Cleaning agent composition, cleaning agent solution and application thereof

Abstract

The present application relates to the technical field of chemical metal plating, and specifically to a cleaning agent composition and a cleaning agent solution thereof and application thereof, wherein the cleaning agent composition comprises a first surfactant, a second surfactant, an alkali and an auxiliary agent; the first surfactant comprises a sulfonic acid aromatic compound having a structure such as formula I; the second surfactant comprises a sulfonic acid fluorocarbon compound having a structure such as formula II. The cleaning agent composition and the cleaning agent solution of the present application can be used in the degreasing process of chemical metal plating, and can be used in the hole-filling process of chemical copper plating, and have good wettability, good effect of reducing the surface tension of the hole wall, and a wide range of applications, and can be applied to large surface through holes and tiny pores such as blind crab legs.

Description

Technical Field

[0001] The present application relates to the technical field of chemical metal plating, and in particular to a cleaning agent composition and a cleaning agent solution and application thereof. Background Art

[0002] Chemical metal plating is an electroless deposition coating technology that can be used to form a conductive layer on the surface of non-conductive materials. It is widely used in electronic appliances, hardware crafts, handicrafts, furniture decoration and other industries. The principle of chemical metal plating is to reduce the metal ions in the solution containing metal ions by a specific chemical reducing agent without an external current and deposit them on the surface of the catalytically pretreated substrate to form a uniform metal layer.

[0003] Degreasing is a very important pretreatment step in the chemical metal plating process. It can improve the adhesion between the coating and the substrate and obtain a high-quality coating. Therefore, it is very necessary to develop a cleaning agent with good degreasing effect.

[0004] Chemical copper plating is a specific application of chemical metal plating technology and can be used for hole metallization of circuit boards. The principle is to plate a thin layer of copper on the inner wall of the hole on the PCB substrate after drilling through a chemical reaction, so that the top and bottom layers of the PCB are connected to each other, realizing the electrical interconnection of the conductive patterns between the layers of double-sided boards and multi-layer boards.

[0005] Hole metallization usually includes the following processes: hole filling, micro-etching, pre-preg, activation, acceleration and chemical copper plating. Hole filling is a very important pretreatment step. It is a treatment of the board and the hole wall before the plated through hole (PTH) process. Its purpose includes adjusting the charge in the hole and cleaning the oil stains so that the subsequent chemical copper plating reaction can proceed smoothly. This step affects the bonding force between the hole wall and the copper layer, which is crucial to ensuring the quality and performance of the circuit board. Therefore, it is very necessary to develop a hole filling agent with good hole filling effect. Summary of the invention

[0006] Based on this, one or more embodiments of the present application provide a cleaning agent composition, a cleaning agent solution and an application thereof. The cleaning agent composition and the cleaning agent solution of the present application can be used in the degreasing process of chemical metal plating and can be used in the hole filling process of chemical copper plating. They have good wettability and are effective in reducing the surface tension of the hole wall. They also have a wide range of applications and can be suitable for large surface through holes and tiny pores such as blind crab feet.

[0007] The technical solution of this application includes the following contents:

[0008] A cleaning agent composition, in parts by weight, comprising:

[0009] 0.01-0.1 part of the first surfactant;

[0010] 0.001-0.02 parts of the second surfactant;

[0011] 5 to 30 parts of alkali; and

[0012] Additives 0.1~2 parts;

[0013] The first surfactant comprises a sulfonic acid aromatic compound having a structure as shown in Formula I;

[0014] I;

[0015] The second surfactant comprises a sulfonic acid fluorocarbon compound of formula II:

[0016] II;

[0017] in,

[0018] Ring A is a phenyl group having at least one R1 substituent;

[0019] X1 is selected from O, C 1~12 Alkylene, -R3-O-R4- and -O-R5-O-;

[0020] R1 is selected from sodium sulfonate and C 1~12 alkyl;

[0021] R2 is selected from C n F 2n+1 ;

[0022] R3, R4 and R5 are independently selected from C 1~12 Alkylene;

[0023] n is an integer selected from 3 to 8;

[0024] The auxiliary agent includes an alkyl alcohol compound;

[0025] The base includes an organic base and an inorganic base in a weight ratio of 1: (0.5-20).

[0026] In some embodiments, the weight ratio of the first surfactant to the second surfactant is (10-100):1.

[0027] In some embodiments, the organic base comprises an organic amine compound.

