CN114230709A - Organic silicon modified resin and application thereof - Google Patents
Organic silicon modified resin and application thereof Download PDFInfo
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- CN114230709A CN114230709A CN202111453181.XA CN202111453181A CN114230709A CN 114230709 A CN114230709 A CN 114230709A CN 202111453181 A CN202111453181 A CN 202111453181A CN 114230709 A CN114230709 A CN 114230709A
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- dry film
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- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
- G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
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- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The invention discloses an organic silicon modified resin and application thereof, belonging to the technical field of photoresist. The dry film photoresist prepared from the organic silicon modified resin contains 30-70 parts by weight of modified high-molecular adhesive (A) containing organic silicon, 20-60 parts by weight of vinyl acrylate photocuring monomer (B), 2-6.0 parts by weight of bisimidazole macromolecular free radical initiator or acridine initiator (C) and 0.01-1 part by weight of metal complexing agent (D).
Description
Technical Field
The invention belongs to the technical field of photoresist, and particularly relates to organic silicon modified resin and application thereof.
Background
In general, the components of the dry film photoresist include a thermoplastic polymer formed from an acrylic or methacrylic monomer, a photopolymerizable monomer, a thermal polymerization inhibitor, a radical photoinitiator, and an ultraviolet absorber. They are usually sold as dry film rolls, the composition being sandwiched between a flexible support film PET and a cover film PE.
With the popularization of 5G and the development of smart phones and household appliances, the circuit density and the fineness of circuit boards of 5G related equipment have higher requirements, the resolution capability in the traditional dry film photoresist can reach 30 micrometers at most, and the thinner the dry film thickness is, the stronger the resolution and the adhesion capability are. However, in practical applications, the thickness uniformity is worse when the dry film is thinner, and therefore, the analysis and adhesion capability of the dry film are more required under the condition that the thickness of the dry film photoresist layer is not changed. The dry film photoresist provided by the invention can further improve the resolving and attaching capabilities of the dry film photoresist under the same thickness.
Disclosure of Invention
The invention aims to provide a modified high-molecular adhesive containing organic silicon, wherein the solid acid value of the adhesive is 70-210, the weight-average molecular weight is 20-150K, and the content of the introduced organic silicon is 5-15%.
Preferably, the silicone-containing modified polymeric binders are of the formula:
wherein, the value ranges of m, n, x, y and z are respectively 0-925, 0-1745, 0-1055, 0-948 and 0-1500.
The second objective of the present invention is to provide a dry film photoresist, which comprises the following components:
the component A is the organic silicon-containing polymer adhesive;
the component B is a vinyl acrylate light-cured monomer;
the component C is a free radical photoinitiator;
preferably, the dry film photoresist further comprises a component D heavy metal complex tetrahydroxypropylethylenediamine.
Wherein the weight portions of the component A, the component B, the component C and the component D are respectively 30-70, 20-60, 2-6 and 0.01-1.
Preferably, the dry film photoresist further comprises an ultraviolet inhibitor, a polymerization inhibitor, an adhesion promoter, a dye and an antioxidant.
The vinyl acrylate photopolymerization monomer (containing one or more vinyl double bonds) can improve the crosslinking density and strength and other properties of the cured film. Commonly used vinyl acrylate based photopolymerizable monomers include: ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ditrimethylolpropane tetraacrylate (DTMPTA), hexafunctional polyester acrylate (PEA), tetrafunctional polyester acrylate (PEA), triethylene glycol diacrylate (TEGDA), 4 (ethoxy) nonylphenol acrylate (NP (EO)4A), 8 (ethoxy) nonylphenol acrylate (NP (EO)8A), and the like.
The above-mentioned radical photoinitiators are conventional photoinitiators, which generate radicals upon excitation by actinic radiation, and which are stable to heat below 185 ℃. Common photoinitiators are bisimidazoles, aromatic ketones, such as Benzophenone (BP) and dimethoxyphenylacetophenone.
