CN113512720A - Copper precipitation pretreatment liquid and pretreatment method thereof - Google Patents
Copper precipitation pretreatment liquid and pretreatment method thereof Download PDFInfo
- Publication number
- CN113512720A CN113512720A CN202110760475.0A CN202110760475A CN113512720A CN 113512720 A CN113512720 A CN 113512720A CN 202110760475 A CN202110760475 A CN 202110760475A CN 113512720 A CN113512720 A CN 113512720A
- Authority
- CN
- China
- Prior art keywords
- copper
- pretreatment liquid
- substrate
- copper precipitation
- cationic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
Abstract
The invention relates to the field of chemical plating on a non-conductive substrate plate, in particular to a copper deposition pretreatment liquid and a pretreatment method thereof. The copper precipitation pretreatment liquid comprises 0.01-100g/L of cationic polymer; the polymer comprises a polymer which is polymerized and quaternized with heterocyclic nitrogen-containing compounds and cations, wherein the heterocyclic nitrogen-containing compounds comprise at least one of epoxy groups, alkenyl groups, active hydrogen and benzene rings. After the copper deposition pretreatment liquid is used, the growth state of copper in holes is good, copper nodules are not generated, the quality of a plating layer is high, the adhesion performance between the plating layer and a resin substrate is excellent, and meanwhile, the backlight grade reaches more than 9 grades, even 10 grades.
Description
Technical Field
The invention relates to the field of electroless plating on non-conductive substrate boards, in particular to C23C 22/78.
Background
CN200510008522 adjusts the concentration of a surface finishing agent by bentonite subjected to surface treatment by using alkyl trialkoxysilane, so that the dispersion stability of the surface finishing agent is excellent, however, the adhesion between a substrate and a plating layer treated by the surface finishing agent is weak, the adhesion is influenced by various components in a copper deposition process, and the copper plating quality is limited by a substrate material; meanwhile, the backlight effect of the plated part obtained by the existing horizontal copper deposition process is poor due to the use of a concentrated activating agent, the cost burden is increased, and the copper deposition rate in the chemical copper deposition process is unstable and difficult to keep balance. CN201811619234 adopts purified water, a phosphopeptide mixture, phosphate, polyoxyethylene ether, an alkaline reagent and a surfactant to provide a liquid surface conditioning agent which is good in storage stability and promotes the formation of a phosphating film coating, but the obtained coating has a poor backlight effect.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a copper precipitation pretreatment liquid in a first aspect, wherein the copper precipitation pretreatment liquid comprises 0.01-100g/L cationic polymer.
In one embodiment, the copper precipitation solution further comprises 1-20g/L of a regulator.
Preferably, the copper precipitation pretreatment liquid comprises 0.1-30g/L of cationic polymer and 10g/L of regulator.
The solvent of the copper deposition solution is deionized water.
In one embodiment, the modifier is one or more of an organic acid, an inorganic acid, and an alkali metal hydroxide.
The organic acid is a monocarboxylic acid, a dicarboxylic acid or a polycarboxylic acid.
Examples of the organic acid include oxalic acid, lactic acid, tartaric acid, malic acid, ascorbic acid (i.e., vitamin c), quinic acid, succinic acid, and the like.
Examples of the inorganic acid include phosphoric acid, boric acid, and sulfuric acid.
In one embodiment, the cationic polymer comprises a polymer formed by polymerizing and quaternizing at least one of an epoxy group, an alkenyl group, an active hydrogen, and a benzene ring with a heterocyclic nitrogen-containing compound.
In one embodiment, the cationic polymer has a degree of polymerization of 1 to 100.
The olefin to be used in the present application is not particularly limited and may be conventionally selected by those skilled in the art.
In one embodiment, the olefin is ethylene and/or propylene.
The cationic polymers described herein may be obtained commercially or prepared by techniques known in the art.
Alkenyl is an alkenyl group, also known as alkenyl. Can be regarded as a hydrocarbon group in which one or more hydrogen atoms are absent from the olefin molecule. For example vinyl CH2CH-. Chloroethylene CH2＝CHCl2Styrene C6H5CH＝CH2And the molecules contain vinyl groups.