[0028] In some embodiments, the organic amine compound includes at least one of monoethanolamine, triethanolamine, cyclohexylamine, tetraethylenediamine and polyacrylamide.

[0029] In some embodiments, the inorganic base includes at least one of aqueous ammonia, potassium hydroxide, and sodium hydroxide.

[0030] In some embodiments, the alkyl alcohol compound includes at least one of cyclohexanedimethanol, hexanediol, neopentyl glycol, undecyl alcohol, ethylene glycol, isopropanol and isooctyl alcohol.

[0031] In some embodiments, the cleaning composition comprises, by weight:

[0032] 0.02-0.08 parts of the first surfactant;

[0033] 0.002-0.008 parts of the second surfactant;

[0034] 10 to 20 parts of the base; and

[0035] 1~2 parts of the auxiliary agent.

[0036] A cleaning solution comprises the cleaning composition described above and a solvent.

[0037] In some embodiments, every 1000 mL of the cleaning solution comprises: 0.01-0.1 g of the first surfactant, 0.001-0.02 g of the second surfactant, 5-30 g of the alkali and 0.1-2 g of the auxiliary agent.

[0038] An application of the above-mentioned cleaning agent composition or cleaning agent solution in chemical metal plating is used as a degreasing agent or a pore-regulating agent.

[0039] The cleaning agent composition of the present application can produce a good oil stain removal effect and can also adjust the surface charge of the substrate through the compounding of the first surfactant, the second surfactant, the alkali and the auxiliary agent. Therefore, it is suitable for the degreasing process of chemical metal plating, and is also suitable for the hole-filling process of chemical copper plating. It can be used as a degreasing agent or a hole-filling agent and ensure the uniformity of subsequent copper plating to prepare high-quality chemically plated parts.

[0040] The cleaning agent composition of the present application includes a sulfonic acid aromatic compound with a structure as shown in Formula I and a sulfonic acid fluorocarbon compound with a structure as shown in Formula II. The two surfactants are used in combination to produce good effects in improving the wettability of aqueous solutions and reducing interfacial tension. In addition, since the van der Waals attraction between the molecules of the sulfonic acid fluorocarbon compound is small, the interaction force between the carbon fluorine chain molecules is small, and the surface activity is high, the cleaning agent composition can have extremely low surface tension when used, and the surface adsorption capacity is very strong, so that the interface adjustment ability between large surface through holes and tiny pores such as blind hole crab legs can be taken into account, the possibility of blind hole leakage plating can be improved, and the electroplating hole filling yield rate can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0042] Figure 1 This is a blind hole crab claw morphology image of the degreaser of Example 1 of the present application. DETAILED DESCRIPTION

[0043] The present application will be further described below in conjunction with the embodiments and examples. It should be understood that these examples are only used to illustrate the present application and are not intended to limit the scope of the present application. In addition, it should be understood that after reading the content taught in the present application, those skilled in the art may make various changes or modifications to the present application, and these equivalent forms also fall within the protection scope of the claims attached to the present application.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0045] the term

[0046] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0047] The term "and / or" used in this article includes any one of two or more related listed items, and also includes any and all combinations of related listed items, and the arbitrary and all combinations include any two related listed items, any more related listed items, or all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly includes technical solutions that are all connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B.

[0048] Herein, "preferred", "preferable", "better", etc. are only used to describe implementation methods or examples with better effects. It should be understood that they do not constitute limitations on the scope of protection of this application.

[0049] In the present application, "further", "further", "particularly" and the like are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present application.

[0050] In this application, "first", "second", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0051] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0052] In this application, when it comes to numerical intervals (i.e., numerical ranges), unless otherwise specified, the optional numerical distribution is considered continuous within the above numerical interval, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical range, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to integers within the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints. In addition, when multiple ranges are provided to describe features or characteristics, these ranges can be combined. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges included therein.

[0053] In the present application, weight may be μg, mg, g, kg or other mass units known in the chemical industry.

[0054] A cleaning agent composition comprises a first surfactant, a second surfactant, an alkali and an auxiliary agent;

[0055] The first surfactant includes a sulfonic acid aromatic compound having a structure as shown in Formula I;

[0056] I;

[0057] The second surfactant comprises a sulfonic acid fluorocarbon compound having a structure such as Formula II:

[0058] II;

[0059] in,

[0060] Ring A is a phenyl group having at least one R1 substituent;

[0061] X1 is selected from O, C 1~12 Alkylene, -R3-O-R4- and -O-R5-O-;

[0062] R1 is selected from sodium sulfonate and C 1~12 alkyl;

[0063] R2 is selected from C n F 2n+1 ;

[0064] R3, R4 and R5 are independently selected from C 1~12 Alkylene;

[0065] n is selected from an integer of 3 to 8.

