alkyl and aryl substituted hydrobenzoquinones and benzoquinones, tert-butyl catechol, pyrogallol, copper resinate, B-naphthol, 2,6-di-tert-butyl-p-cresol, 2,2’-methylene-bis(4-ethyl-6-tert-butylphenol), p - toluene benzoquinone, Tetrachlorobenzoquinone, aryl phosphite and alkyl aryl phosphite.
The photoresist also comprises some optional additives in the photo - polymerization components, such as leuco dye, background dye, adhesion promoters and antioxidants, all of which are mentioned in public information but are not necessary to the present disclosure.
The basic photo - polymerization component is formed by mixing a series of different compounds with solvents and evenly stirring. The used solvents generally include alcohols, ketones, halogenated hydrocarbons, ethers, etc. After evenly mixing, the photo - polymerization component is coated onto a layer of flexible carrier film and the solvent is evaporated, and then the next layer of photo - polymerization component is coated until the coating of the multilayer dry film photoresist is completed, and then a protective film is covered.
In the present disclosure, the photo - polymerization component, as a photoresist, is used in production of printed circuit boards. Generally speaking, the component is pressed onto the copper layer surface of a copper foil substrate, an invisible image is formed through exposure of a negative film under the irradiation of UV, and then developed in a known aqueous developer so as to remove the component that is not polymerized from the copper surface, thereby forming a bare copper surface. These thin copper layers can be processed by known means,
such as electroplating or etching procedure, while the polymerized material protects the copper layer it covers at this moment.
For the photo - polymerization component in the present disclosure, its cover film is removed by adopting a known method, such as a hot plate or hot cylinder laminating machine, then the dry film together with the carrier is hot pressed onto the cooper foil substrate, and the carrier film is removed during the development after exposure polymerization. Generally speaking, the amount of light used for the polymerization of the component is about 35 - 150 mj/cm?. The precise amount of light depends on the specific component and other factors such as types of exposure negative films.
The copper foil substrate is any known copper/insulation laminate used for production of circuit boards, such as copper foil laminate made of ethylene oxide resins enhanced by glass fibres.
The aqueous solution developer used in the present disclosure is an alkaline reagent having a concentration of 0.5wt% - 10wt%, preferably 0.5 wt% - 1wt%. The unpolymerized component in the above invisible image takes enough time to be washed away in the developer.
The used alkaline agents are alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and alkali metal salts that react with weak acids, such as sodium carbonate, sodium bicarbonate, alkali metal phosphate and pyrophosphate, wherein sodium carbonate is preferred.
Compared with the prior art, the present disclosure has the beneficial effects:
The resistance welding dry film photoresist provided by the present disclosure can combine the resistance welding dry film with the high - resolution dry film photoresist to form the dry film with various good performances.
FIG.1 is a structural diagram of a resistance welding dry film photoresist according to the present disclosure.
FIG.2 is a structural diagram of a resistance welding dry film photoresist after being pressed with a base material according to the present disclosure.
Example 1
A method for preparing a resistance welding dry film photoresist comprises the following steps: (1) All of photo - polymerization components were added into a blending device based on formulas of 3A and 3B according to Table 1, and evenly stirred at room temperature (below 25°C) under a mechanical stirring speed of 1000 rpm to form a coating liquid.
The coating liquid was evenly coated onto a polyester film (PET), and then baked in an oven at 110°C for 5 min so that the solvent was volatilized, so as to prepare a photoresist layer 3.
Table 1 Formula of coating liquid of photoresist layer 3
Percentages of
Names of compounds 2,6 - di - tert - butyl - 4 - methylphenol 0.01 0.01 on 4,4’ - bis(N,N - dimethylamino) - benzophenone (Michler's 0.2 0.2 es
Trimethylolpropane triacrylate 10 10 oe ae (plasticizer) 5 (2) All of photo - polymerization components were added into the blending device based on formulas of 2A and 2B according to Table 2, and evenly stirred at room temperature (below 25°C) under the mechanical stirring speed of 1000 rpm to form a coating liquid.
The coating liquid was evenly coated onto the photoresist layer 3, and then baked in an oven at 110°C for 5 min so that the solvent was volatilized.
Table 2 Formula of coating liquid of photoresist layer 2
Pa ee eee | Tw
DPHA is dipentaerythritol pentaacrylate (3) All of photo - polymerization components were added into the blending device based on formulas of 1A and 1B according to Table 3, and evenly stirred at room temperature (below 25°C) under the mechanical stirring speed of 1000 rpm to form a coating liquid.
The coating liquid was evenly coated onto the photoresist layer 2, and then baked in an oven at 110°C for 5 min so that the solvent was volatilized, and a layer of protective film
PE was covered so that the coating thickness of the photoresist was controlled within the range of 20 - 80 um.
Table 3 Formula of coating liquid of photoresist layer 1
Teena EE ese |E
Examples 2 -8
Methods for preparing the resistance welding dry film photoresist in examples 2 - 8 are the same as that in example 1, and specific components are seen in Table 4, wherein 1A and 1B are the same as those in Table 2; 2A and 2B are the same as those in Table 2; and 3A and 3B are the same as those in Table 1.
Table 4
Formula of Formula of Formula of
Claims (10)
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NL2032627A NL2032627B1 (en) | 2022-07-28 | 2022-07-28 | Resistance welding dry film photoresist as well as preparation method use thereof |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4660826B2 (en) * | 2006-08-18 | 2011-03-30 | 山栄化学株式会社 | Method for forming resist pattern |
US9497856B2 (en) * | 2012-03-30 | 2016-11-15 | Taiyo Ink Mfg. Co., Ltd. | Laminated structure, dry film and method of producing laminated structure |
CN108227379A (en) * | 2017-12-11 | 2018-06-29 | 珠海市能动科技光学产业有限公司 | A kind of dry film photoresist containing cellulosic material |
US10368438B2 (en) * | 2016-04-14 | 2019-07-30 | Ibiden Co., Ltd. | Printed wiring board and method for manufacturing the same |
CN112034685B (en) * | 2020-09-01 | 2022-03-18 | 珠海市能动科技光学产业有限公司 | High-resolution dry film photoresist |
CN114545734A (en) * | 2022-03-09 | 2022-05-27 | 珠海市能动科技光学产业有限公司 | Solder-resisting dry film photoresist, preparation method and application thereof |
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2022
- 2022-07-28 NL NL2032627A patent/NL2032627B1/en active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4660826B2 (en) * | 2006-08-18 | 2011-03-30 | 山栄化学株式会社 | Method for forming resist pattern |
US9497856B2 (en) * | 2012-03-30 | 2016-11-15 | Taiyo Ink Mfg. Co., Ltd. | Laminated structure, dry film and method of producing laminated structure |
US10368438B2 (en) * | 2016-04-14 | 2019-07-30 | Ibiden Co., Ltd. | Printed wiring board and method for manufacturing the same |
CN108227379A (en) * | 2017-12-11 | 2018-06-29 | 珠海市能动科技光学产业有限公司 | A kind of dry film photoresist containing cellulosic material |
CN112034685B (en) * | 2020-09-01 | 2022-03-18 | 珠海市能动科技光学产业有限公司 | High-resolution dry film photoresist |
CN114545734A (en) * | 2022-03-09 | 2022-05-27 | 珠海市能动科技光学产业有限公司 | Solder-resisting dry film photoresist, preparation method and application thereof |
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