In one embodiment, the active hydrogen includes, but is not limited to, carboxyl, hydroxyl, amino, and the like.
In the field of electroless copper plating, various sulfur-containing flattening agents, brightening agents and the like are added into a plating solution to improve the glass strength between a plating layer and a substrate in the prior art, however, the method is greatly influenced by the preliminary treatment of copper plating, if the preliminary treatment is insufficient, the plating layer is easy to be unstable, and the difference between batches and within the batches is large, the applicant has surprisingly found that when the preliminary treatment solution for copper precipitation comprises (a) a polymer polymerized by a non-heterocyclic nitrogen-containing compound containing at least one of alkenyl, active hydrogen and a benzene ring and/or (b) a polymer polymerized by a heterocyclic nitrogen-containing compound, and the polymerization degree of a cationic polymer is 1-100, the peeling strength is more than 600N/m, the applicant considers that the possible reason is that the cationic polymer with the polymerization degree of 1-100 in the application can effectively act on the surface of the substrate, especially, on the undercut anchor point obtained in the substrate after the preliminary treatment, the permeability of the hole wall is enhanced, the subsequent complexing coordination capacity of the base on palladium ions is improved, and the bonding strength of the plating layer is improved.
In one embodiment, the acyclic or non-heterocyclic nitrogen-containing compound containing at least one alkenyl group, active hydrogen, or benzene ring is selected from methacrylamide
N, N-dimethylallylamine
Diallylamine
D-allylglycine
4-vinylbenzylamine
Triallylamine
3- (dimethylamino) acrylic acid ethyl ester
Oleic acid amide, tert-butyloxycarbonylsarcosine
Phenylhydrazine
Para-aminophenol
Carboxanilides
N, N-dimethylaniline
P-aminobenzamide
Para aminobenzoic acid
One or more of them.
Preferably, the non-heterocyclic nitrogen-containing compound containing at least one of an alkenyl group, an active hydrogen, or a benzene ring is selected from one or more of N, N-dimethylallylamine, methacrylamide, 4-vinylbenzylamine, N-dimethylaniline, and p-aminobenzamide.
In one embodiment, the heterocyclic nitrogen-containing compound has the structure
Or
Wherein Q, W, K can be the same or different and are each independently selected from C, O, N, and at least one of Q, W, K is N; r4、R5、R6Each independently selected from any one of hydrogen, oxygen, and chemically acceptable substituent groups; x, Y, Z can be the same or different, each is independently selected from C, O, N, and at least one of X, Y, Z is N; r1、R2、R3Each independently selected from any one of hydrogen, oxygen, and chemically acceptable substituent groups.
Examples of the chemically acceptable substituent group in the present application include a carboxyl group, an aldehyde group, an alkoxy group, a cyano group, an amino group, a mercapto group, an amide group, an olefin group, a hydroxyl group, a substituted or unsubstituted phenyl group, a cycloalkyl group, and a hydroxyl group.
In one embodiment, the unpolymerized and quaternized monomer of formula (2) is selected from the group consisting of 1-vinylimidazole
1-acetyl imidazole
Poly (1-propylimidazole)
1H-imidazole-4-carboxylic acid
3-hydroxymethyl isoxazoles, 2-phenylimidazolines
5-amino-2-benzimidazolones
Antazoline
1-acetyl-2-imidazolidinones
1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene
Alatin 1-hexyl-3-methylimidazolium chloride salt
2, 6-bis (2-benzimidazolyl) pyridine, 4-imidazoleacrylic acid
Any of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin.
Preferably, the formula (2) is 1-hexyl-3-methylimidazolium chloride
Or 1H-imidazole-4-carboxylic acid
In one embodiment, the unpolymerized and quaternized monomer of formula (1) is selected from 2-hydrazinopyridines
2-pyridinecarboxylic acid
2-Pyridinemethanol
2-hydroxypyridines
4-acetylpyridine
4-Pyridinebutanol
4-aminopyridines
4-hydroxypyridines
Pyridine-4-carbaldehyde
Bis (2-pyridone) ketones
2-butyrylpyridine
2-pyridine carboxylic acid hydrazides
4,4' -Azopyridines
4-vinylpyridines
4-methylaminopyridines
Any of the above.