[0066] In the above, ring A refers to , in this article, ” refers to the attachment site.

[0067] As used herein, "alkyl" refers to a saturated hydrocarbon containing primary (normal) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or a combination thereof. Phrases containing this term, such as "C 6~14 "Alkyl" refers to an alkyl group containing 6 to 14 carbon atoms, and each occurrence can be independently C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C 10 Alkyl, C 11 Alkyl, C 12 Alkyl, C 13 Alkyl or C 14 alkyl. Suitable examples include, but are not limited to, 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3, and octyl (-(CH2)7CH3).

[0068] The term "alkylene" refers to a hydrocarbon group having two monovalent radical centers derived from an alkyl group by removing a hydrogen atom, which may be a saturated branched alkyl group or a saturated straight chain alkyl group. 12"Alkylene" means that the alkylene portion contains 1 to 12 carbon atoms, and each occurrence can be independently C1 alkylene, C2 alkylene, C3 alkylene, C4 alkylene, C5 alkylene, C6 alkylene, C7 alkylene, C8 alkylene, C9 alkylene, C 10 Alkylene, C 11 Alkylene or C 12 Alkylene. Suitable examples include, but are not limited to, methylene (—CH2—), 1,1-ethyl (—CH(CH3)—), 1,2-ethyl (—CH2CH2—), 1,1-propyl (—CH(CH2CH3)—), 1,2-propyl (—CH2CH(CH3)—), 1,3-propyl (—CH2CH2CH2—), and 1,4-butyl (—CH2CH2CH2CH2—).

[0069] In some embodiments, the sulfonic acid aromatic compound of formula I is selected from:

[0070] ;

[0071] and

[0072] ;

[0073] R 11 and R 12 are independently selected from C 1~12 alkyl.

[0074] In some embodiments, R 11 and R 12 are independently selected from C 6~12 alkyl.

[0075] In some embodiments, X1 is selected from O.

[0076] In some embodiments, X1 is selected from C 1~12 Alkylene, further selected from C 6~12 Alkylene.

[0077] In some embodiments, X1 is selected from -R3-O-R4-, wherein R3 and R4 are independently selected from C 1~12 Alkylene, further selected from C 6~12 Alkylene.

[0078] In some embodiments, X1 is selected from -O-R5-O-; wherein R5 is selected from C 1~12 Alkylene, further selected from C 6~12 Alkylene.

[0079] In some embodiments, R1 is selected from a sodium sulfonate group, the structural formula is .

[0080] In some embodiments, R1 is selected from C 1~12 Alkyl, further selected from C 6~12 alkyl.

[0081] In some embodiments, R2 is selected from C n F 2n+1 , n is selected from an integer ranging from 3 to 8.

[0082] In some embodiments, the weight ratio of the first surfactant to the second surfactant is (10-100):1, for example 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, etc.

[0083] In some embodiments, the base comprises an organic base and an inorganic base in a weight ratio of 1:(0.5-20);

[0084] Organic bases include organic amine compounds;

[0085] The inorganic base includes at least one of aqueous ammonia, potassium hydroxide and sodium hydroxide.

[0086] In some embodiments, the weight ratio of the organic base to the inorganic base is 1:(0.5-20), for example 1:0.5, 1:2, 1:5, 1:10, 1:12, 1:15, 1:18, 1:20, etc.

[0087] In some embodiments, the organic amine compound includes at least one of monoethanolamine, triethanolamine, cyclohexylamine, tetraethylenediamine and polyacrylamide.

[0088] In some embodiments, the auxiliary agent includes an alkyl alcohol compound.

[0089] In some embodiments, the alkyl alcohol compound includes at least one of cyclohexanedimethanol, hexylene glycol, neopentyl glycol, undecyl alcohol, ethylene glycol, isopropyl alcohol, and isooctyl alcohol.

[0090] In some embodiments, the cleaning composition comprises, by weight:

[0091] 0.01-0.1 part of the first surfactant;

[0092] 0.001-0.02 parts of the second surfactant;

[0093] 5 to 30 parts of alkali; and

[0094] Additives 0.1~2 parts.