The modified silicone-containing polymeric binder is synthesized from one or more vinylic monomers and one or more α, β -vinylic unsaturated carboxyl-containing monomers having from 3 to 15 carbon atoms, the resulting binder being water-soluble. Examples of useful vinylic monomers are alkanes and hydroxyalkyl acrylates and methacrylates having 3 to 15 carbon atoms, styrene and alkyl-substituted styrenes. Acrylates and methacrylates are preferred. Examples of useful carboxyl group-containing monomers are cinnamic acid, crotonic acid, fumaric acid, sorbic acid, acrylic acid, methacrylic acid, itaconic acid, propiolic acid, maleic acid, and anhydrides thereof. Among them, acrylic acid and methacrylic acid are preferred. The organic silicon is introduced into the high molecular adhesive, the silicon is insensitive to developing solution and temperature, the swelling is reduced in development, the speed is increased, the thermal deformation can be reduced in baking, the corrosion resistance of the dry film photoresist is improved, and the resolution is improved.
The thermal polymerization inhibitor used in the present invention is used to prevent thermal polymerization of the resist during drying and storage. Examples of useful thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, alkyl and aryl substituted hydroquinones and quinones, t-butyl catechol, pyrogallol, cuprate, β -naphthol, 2, 6-di-t-butyl-p-cresol, 2, 2' -methylene-bis (4-ethyl-6-t-butylphenol), p-toluquinone, tetrachlorobenzoquinone, aryl phosphites, and alkylaryl phosphites.
The photoresist may also optionally contain additives to the photopolymerizable components such as: leuco dye, ground dye, adhesion promoter, antioxidant, etc. These are mentioned in the disclosure, but are not necessarily essential to the invention.
The basic photopolymerizable component is prepared by mixing a series of different compounds with a solvent and stirring the mixture uniformly. The solvents used generally include: alcohols, ketones, halogenated hydrocarbons, ethers, and the like. After mixing, the photopolymerizable composition is applied to a flexible carrier film and the solvent is evaporated, and a protective film is applied, preferably to a photoresist thickness of 10 to 80 μm and preferably to a carrier film thickness of 0.0254 to 0.0508mm, as described in the publication.
The dry film of the present invention may be placed on a flexible or non-flexible support or may be formed into a laminate or roll.
The dry film photoresist of the present invention is used in the production of printed circuit boards, generally speaking, the dry film photoresist is heated and pressed to adhere to the surface of the copper layer of a copper foil substrate, a latent image is formed by exposure through a negative film under the irradiation of ultraviolet light, then the dry film photoresist is developed in a known aqueous solution developing solution to remove unpolymerized components from the copper surface to form a bare copper surface, the copper thin layers can be processed by known means, such as electroplating or etching procedures, the polymerized substances now protect the copper layer covered by the polymerized substances, and finally the polymerized substances can be stripped by a known stripping solution.
The photopolymerizable composition of the invention is thermally pressed onto the copper foil substrate by a known method such as a hot plate or a hot barrel laminator together with the carrier film after the cover film is removed, and the carrier film is removed at the time of development after exposure polymerization. Generally, the amount of light used for polymerization of the component is about 20 to 120mj/cm2The precise amount of light depends on the particular composition and the type of film being exposed, among other factors.
The copper foil base is any known copper/insulation laminate used in the production of circuit boards, such as a glass fiber reinforced ethylene oxide resin copper foil laminate.
The aqueous developer used in the present invention is an alkaline agent having a concentration of 0.5 to 10% by weight, preferably 0.5 to 2.0% by weight. The unpolymerized constituents are washed away in the developer for a sufficient time. The alkaline agent used is an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and an alkali metal salt reactive with a weak acid such as sodium carbonate, sodium bicarbonate, and alkali metal phosphates and pyrophosphates, among which sodium carbonate is preferred, and the wiring board may be immersed in a developer or the developer may be sprayed onto the wiring substrate.
In general, stripping solutions adapted according to the invention for stripping off polymerized component species are heated aqueous alkaline solutions, such as aqueous alkaline solutions having a higher concentration of the same developing solution, generally in the range of from 1 to 10%, preferably from 2 to 4%, and generally at a temperature of from about 45 to 68 ℃ and preferably in the range of from 50 to 55 ℃, such as by spraying the substrate with the heated stripping solution, or preferably by agitating the substrate in the heated stripping solution.
The techniques and equipment for exposure, including light source, light intensity and exposure time, developing and stripping solutions and techniques and laminate components are all mentioned in the disclosure.
The invention also aims to provide the application of the modified high-molecular adhesive containing the organic silicon in the field of dry film photoresist.
Compared with the prior art, the invention has the following beneficial effects:
the dry film photoresist prepared by the invention has better resolution.