Preferably, the unpolymerized and quaternized monomers of formula (1) are selected from pyridine-4-carbaldehyde
4-aminopyridines
4-hydroxypyridines
4-methylaminopyridines
2-Pyridinemethanol
Any of the above.
The applicant found in experiments that when the conventional polyquaternium compound is used, the backlight grade is lower than 5 grades, even 0 grades after the roughness of a substrate is larger than 400nm, and unexpectedly found in experiments that when the cationic polymer in the copper precipitation pretreatment solution comprises a polymer formed by polymerizing and quaternizing at least one of a compound containing epoxy, alkenyl, active hydrogen and benzene ring and a heterocyclic nitrogen-containing compound, the polymerization degree of the cationic polymer is 1-100, and the structure of the heterocyclic nitrogen-containing compound is (formula 1) or (formula 2); wherein Q, W, K are each independently selected from any one of C, O, N, and at least one of Q, W, K is N; r4, R5 and R6 are selected from one or more of hydrogen, oxygen and chemically acceptable substituent groups; x, Y, Z are each independently selected from any of C, O, N, and X, Y, Z has at least one N; r1, R2 and R3 are selected from one or more of hydrogen, oxygen and chemically acceptable substituent groups.
The non-cyclic and non-heterocyclic nitrogen-containing compound containing at least one alkenyl, active hydrogen or benzene ring is selected from one or more of methacrylamide, N-dimethylallylamine, diallylamine, D-allylglycine, 4-vinylbenzylamine, triallylamine, ethyl 3- (dimethylamino) acrylate, oleamide, tert-butoxycarbonylsarcosine, phenylhydrazine, para-aminophenol, formanilide, N-dimethylaniline, para-aminobenzamide and para-aminobenzoic acid, when the roughness of the substrate is more than 400nm and even reaches 1000nm, the backlight grade after copper deposition is more than or equal to 9, and the applicant considers that the possible reason is that the conventional polyquaternary ammonium salt compounds can generate bubbles in holes during use, are easy to be adsorbed on the hole walls, and cause no copper plating in the holes, the cationic polymer formed by the specific structure in the application has stronger binding force to the substrate material with the roughness of 450-1000nm, can effectively and completely neutralize the negative charges in the hole wall, and simultaneously has a structure which does not cause the generation of bubbles when acting on the substrate material, thereby improving the backlight effect.
In one embodiment, the preparation method of the copper precipitation pretreatment liquid comprises the following steps: and mixing all the components of the copper precipitation pretreatment liquid to obtain the copper precipitation pretreatment liquid.
The second aspect of the present invention provides a pretreatment method, comprising the steps of:
(1) preparing a substrate;
(2) treating the substrate with the copper precipitation pretreatment liquid for 0.5-3 min.
In one embodiment, step (2) is preceded by the step of contacting the substrate with a leavening agent.
In one embodiment, the step (2) is preceded by a step of contacting the substrate with a strong oxidizing agent.
The step of contacting the substrate with the leavening agent and the step of contacting the substrate with the strong oxidizing agent in this application are not particularly limited and may be routinely selected by one of ordinary skill in the art.
The leavening agent and the strong oxidizing agent are not particularly limited in this application and may be conventionally selected by those skilled in the art.
In one embodiment, the substrate has a roughness of 450-1000 nm.
In one embodiment, the substrate has a roughness of 450-500nm or 900-1000 nm.
The roughness is measured by a roughness tester in this application.
The substrate in this application is a resin substrate.