[0095] In this embodiment, the weight portion of the first surfactant can be selected from 0.01 to 0.1 parts, for example, 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 0.1 parts, etc., and the weight portion of the second surfactant can be selected from 0.001 to 0.02 parts, for example, 0.001 parts, 0.00 2 parts, 0.005 parts, 0.01 parts, 0.015 parts, 0.02 parts, etc., the weight parts of the alkali can be selected from 5 to 30 parts, for example, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 20 parts, 25 parts, 30 parts, etc., the weight parts of the auxiliary agent can be selected from 0.1 to 2 parts, for example, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 2 parts, etc.

[0096] In this embodiment, 5 to 30 parts of the base contain an organic base and an inorganic base in a weight ratio of 1:(0.5 to 20), and the weight ratio of the organic base to the inorganic base is, for example, 1:0.5, 1:2, 1:5, 1:10, 1:12, 1:15, 1:18, 1:20, etc.

[0097] A cleaning solution comprises the above cleaning composition and a solvent.

[0098] In some embodiments, every 1000 mL of the cleaning agent solution includes: 0.01-0.1 g of the first surfactant, 0.001-0.02 g of the second surfactant, 5-30 g of the base and 0.1-2 g of the auxiliary agent.

[0099] A use of the above cleaning agent composition or cleaning agent solution in chemical metal plating as a degreasing agent or a pore-conditioning agent.

[0100] The cleaning agent composition of the present application can produce a good oil stain removal effect and can also adjust the surface charge of the substrate through the compounding of the first surfactant, the second surfactant, the alkali and the auxiliary agent. Therefore, it is suitable for the degreasing process of chemical metal plating, and is also suitable for the hole-filling process of chemical copper plating. It can be used as a degreasing agent or a hole-filling agent and ensure the uniformity of subsequent copper plating to prepare high-quality chemically plated parts.

[0101] The cleaning agent composition of the present application includes a sulfonic acid aromatic compound with a structure as shown in Formula I and a sulfonic acid fluorocarbon compound with a structure as shown in Formula II. The two surfactants are used in combination to produce good effects in improving the wettability of aqueous solutions and reducing interfacial tension. In addition, since the van der Waals attraction between the molecules of the sulfonic acid fluorocarbon compound is small, the interaction force between the carbon fluorine chain molecules is small, and the surface activity is high, the cleaning agent composition can have extremely low surface tension when used, and the surface adsorption capacity is very strong, so that the interface adjustment ability between large surface through holes and tiny pores such as blind hole crab legs can be taken into account, the possibility of blind hole leakage plating can be improved, and the electroplating hole filling yield rate can be improved.

[0102] The following are some specific embodiments.

[0103] The raw materials and reagents involved in the following specific examples can be obtained from commercial sources, or can be prepared by those skilled in the art according to known methods.

[0104] Among them, C8-sodium fluorocarbon chain sulfonate (Zhongtian Chemical) and other reagents can be purchased from manufacturers such as Aladdin and McLean.

[0105] 1. Preparation of degreasing agent

[0106] The raw materials of each example were prepared according to Table 1 and Table 2. After the raw materials of each example were mixed, about 100 mL of water was added to dissolve them, and after they were completely dissolved, water was added to make the volume 1 L.

[0107] Table 1 Raw material formula of Example 1 and each comparative example

[0108]

[0109] Table 2 Raw material formula of each embodiment

[0110]

[0111] In Table 1 and Table 2:

[0112] The structure of C12-alkyl benzene ether sodium sulfonate surfactant is ;

[0113] The structure of C12-MADS is ;

[0114] The structure of sodium dodecyl sulfate is ;

[0115] The structure of sodium 2-ethylhexyl sulfonate is ;

[0116] The structure of sodium dodecylbenzene ether sulfonate is ;

[0117] The structure of C8-sodium fluorocarbon chain sulfonate is .

[0118] 2. Performance test of degreaser

[0119] 1. Surface tension comparison test

[0120] The surface tension of the degreasing agents of Comparative Examples 1 to 5 and Examples 1 to 9 was tested by an automatic surface tension tester. The test results are shown in Table 3.