Drawings
FIG. 1 is a diagram showing a process for synthesizing a silicone-containing modified polymer adhesive in example 1.
Detailed Description
Example 1
The synthesis process of the modified high molecular adhesive containing the organic silicon is shown in figure 1, and the specific synthesis process is as follows:
(1) 100ml of butanone with the water content of 252.1ppm is taken to be put into a reaction bottle and heated to 80 ℃ for standby;
(2) dissolving 0.7g of azobisisobutyronitrile in 77.3ml of butanone, and stirring until the azodiisobutyronitrile is completely dissolved for later use;
(3) 40.5g of methacrylic acid, 119g of methyl methacrylate, 31g of butyl methacrylate, 20g of phenyl methacrylate, 21g of methacrylic acid, 20g of trimethylsilyl methacrylate and the initiator solution of step (2) were added dropwise to the preheated butanone of step (1) and reacted at a constant temperature of 80 ℃ for 5 hours.
(4) After the reaction is finished, cooling to room temperature, and filtering to obtain the modified high-molecular adhesive containing the organic silicon;
(5) modified silicone-containing polymeric binder: the acid value was 115.1, the weight average molecular weight was 81311, and the silicone content was 8.6%.
Example 2
A dry film photoresist was prepared using the modified polymer binder of example 1, the procedure was as follows:
(1) adding the materials in the dry film photoresist formula into a modified high-molecular adhesive containing organic silicon, stirring and dispersing uniformly to prepare a liquid dry film photoresist;
(2) coating a liquid dry film photoresist on a PET film by using a coating instrument, drying at 100 ℃, attaching a PE protective film, and processing the dry film photoresist;
(3) tearing off the dry film photoresist protective layer PE, and sticking the dry film photoresist on the processed copper plate through a hot roller;
(4) exposing and developing the copper plate pasted with the dry film photoresist, and reading analytic data and adhesion capacity data;
examples 3 to 7
Examples 3-7 dry film photoresists were prepared as in example 2, except that different specific components were used, as shown in table 1.
TABLE 1
Note: 1. the control is the company existing system.
2. Acrylate adhesive a: is prepared from methyl acrylate (70%), methacrylic acid (18%), organosilicon-contained methyl acrylate (12%) and methyl ethyl ketone through polymerizing.
C1 is a product of a bisimidazole macromolecular photoinitiator BCIM, Changzhou powerful new electronic material Co.
C2 is acridine photoinitiator PAD-201, a commodity of Changzhou powerful new electronic material GmbH.
B1 is ethoxylated bisphenol A methacrylate.
B2 is ethoxy and propoxy co-modified polyurethane.
B3 is ethoxy modified TMPTA.
D is commercial EDTP (tetrahydroxypropylethylenediamine) having the formula:
adhesion test
The dry films prepared in examples 2-7 were adhered to a copper plate as measured by the following pass/fail test: the copper plate is first cleaned in a suitable manner and the film is laminated to the surface of the copper plate. After 15min, the film covered on the film is torn off, and the adhesive tape is stuck on the surface of the film, so that the adhesive tape has better adhesion with the film. The adhesive tape is pulled hard to be quickly stripped from the film, and if the film and the adhesive tape are stripped from the copper surface together, the test fails; the test is passed if the film is still adhered to the copper side. This evaluation uses a 3M type scotch tape. The same test can be applied to the adhesion test of the cured part.
Resolution testing
After development, the resolution was determined using a microscope.
[ test analysis graph ]
Line width is line distance: 12.5, 15, 17.5, 20, 25, 30, 40, 50 um.
Line adhesion test
After development, the resolution was determined using a microscope.
[ test analysis graph ]
Line spacing of 400um
Line width: 12.5, 15, 17.5, 20, 25, 30, 40, 50 um.
TABLE 2
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. The modified polymer adhesive containing the organic silicon is characterized in that the solid acid value in the adhesive is 70-210, the weight average molecular weight is 20-150K, and the content of the introduced organic silicon is 5-15%.
2. The modified silicone-containing polymeric binder of claim 1, wherein the modified silicone-containing polymeric binder has the formula:
wherein, the value ranges of m, n, x, y and z are respectively 0-925, 0-1745, 0-1055, 0-948 and 0-1500.