The present substrate for copper plating comprises various inorganic and organic materials, wherein the organic material is thermosetting resin or thermoplastic resin, the resin is conventionally selected as the substrate material, after the treatment by the pretreatment liquid for copper deposition in the present application, the peel strength between the resin substrate and the plating layer is not satisfactory after the copper deposition, the applicant has unexpectedly found in experiments that when the roughness of the substrate is 450-1000nm, the peel strength is greater than 570N/m, especially the roughness is 450-500nm or 900-1000nm, the peel strength is further improved, the applicant considers that the possible reason is copper deposition in the substrate, the roughness makes the copper deposition rate relatively stable during the copper deposition, makes the copper particles finer, and the quality of the deposited copper is stable, so that the internal stress of the plating layer is reduced, and the peel strength is improved. In addition, the applicant unexpectedly finds that under the condition that the roughness of the cationic polymer and the roughness of the substrate are simultaneously satisfied, the generation of copper nodules in the holes can be avoided in the later copper deposition process, and the applicant considers that the possible reason is that under the substrate with specific roughness, the cationic polymer treats the substrate, the hole walls are in a better state, and in the copper deposition process, the bonding force of each undercut anchor of the hole walls to copper is the same or similar, so that the possibility of copper particle aggregation growth or dendritic crystal occurrence caused by the difference is avoided.
Compared with the prior art, the invention has the following beneficial effects:
(1) when the cationic polymer comprises a polymer formed by polymerizing and quaternizing at least one of an epoxy group, an alkenyl group, active hydrogen and a benzene ring and a heterocyclic nitrogen-containing compound, and the polymerization degree is 1-100, the viscosity strength between a copper layer and a substrate is enhanced after the treatment of the copper precipitation pretreatment liquid, and meanwhile, when the cationic polymer with a specific structure in the application is adopted, the backlight effect can be improved;
(2) when the substrate with the roughness of 450-1000nm in the substrate is adopted, the peeling strength between the coating and the substrate can be further improved;
(3) after the copper deposition pretreatment liquid is used, the growth state of copper in holes is good, copper nodules are not generated, and the quality of a plating layer is high.
Drawings
FIGS. 1 to 16 are the backlight effect diagrams of the copper deposition after the copper deposition pretreatment liquid treatment in examples 1 to 16, respectively.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Examples
Examples 1 to 16
Examples 1 to 16 of the present invention provide a copper deposition pretreatment liquid, the components of which are shown in the following table.
Wherein the resin substrate 1 represents roughness Ra: 590 + 630nm, available from Biotech, model S1000-M.
The resin substrate 2 represents roughness Ra: 480- "500 nm", available from Biotechnology under model number S1150G.
Resin matrix 3 represents an epoxy resin substrate, roughness Ra: 900 to 1000nm, available from Biotech, type S1141.
Nitrogen-containing non-quaternized compound a: 2-hydrazinopyridine (from Shanghai Michelin Biochemical technology Co., Ltd., cat # H831435, CAS # 4930-98-7)
Nitrogen-containing non-quaternized compound B: 4-imidazole acrylic acid (from Shanghai Michelin Biotechnology Ltd., cat # U833629, CAS # 104-98-3)
Cationic polymer C: copolymer containing six-membered heterocyclic ring of pyridine (available from Guangdong Shuichi Co., Ltd., type SCC-A03)
Cationic polymer D: imidazole-containing six-membered heterocycle copolymer (from Guangdong Shuichi Co., Ltd., type SCC-A03H)
Examples 1 to 16 include a cationic polymer or a cationic compound in an amount of 20ppm, and deionized water as a solvent, wherein examples 1 to 12 further include a 10g/L conditioning agent, and examples 13 to 16 further include a conditioning agent, and the pH of the copper deposition pretreatment solution is respectively 2.26, 3.26, 4.26, and 5.26 by controlling the content of the conditioning agent.
TABLE 1
The preparation method of the pretreatment liquid for copper precipitation in the embodiments 1 to 16 comprises the following steps: mixing the above materials.
Performance evaluation
1. Adhesion strength test:
1. the substrates of examples 1-16 were each treated with a leavening agent to expand at 80 ℃ for 6 minutes. The leavening agent is an aqueous solution containing 10 wt% propylene glycol ethyl ether and 35g/L sodium hydroxide. The leavening agent is available from Guangdong Shuichi Co., Ltd, and is SCC-A01H.