[0121] Table 3 Surface tension test results of various comparative examples and embodiments

[0122]

[0123] According to Table 3, the sulfonic acid aromatic hydrocarbon surfactant of Example 1 is compounded with the fluorinated surfactant to reduce the surface tension to 26 mN / m, so that the degreasing agent can better wet the fine pores of the substrate. Since no surfactant is added to Comparative Example 1, its surface tension is similar to that of water (72 mN / m), and the surface tension is relatively large. When only sulfonic acid aromatic hydrocarbon surfactants are added to Comparative Examples 2 and 3, the surface tension is about 50 mN / m, and the reduction effect is not obvious. Comparative Example 4 uses sodium dodecyl sulfonate and C8-sodium fluorocarbon chain sulfonate to compound, but the surface tension reduction effect is not as good as that of Example 1. Comparative Example 5 only uses sodium 2-ethylhexyl sulfonate, which contains a shortened hydrocarbon chain and a branched structure, and can reduce the surface to 35 mN / m, but the surface tension reduction effect is not as good as that of Example 1.

[0124] According to Table 2, it can be found that the effects of Examples 2, 3, 7 and 8 are not much different from those of Example 1, indicating that the base can be selected within a suitable range according to actual needs, while the effects of Examples 4 and 9 are slightly reduced after the type or ratio of the auxiliary agent is changed, indicating that the compounding of the auxiliary agent and the surfactant has an important synergistic effect, and the effects of Examples 5 and 6 are slightly reduced after the ratio of the two surfactants is changed, but there is still a significant improvement compared with Comparative Examples 1 to 5, indicating that the addition amount of each component can be adjusted within a suitable range according to actual needs.

[0125] 3. Application of degreasing agent in chemical metal plating

[0126] 1. Evaluation of oil removal effect

[0127] The conventional process of existing chemical metal plating includes expansion, degumming, neutralization, degreasing, microetching, activation, reduction and finally immersion in chemical metal plating liquid to deposit the target metal. The specific conditions of each process in the process can be carried out according to Table 4, and there is a water washing step between each process.

[0128] Table 4 Chemical metal plating process

[0129]

[0130] According to the process of chemical metal plating in Table 4, 14 examples of FR-4 resin (containing glass fiber) were taken in parallel for chemical copper plating. During the degreasing process, the degreasing agents of Comparative Examples 1 to 5 and Examples 1 to 9 were used for immersion treatment, and other chemical plating operations were the same.

[0131] After the above 14 examples of FR-4 resin (containing glass fiber) completed the entire chemical copper plating process, the backlight level of each plated part was observed. The backlight level results are shown in Table 5.

[0132] Table 5 Backlight performance test results of various comparative examples and embodiments

[0133]

[0134] According to Table 5, the compounding of the sulfonic acid aromatic hydrocarbon surfactant and the fluorine-containing special surfactant in Example 1 can improve the adsorption capacity of the degreasing agent, so that the backlight performance of through holes with different apertures can reach level 10. In Comparative Example 1, since no surfactant was added, the backlight performance was only level 7 to 8, indicating that the degreasing agent can better treat the hole wall to improve the backlight performance when the surface tension is low. When only sulfonic acid aromatic hydrocarbon surfactants were added to Comparative Examples 2 and 3, the backlight performance of different apertures was level 8 to 9.5, which is only applicable to some apertures and the effect is not as good as that of Example 1. Comparative Example 4 uses sodium dodecyl sulfate and C8-sodium fluorocarbon chain sulfonate for compounding, but the backlight performance can only reach level 9, which is not as good as that of Example 1. Comparative Example 5 uses only sodium 2-ethylhexyl sulfonate to reduce the surface tension (see the surface tension test results in Table 3), but the improvement effect of the backlight performance is not as good as that of Example 1 (even not as good as the effect of adding only sulfonic acid aromatic hydrocarbon surfactants in Comparative Examples 2-3). It can be seen that simply reducing the surface tension but the adsorption capacity of the surfactant is weak cannot effectively improve the backlight performance, especially for large pores (pore size of 0.5-1.0 mm). The backlight level of Comparative Example 5 for large pores only reaches level 7-8.

[0135] According to Table 5, it can be found that Examples 2, 3, 4, 5 and 9 are not much different from Example 1, indicating that the type and addition amount of each component can be selected within a suitable range according to actual needs, while the effects of Examples 7 and 8 are slightly reduced after the ratio of the base is changed, indicating that the compounding of the organic base and the inorganic base has an important synergistic effect.

[0136] 2. Blind hole TP capability comparison

[0137] The TP of a blind hole is calculated by dividing the average copper thickness at the bottom of the hole by the average copper thickness at the hole mouth.

[0138] According to the process of chemical metal plating in Table 4, 14 blind hole test boards were taken in parallel for chemical copper plating. The pore size of the blind hole test board was 110 μm, and the dielectric thickness was 80 μm. During the degreasing process, the degreasing agents of Comparative Examples 1 to 5 and Examples 1 to 9 were used for immersion treatment, respectively, and other chemical plating operations were the same.