3. The modified silicone-containing polymeric binder of claim 2, wherein the modified silicone-containing polymeric binder is synthesized by:
(1) heating the organic solvent containing quantitative moisture to 50-100 ℃ to obtain a preheated organic solvent containing quantitative moisture;
(2) dissolving an initiator in the organic solvent with the same water content in the synchronous step (1), and stirring until the initiator is completely dissolved for later use;
(3) dropwise adding the monomer and the initiator solvent dissolved in the step (2) into the preheated organic solvent containing quantitative water in the step (1) at regular time, and reacting for 2-10 hours at constant temperature;
(4) after the reaction is finished, cooling to room temperature, and filtering to obtain the modified high molecular adhesive containing the organic silicon.
4. A dry film photoresist, comprising the following components:
component A is the silicone-containing polymeric binder of claim 1;
the component B is a vinyl acrylate light-cured monomer;
and the component C is a free radical photoinitiator.
5. The dry film photoresist of claim 4, further comprising component D heavy metal complex tetrahydroxypropylethylenediamine.
6. The dry film photoresist of claim 5, wherein the weight parts of component A, component B, component C, and component D in the dry film photoresist are 30-70, 20-60, 2-6, and 0.01-1, respectively.
7. The dry film photoresist of any one of claims 4 to 6, wherein the vinyl acrylate based photocurable monomer is at least one of ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ditrimethylolpropane tetraacrylate (DTMPTA), hexafunctional polyester acrylate (PEA), tetrafunctional polyester acrylate (PEA), triethylene glycol diacrylate (TEGDA), 4 (ethoxy) nonylphenol acrylate (NP (EO)4A), 8 (ethoxy) nonylphenol acrylate (NP (EO) 8A).
8. The dry film photoresist according to claim 7, wherein the radical photoinitiator is a bisimidazole-based macro-radical initiator or an acridine-based initiator.
9. The dry film photoresist according to claim 5 or 6, wherein the dry film photoresist is prepared by the following process:
(1) adding the materials in the dry film photoresist formula into a modified high-molecular adhesive containing organic silicon, stirring and dispersing uniformly to prepare a liquid dry film photoresist;
(2) coating a liquid dry film photoresist on a PET film by using a coating instrument, drying at 100 ℃, attaching a PE protective film, and processing the dry film photoresist;
(3) tearing off the dry film photoresist protective layer PE, and sticking the dry film photoresist on the processed copper plate through a hot roller;
(4) and exposing and developing the copper plate pasted with the dry film photoresist, and reading analytic data and adhesion capacity data.
10. Use of the modified silicone-containing polymeric binder of claim 1 in the field of dry film photoresists.
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| CN202111453181.XA CN114230709A (en) | 2021-12-01 | 2021-12-01 | Organic silicon modified resin and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111453181.XA CN114230709A (en) | 2021-12-01 | 2021-12-01 | Organic silicon modified resin and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004325596A (en) * | 2003-04-22 | 2004-11-18 | Fuji Photo Film Co Ltd | Dry film photoresist |
| CN1818781A (en) * | 2006-03-13 | 2006-08-16 | 苏州华飞微电子材料有限公司 | Dark ultraviolet negative photoresist and filming resin |
| CN102050908A (en) * | 2010-11-22 | 2011-05-11 | 昆山西迪光电材料有限公司 | Chemical amplitude-increasing type silicon-containing I-line ultraviolet negative photoresist and forming resin thereof |
| CN112159639A (en) * | 2020-11-09 | 2021-01-01 | 珠海市能动科技光学产业有限公司 | Modified high-molecular adhesive and dry film photoresist containing same |
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- 2021-12-01 CN CN202111453181.XA patent/CN114230709A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004325596A (en) * | 2003-04-22 | 2004-11-18 | Fuji Photo Film Co Ltd | Dry film photoresist |
| CN1818781A (en) * | 2006-03-13 | 2006-08-16 | 苏州华飞微电子材料有限公司 | Dark ultraviolet negative photoresist and filming resin |
| CN102050908A (en) * | 2010-11-22 | 2011-05-11 | 昆山西迪光电材料有限公司 | Chemical amplitude-increasing type silicon-containing I-line ultraviolet negative photoresist and forming resin thereof |
| CN112159639A (en) * | 2020-11-09 | 2021-01-01 | 珠海市能动科技光学产业有限公司 | Modified high-molecular adhesive and dry film photoresist containing same |
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