2. The resulting material was then rinsed in tap water at 25 ℃ for 1 minute at room temperature.
3. The treatment is carried out at 80 ℃ for 12 minutes using an aqueous solution containing 50 to 60g/L of a degelling agent, i.e. potassium permanganate with a pH of 12. The glue removing agent is selected from SCC-A02 of Guangdong Shuichi technologies, Inc.
4. The resulting material was rinsed in tap water at 25 ℃ for 1 minute at room temperature.
5. The neutralized solution was then used for 1 minute at 50 ℃. The neutralizer is from Guangdong Shuichi Kogyo Co., Ltd, and is in the type of SCC-A03H, the neutralizer solution is 100ml/L SCC-A03H, and 90ml sulfuric acid (50% sulfuric acid) is added to prepare the solution.
6. The resulting material was rinsed in tap water at 25 ℃ for 1 minute.
7. The substrates were treated at 50 ℃ for 1 minute using the copper deposition pretreatment liquids in the examples, respectively.
8. The conditioned substrate from step 7 was then rinsed in tap water at 25 ℃ for 1 minute at room temperature.
9. Immersing the substrate into a sodium persulfate solution to carry out soft etching for 60s at 25 ℃; the sodium persulfate solution is prepared from 80g/L of sodium persulfate and 4 wt% of sulfuric acid (98%);
10. immersing in a presoaking agent (from Guangdong Shuichi Co., Ltd., model SCC-A05LP/A05H) at 45 deg.C for 20 s;
11. the step 10 treated substrate was treated in an activator solution at 45 ℃ for 45 s. Wherein the activator solution is a pH buffer of sodium carbonate sufficient to provide a pH of 9, and wherein the activator is from Kagaku Kogyo, Guangdong, Inc. under the reference SCC-A06H.
12. The substrate was then soaked in tap water at 25 ℃ for 1 minute at room temperature.
13. Then treated with a reducing agent at 35 ℃ for 35s, the pH of the reducing agent being 9. + -. 0.5. The reducing agent is obtained from Guangdong Shuichi Co., Ltd, and has a model of SCC-A07H.
14. Then, the electroless copper plating is carried out for 30 minutes in a copper precipitation solution at the temperature of 33 ℃, wherein the copper precipitation solution is from Guangdong Shuichi technologies, Inc., and is of a model SCC-A08H.
The surface of the resulting plated material was washed with deionized water at room temperature for 3 minutes, and then heated and dried (180 ℃, 60 minutes). The resulting copper plating film had a film thickness of 20 to 25 μm and the plating film was cut into a width of 1cm, and the adhesion strength between the substrate and the plating film was measured at an angle of 90 ℃ at a tensile speed of 50 mm/min in accordance with printed circuit board test method JIS C5012 using INSTON-5564 tester.
2. Backlight grade
1. The substrates of examples 1-16 were each treated with a leavening agent to expand at 80 ℃ for 6 minutes. The leavening agent is an aqueous solution containing 10 wt% propylene glycol ethyl ether and 35g/L sodium hydroxide. The leavening agent is available from Guangdong Shuichi Co., Ltd, and is SCC-A01H.
2. The resulting material was then rinsed in tap water at 25 ℃ for 1 minute at room temperature.
3. The treatment is carried out at 80 ℃ for 12 minutes using an aqueous solution containing 50 to 60g/L of a degelling agent, i.e. potassium permanganate with a pH of 12. The glue removing agent is selected from SCC-A02 of Guangdong Shuichi technologies, Inc.
4. The resulting material was rinsed in tap water at 25 ℃ for 1 minute at room temperature.
5. The neutralized solution was then used for 1 minute at 50 ℃. The neutralizer is from Guangdong Shuichi Co., Ltd, and has a model of SCC-A03H; the neutralizer solution was prepared from 100ml/L SCC-A03H, plus 90ml sulfuric acid (50 wt% sulfuric acid).
6. The resulting material was rinsed in tap water at 25 ℃ for 1 minute.
7. The substrates were treated at 50 ℃ for 1 minute using the copper deposition pretreatment liquids in the examples, respectively.