[0139] The TP capabilities of the bottom holes of the above 14 blind via test boards are shown in Table 6.

[0140] Table 6 Blind hole TP capability test results of each comparative example and embodiment

[0141]

[0142] According to Table 6, the reduction of the surface tension of the degreasing agent can effectively infiltrate the bottom of the blind hole, enhance its adsorption capacity for palladium ions, and increase its copper deposition thickness. However, Comparative Example 5 shows that when the surface tension is reduced and the adsorption capacity of the surfactant is insufficient, the palladium adsorption capacity at the bottom of the blind hole cannot be significantly enhanced. The degreasing agent compounded with the sulfonic aromatic surfactant and the fluorine-containing special surfactant can effectively infiltrate and adjust the charge of the fine pores at the bottom of the blind hole, enhance the palladium adsorption capacity of each site, and improve the uniformity of copper deposition.

[0143] According to Table 6, it can be found that the effects of Examples 2, 3 and 8 are not much different from those of Example 1, indicating that the alkali can be adjusted within a suitable range according to actual needs, while the effects of Examples 4, 5, 6 and 9 are slightly reduced after changing the ratio of the auxiliary agent or surfactant, indicating that the compounding of the auxiliary agent and the surfactant has an important synergistic effect.

[0144] The morphology of the blind crab legs using the degreasing agent of Example 1 is as follows Figure 1 As shown. Figure 1 It can be seen that the larger blind crab legs caused by neutralization and micro-etching in the pre-treatment can be completely coppered after being adjusted by the degreasing agent in Example 1, reducing the possibility of leak plating.

Claims

1. A cleaning composition, characterized in that In parts by weight, it includes: 0.01-0.1 part of the first surfactant; 0.001-0.02 parts of the second surfactant; 5 to 30 parts of alkali; and Additives 0.1~2 parts; The first surfactant comprises a sulfonic acid aromatic compound having a structure as shown in Formula I; I； The second surfactant comprises a sulfonic acid fluorocarbon compound of formula II: II; in, Ring A is a phenyl group having at least one R1 substituent; X1 is selected from O, C 1~12 Alkylene, -R3-O-R4- and -O-R5-O-; R1 is selected from sodium sulfonate and C 1~12 alkyl; R2 is selected from C n F 2n+1 ; R3, R4 and R5 are independently selected from C 1~12 Alkylene; n is an integer selected from 3 to 8; The auxiliary agent includes an alkyl alcohol compound; The base includes an inorganic base and an organic base in a weight ratio of 1: (0.5-20).

2. The cleaning composition according to claim 1, characterized in that The weight ratio of the first surfactant to the second surfactant is (10-100):

1.

3. The cleaning composition according to claim 1 or 2, characterized in that The organic base includes organic amine compounds.

4. The cleaning composition according to claim 3, characterized in that The organic amine compound includes at least one of monoethanolamine, triethanolamine, cyclohexylamine, tetraethylenediamine and polyacrylamide.

5. The cleaning composition according to claim 1 or 2, characterized in that The inorganic base includes at least one of ammonia water, potassium hydroxide and sodium hydroxide.

6. The cleaning composition according to claim 1 or 2, characterized in that The alkyl alcohol compound includes at least one of cyclohexanedimethanol, hexanediol, neopentyl glycol, undecyl alcohol, ethylene glycol, isopropanol and isooctyl alcohol.

7. The cleaning composition according to any one of claims 1, 2 and 4, characterized in that The cleaning agent composition comprises, by weight: 0.02-0.08 parts of the first surfactant; 0.002-0.008 parts of the second surfactant; 10 to 20 parts of the base; and 1~2 parts of the auxiliary agent.

8. A cleaning solution, characterized in that The cleaning agent comprises the cleaning agent composition according to any one of claims 1 to 7 and a solvent.

9. The cleaning solution according to claim 8, characterized in that Every 1000 mL of the detergent solution includes: 0.01-0.1 g of the first surfactant, 0.001-0.02 g of the second surfactant, 5-30 g of the alkali and 0.1-2 g of the auxiliary agent.

10. Use of the cleaning agent composition according to any one of claims 1 to 7 or the cleaning agent solution according to any one of claims 8 to 9 in chemical metal plating, characterized in that: Used as a degreasing agent or pore-correcting agent.

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