8. The conditioned substrate from step 7 was then rinsed in tap water at 25 ℃ for 1 minute at room temperature.
9. Immersing the substrate into a sodium persulfate solution to carry out soft etching for 60s at 25 ℃; the sodium persulfate solution is prepared from 80g/L of sodium persulfate and 4 wt% of sulfuric acid (98%);
10. immersing in a presoaking agent (from Guangdong Shuichi Co., Ltd., model SCC-A05LP/A05H) at 45 deg.C for 20 s;
11. the step 10 treated substrate was treated in an activator solution at 45 ℃ for 45 s. Wherein the activator solution is a pH buffer of sodium carbonate sufficient to provide a pH of 9, and wherein the activator is from Kagaku Kogyo, Guangdong, Inc. under the reference SCC-A06H.
12. The substrate was then soaked in tap water at 25 ℃ for 1 minute at room temperature.
13. Then treated with a reducing agent at 35 ℃ for 35s, the pH of the reducing agent being 9. + -. 0.5. The reducing agent is obtained from Guangdong Shuichi Co., Ltd, and has a model of SCC-A07H.
14. Then, the electroless copper plating is carried out for 30 minutes in a copper precipitation solution at the temperature of 33 ℃, wherein the copper precipitation solution is from Guangdong Shuichi technologies, Inc., and is of a model SCC-A08H.
15. After electroless copper plating, the plate was rinsed in tap water at 25 ℃ for 1 minute at room temperature.
16. Each substrate was cut on the side to expose the copper plated walls of the through holes. Side sections of 1mm thickness were selected from the cut walls of each plate, and the sections of each substrate were observed under a metallographic optical microscope at a magnification of 50X. The quality of the deposited copper film is measured by illumination under a microscope, the through hole wall film thickness is measured by adopting a backlight classification table, and the backlight classification is 1 grade: light transmission, wherein the light transmission area is more than 90%; and 2, stage: transmitting light, wherein 80 percent of light transmitting area is less than or equal to 90 percent; and 3, level: light transmission, 70 percent < the light transmission area is less than or equal to 80 percent; 4, level: light transmission, 60 percent < the light transmission area is less than or equal to 70 percent; and 5, stage: light transmission, 50% and less than or equal to 60% of a light transmission area; and 6, level: dark light, 40% < the visible light area is less than or equal to 50%, and the fiber shape is clear; and 7, stage: dark light, 30% < the visible light area is less than or equal to 40%, the dark light is fibrous; and 8, stage: dark light, 20 percent < the visible light area is less than or equal to 30 percent, and part of the dark light is in a fiber shape initially; stage 8.5: dark light, 10% < visible light area less than or equal to 20%, initial light <10 point scattered dark light distribution; and 9, stage: dark light, 5% < visible light area less than or equal to 10%, and initial light <5 scattered dark light distribution; 9.5 level: 1% of dark light, wherein the visible light area is less than or equal to 5%, and the initial light is less than 2 points and distributes the dark light in a scattered manner; 10 level: all black.
3. Resin plate palladium adsorption amount test: the steps 1 to 13 in the backlight gradation test were repeated, and after soaking in tap water at 25 ℃ for 1 minute, the container was dissolved with 40mL of aqua regia for half an hour, and then the container was rinsed with 20mL of pure water, and the test was performed using an atomic absorption tester for neutralization test.
TABLE 2
It can be seen from the above table that, by using the pretreatment liquid for copper deposition solution in the present application, the viscosity strength between the copper layer and the substrate is strong, and meanwhile, the pretreatment liquid for copper deposition solution in the present application is less affected by pH.
FIGS. 1 to 16 are the backlight effect diagrams of the copper deposition after the copper deposition pretreatment liquid treatment in examples 1 to 16, respectively. As can be seen from the figure, the backlight grade after using the copper deposition pretreatment liquid of the present application is excellent.
Claims (10)
1. The copper precipitation pretreatment liquid is characterized by comprising 0.01-100g/L of cationic polymer; the cationic polymer comprises a cationic polymer formed by polymerizing and quaternizing at least one of epoxy group, alkenyl group, active hydrogen and benzene ring and heterocyclic nitrogen-containing compound.
2. The copper precipitation pretreatment liquid as claimed in claim 1, wherein the heterocyclic nitrogen-containing compound has a structure of
Wherein Q, W, K are each independently selected from any one of C, O, N, and at least one of Q, W, K is N; r4、R5、R6Are respectively and independently selected from hydrogen and oxygenAny one of a chemically acceptable substituent group; x, Y, Z are each independently selected from any of C, O, N, and X, Y, Z has at least one N; r1、R2、R3Each independently selected from any one of hydrogen, oxygen, and chemically acceptable substituent groups.
3. The copper precipitation pretreatment liquid according to claim 2, wherein the degree of polymerization of the cationic polymer is 1 to 100.
4. The copper deposition pretreatment liquid according to claim 2 or 3, the non-polymerized and quaternized monomer of formula (2) is selected from any one of 1-vinylimidazole, 1-acetylimidazole, poly-1-propylimidazole, 1H-imidazole-4-carboxylic acid, 3-hydroxymethylisoxazole, 2-phenylimidazoline, 5-amino-2-benzimidazolone, antazoline, 1-acetyl-2-imidazolidinone, 1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene, 1-hexyl-3-methylimidazolium chloride salt, 2, 6-bis (2-benzimidazolyl) pyridine, 4-imidazoleacrylic acid, 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin.
5. The copper precipitation pretreatment liquid according to claim 2 or 3, wherein the unpolymerized and quaternized monomer of formula (1) is any one selected from the group consisting of pyridine-4-carbaldehyde, 4-aminopyridine, 4-hydroxypyridine, 4-methylaminopyridine and 2-pyridinemethanol.
6. The copper precipitation pretreatment liquid according to claim 2, further comprising 10g/L of a conditioning agent.
7. The copper precipitation pretreatment liquid according to claim 6, wherein the regulator comprises one or more of an organic acid, an inorganic acid, and an alkali metal hydroxide.
8. A pretreatment method is characterized by comprising the following steps:
(1) preparing a substrate;
(2) treating the substrate for 0.5-3min by using the copper deposition pretreatment liquid as defined in any one of claims 1-7.
9. The pretreatment method according to claim 8, further comprising a step of contacting the substrate with a strong oxidizing agent before the step (2).
10. The pretreatment method according to claim 8 or 9, wherein the roughness of the substrate is 450-1000 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110760475.0A CN113512720B (en) | 2021-07-05 | 2021-07-05 | Copper precipitation pretreatment liquid and pretreatment method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110760475.0A CN113512720B (en) | 2021-07-05 | 2021-07-05 | Copper precipitation pretreatment liquid and pretreatment method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113512720A true CN113512720A (en) | 2021-10-19 |
| CN113512720B CN113512720B (en) | 2022-06-17 |
Family
ID=78066511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110760475.0A Active CN113512720B (en) | 2021-07-05 | 2021-07-05 | Copper precipitation pretreatment liquid and pretreatment method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113512720B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115110071A (en) * | 2022-07-29 | 2022-09-27 | 电子科技大学 | Pretreatment method for chemical plating of insulating substrate and chemical plating method |
| CN115125593A (en) * | 2022-06-01 | 2022-09-30 | 生益电子股份有限公司 | Application of chelating agent in PCB preparation |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013073277A1 (en) * | 2011-11-14 | 2013-05-23 | 石原薬品株式会社 | Pretreatment solution for electroless copper plating, and electroless copper plating method |
| WO2017016965A1 (en) * | 2015-07-30 | 2017-02-02 | Basf Se | Process for metallizing plastic surfaces |
| CN107532305A (en) * | 2015-04-15 | 2018-01-02 | 汉高股份有限及两合公司 | The pre-rinsing for including polymer before conversion processing |
| US20180216233A1 (en) * | 2015-07-30 | 2018-08-02 | Basf Se | Process for pretreatment of plastic surfaces for metallization |
| CN108441844A (en) * | 2018-04-03 | 2018-08-24 | 广东东硕科技有限公司 | Activating solution and preparation method thereof for non-conductive substrate chemical plating |
-
2021
- 2021-07-05 CN CN202110760475.0A patent/CN113512720B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013073277A1 (en) * | 2011-11-14 | 2013-05-23 | 石原薬品株式会社 | Pretreatment solution for electroless copper plating, and electroless copper plating method |
| CN107532305A (en) * | 2015-04-15 | 2018-01-02 | 汉高股份有限及两合公司 | The pre-rinsing for including polymer before conversion processing |
| WO2017016965A1 (en) * | 2015-07-30 | 2017-02-02 | Basf Se | Process for metallizing plastic surfaces |
| US20180216233A1 (en) * | 2015-07-30 | 2018-08-02 | Basf Se | Process for pretreatment of plastic surfaces for metallization |
| CN108441844A (en) * | 2018-04-03 | 2018-08-24 | 广东东硕科技有限公司 | Activating solution and preparation method thereof for non-conductive substrate chemical plating |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115125593A (en) * | 2022-06-01 | 2022-09-30 | 生益电子股份有限公司 | Application of chelating agent in PCB preparation |
| CN115125593B (en) * | 2022-06-01 | 2023-12-05 | 生益电子股份有限公司 | Application of chelating agent in PCB preparation |
| CN115110071A (en) * | 2022-07-29 | 2022-09-27 | 电子科技大学 | Pretreatment method for chemical plating of insulating substrate and chemical plating method |
| CN115110071B (en) * | 2022-07-29 | 2023-09-01 | 电子科技大学 | Method for treating insulating substrate before electroless plating and electroless plating method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113512720B (en) | 2022-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113512720B (en) | Copper precipitation pretreatment liquid and pretreatment method thereof | |
| JPS61166977A (en) | Reduced fine particle catalytic metal | |
| JP5715748B2 (en) | Conditioner for electroless plating | |
| KR101340022B1 (en) | Method for coating polydopamine | |
| US20100273014A1 (en) | Metal-clad substrate, and method for production thereof | |
| JP2009174041A (en) | Process for adsorbing plating catalyst, process for production of substrate provided with metal layer and plating catalyst fluid for use in both process | |
| TWI805550B (en) | Manufacturing method of printed wiring board | |
| JP2011162806A (en) | Pretreatment liquid for electroless plating | |
| TW201823511A (en) | Method for producing printed wiring board | |
| CN102037063B (en) | Method for conditioning insulating resin and its use | |
| TWI572741B (en) | Electroless copper plating solution | |
| JP2002335067A (en) | Swelling solvent composition for texturing resin material and desmearing and removing resin material | |
| EP3257967B1 (en) | Pretreatment agent for electroless plating, and pretreatment method and manufacturing method for printed wiring board in which pretreatment agent for electroless plating is used | |
| CA2920633A1 (en) | Forming a conductive image using high speed electroless platin | |
| WO2010047330A1 (en) | Resin complex and laminate | |
| EP2230328A1 (en) | Plating method, method for forming metal thin film, and plating catalyst liquid | |
| KR102010637B1 (en) | Method for treatment of recessed structures in dielectric materials for smear removal | |
| CN113543523B (en) | Substrate hole processing method and application thereof | |
| TWI668054B (en) | Electroless plating method | |
| JP2006077289A (en) | Pretreatment method for electroless plating, and pretreatment liquid used therefor | |
| EP0139233B1 (en) | Method for conditioning a surface of a dielectric substrate for electroless plating | |
| TWI606140B (en) | Electroless copper plating bath and electroless copper plating method for increasing hardness of copper plating | |
| TWI655318B (en) | Method for electroless plating | |
| WO2011033819A1 (en) | Method for forming polymer layer | |
| KR101243282B1 (en) | Copper-polymer resin bonded component and method of preparing the component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 512000 chlor alkali characteristic industrial base of hougongdu Economic Development Zone, Rucheng Town, Ruyuan County, Shaoguan City, Guangdong Province Applicant after: Guangdong Shuocheng Technology Co.,Ltd. Address before: 512000 chlor alkali characteristic industrial base of hougongdu Economic Development Zone, Rucheng Town, Ruyuan County, Shaoguan City, Guangdong Province Applicant before: GUANGDONG SHUOCHENG TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |