PROTECTIVE COATING COMPOSITION FOR CIRCUIT BOARD

Abstract

The present disclosure provides a protective coating composition for circuit boards, the composition capable of i) forming a protective coating for effectively protecting a circuit board and an electrical/electronic component mounted thereon, from moisture, foreign materials, and corrosive gas, ii) reducing the formation time of a protective coating, iii) forming a protective coating capable of achieving optimal protective performance with a smaller thickness, and iv) forming a protective coating that is easier to remove. According to one aspect of the present disclosure, an embodiment of the protective coating composition for circuit boards includes a polyketone, and a solvent.

Claims

1. A protective coating composition for circuit boards, comprising: a polyketone; and a solvent.

2. The protective coating composition of claim 1, wherein the polyketone comprises a repeat unit represented by Equation 2, ##STR00003## wherein, R1 is hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, a linear or branched alkyl ether group having 1 to 12 carbon atoms, an aryl ether group having 6 to 30 carbon atoms, a linear or branched alkyl ester group having 1 to 12 carbon atoms, or an aryl ester group having 6 to 30 carbon atoms, and wherein x:y is 1:999 to 999:1.

3. The protective coating composition of claim 2, wherein R1 is hydrogen, or a linear or branched alkyl group having 1 to 5 carbon atoms.

4. The protective coating composition of claim 2, wherein R1 is hydrogen or a methyl group.

5. The protective coating composition of claim 1, further comprising an ethylene vinyl alcohol resin.

6. The protective coating composition of claim 1, wherein the solvent comprises ethyl alcohol, isopropyl alcohol, methyl isobutyl ketone, normal butyl alcohol, propylene glycol monomethyl ether, xylene, toluene, methyl ethyl ketone, acetone, hexanone, or a combination thereof.

7. The protective coating composition of claim 1, wherein the solvent comprises ethyl alcohol, isopropyl alcohol, methyl isobutyl ketone, normal butyl alcohol, propylene glycol monomethyl ether, or a combination thereof.

8. The protective coating composition of claim 1, wherein the solvent comprises a mixture of ethyl alcohol and normal butyl alcohol, or a mixture of ethyl alcohol and propylene glycol monomethyl ether.

9. A method of forming a protective coating for circuit boards, the method comprising: performing, at least once, a process of applying the protective coating composition according to claim 1 on at least a portion of a surface of a circuit board on which an electrical/electronic component is mounted and then drying the protective coating composition.

10. The method of claim 9, wherein a thickness of a protective coating finally formed is about 2 μm to about 5 μm.

11. A laminate comprising: a circuit board on which an electrical/electronic component is mounted; and a protective coating formed on at least a portion of a surface of the circuit board, wherein the protective coating comprises a polyketone, or a combination of a polyketone and an ethylene vinyl alcohol resin.

12. The laminate of claim 11, wherein a thickness of the protective coating is about 2 μm to about 5 μm.

Description

BEST MODE

Polyketones

[0017] In the present disclosure, the term ‘polyketone’ refers to any polymer and copolymer including a repeat unit containing a carbonyl group (—C(═O)—). The polyketone includes a ketone resin and a ketone/aldehyde resin. The ketone/aldehyde resin refers to a resin formed by condensation of a ketone and an aldehyde. The polyketone may include, for example, at least one of repeat units represented by Equation 1 below.

##STR00001##

[0018] Here, R may be a linear or branched alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 30 carbon atoms, a linear or branched alkyl ether group having 2 to 12 carbon atoms, an aryl ether group having 6 to 30 carbon atoms, a linear or branched alkyl ester group having 2 to 12 carbon atoms, or an aryl ester group having 6 to 30 carbon atoms.

[0019] The polyketone may be prepared, for example, by condensing ketones (for example, alicyclic ketones, such as, cyclohexanone or a derivative thereof), in combination with an aldehyde (for example, formaldehyde) where appropriate, in the presence of an alkaline catalyst. Alternatively, the polyketone may be prepared, for example, by a reaction between a compound containing an unsaturated double bond and carbon monoxide. Alternatively, the polyketone may be, for example, an alternating copolymer prepared by a reaction between at least one ethylene-based unsaturated hydrocarbons and carbon monoxide. Alternatively, the polyketone may be prepared, for example, by a gas-phase reaction of ethylene and/or propylene with carbon monoxide in the presence of a palladium (II) catalyst.

[0020] A number average molecular weight of a polyketone, when measured by gel permeation chromatography, may be, for example, from about 1,000 g/mol to about 200,000 g/mol, or from about 20,000 g/mol to about 90,000 g/mol, but may be outside these ranges.

[0021] In carbonyl groups positioned on the main chain of the polyketone, as oxygen atoms strongly attract electrons in carbon atoms, the carbonyl groups show polarity. Due to such polarity of carbonyl groups, an electric attraction occurs between polyketone chains. Due to such electric attraction, distances between the polyketone chains decrease. Such a densely arranged structure of the polyketone chains makes it extremely difficult for corrosive gas to penetrate a polyketone layer. Accordingly, the protective coating composition for circuit boards of the present disclosure, containing a polyketone, may form a protective coating that effectively prevents the infiltration of corrosive gas.

[0022] In another embodiment, the polyketone may include a repeat unit represented by Equation 2 below.

##STR00002##

[0023] Here, R1 may be hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, a linear or branched alkyl ether group having 1 to 12 carbon atoms, an aryl ether group having 6 to 30 carbon atoms, a linear or branched alkyl ester group having 1 to 12 carbon atoms, or an aryl ester group having 6 to 30 carbon atoms, wherein x:y may be about 1:999 to about 999:1.

[0024] The bigger the size of R1 group, the more it is hindered for polyketone chains to form a dense arrangement. Conversely, the smaller the size of R1 group, the less it is hindered for polyketone chains to form a dense arrangement. Accordingly, the smaller the size of R1 group, the more effective the blocking of corrosive gas by a polyketone layer. In this respect, R1 may be preferably hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms, may be more preferably hydrogen or a methyl group, and may be most preferably, hydrogen.

[0025] As described above, the smaller the size of R1 group, the more densely the polyketone chains are arranged, and as a result, the crystallinity of the polyketone layer increases. The polyketone layer with a greater crystallinity may have a greater brittleness. Conversely, as the size of R1 group increases, the polyketone layer may have a reduced crystallinity and consequently, a reduced brittleness (that is, increased flexibility). Therefore, to provide a polyketone layer having both excellent corrosive gas protection characteristics and flexibility, R1 may be more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and may be most preferably, a methyl group.

[0026] The amount of polyketones in the protective coating composition may be about 0.1 wt % to about 90 wt % with respect to the total weight of the protective coating composition. The smaller the amount of the polyketones in the protective coating composition, the lower the viscosity of the protective coating composition. Such a protective coating composition with a low viscosity may be suitable for a spray method. The greater the amount of the polyketones in the protective coating composition, the greater the viscosity of the protective coating composition. Such a protective coating composition with a high viscosity may be suitable for a painting method.

Ethylene Vinyl Alcohol Resin

[0027] In another embodiment of the present disclosure, the protective coating composition may further include an ethylene vinyl alcohol resin. As commonly known, ethylene vinyl alcohol resins can block gases, such as oxygen and hydrogen, extremely effectively. However, ethylene vinyl alcohol resins are extremely costly. Furthermore, such ethylene vinyl alcohol resins are hydrophilic due to the presence of —OH groups, and as a result, exhibit inferior moisture protection characteristics. Therefore, ethylene vinyl alcohol resins alone cannot be used in a protective coating composition.

[0028] However, when an ethylene vinyl alcohol resin is used in combination with polyketones, due to excellent moisture protection characteristics of polyketones, inferior moisture protection characteristics of the ethylene vinyl alcohol resin may be compensated. In addition, due to excellent gas protection characteristics of the ethylene vinyl alcohol resin, corrosive gas protection characteristics of polyketones may be enhanced. When a combination of polyketones and an ethylene vinyl alcohol resin is used, the weight ratio of the ethylene vinyl alcohol resin to the polyketones may be, for example, about 1:999 to about 999:1. In the protective coating composition, the amount of a combination of a polyketone and an ethylene vinyl alcohol resin may be, for example, about 0.1 wt % to about 90 wt % with respect to the total weight of the protective coating composition.

[0029] The ethylene vinyl alcohol resin may be prepared as follows, for example: first, forming an ethylene vinyl acetate copolymer by copolymerizing an ethylene and a vinyl acetate, and hydrolyzing the ethylene vinyl acetate copolymer to thereby produce the ethylene vinyl alcohol resin. Alternatively, the ethylene vinyl alcohol resin may be commercially available.

Solvent

[0030] The solvent of the protective coating composition of the present disclosure may be any solvent capable of dissolving polyketones (or, a combination of polyketones and ethylene vinyl alcohol resin). Examples of the solvent may include ethyl alcohol, isopropyl alcohol, methyl isobutyl ketone, normal butyl alcohol, propylene glycol monomethyl ether, xylene, toluene, methyl ethyl ketone, acetone, hexanone, or a combination thereof. Preferably, the solvent may include ethyl alcohol, isopropyl alcohol, methyl isobutyl ketone, normal butyl alcohol, propylene glycol monomethyl ether, or a combination thereof, and these solvents are highly effective at dissolving polyketones and can be dried at a fast rate due to a low boiling point. Most preferably, the solvent may include a mixture of ethyl alcohol and normal butyl alcohol, or a mixture of ethyl alcohol and propylene glycol monomethyl ether. The inventors have discovered that such a mixture of ethyl alcohol and normal butyl alcohol, or a mixture of ethyl alcohol and propylene glycol monomethyl ether, has a fast drying rate, and also, prevents blushing from occurring in the formed protective coating. In the mixture of ethyl alcohol and normal butyl alcohol, the weight ratio of normal butyl alcohol to ethyl alcohol may be, for example, about 1:99 to about 99:1. In the mixture of ethyl alcohol and propylene glycol monomethyl ether, the weight ratio of propylene glycol monomethyl ether to ethyl alcohol may be, for example, about 1:99 to about 99:1. The amount of solvent in the protective coating composition is a remainder amount in the protective coating composition, except for polyketones (or, combination of a polyketone and an ethylene vinyl alcohol resin) and additives.

Additives

[0031] Another embodiment of the protective coating composition of the present disclosure may further include an additive. Examples of the additive may include a low-molecular weight acrylic levelling agent, a fluorescent bleaching agent, or a combination thereof. The low-molecular acrylic levelling agent can lower the surface tension of the protective coating composition, thereby increasing smoothness of the protective coating. The amount of additives in the protective coating composition may be about 0.01 wt % to about 20 wt % with respect to the total weight of the protective coating composition.

Preparation of Protective Coating Composition

[0032] The protective coating composition of the present disclosure may be prepared by dissolving, in a solvent, polyketones (or a combination of polyketones and ethylene vinyl alcohol resin) and optionally, an additive.

Formation of Protective Coating

[0033] A method of forming a protective coating according to another aspect of the present disclosure includes performing, at least once, a process of applying a protective coating composition according to one aspect of the present disclosure on at least a portion of a surface of a circuit board on which an electrical/electronic component is mounted, and then drying the applied protective coating composition. The application of the protective coating composition may be performed by, for example, a spray method, a painting method, or a combination thereof. The drying of the applied protective coating composition refers to removal of a solvent from the applied protective coating composition. The time and temperature for the drying of the applied protective coating composition may vary depending on the solvent used. For example, the drying time may be about 1 second to about 1 hour, or about 10 seconds to about 10 minutes, or about 30 seconds to about 3 minutes, or about 1 minute to about 2 minutes. For example, the drying temperature may be about 0° C. to about 60° C., about 5° C. to about 50° C., or about 10° C. to about 40° C., or about 20° C. to about 30° C.

[0034] The thickness of the finally formed protective coating increases as the number of the above processes performed. The thickness of the finally formed protective coating may be, for example, about 1 μm or more, or about 2 μm or more, or about 3 μm or more, or about 5 μm or more, or about 12 μm or more, or about 16 μm or more. The thickness of the finally formed protective coating may be, for example, about 20 μm or less, or about 16 μm or less, or about 12 μm or less, or about 5 μm or less, or about 3 μm or less. It was found that when the finally formed protective coating has a thickness of about 2 μm or more, the infiltration of corrosive gas (hydrogen sulfide in particular) is extremely effectively prevented. Therefore, preferably, the thickness of the finally formed protective coating may be, for example, about 2 μm to about 5 μm. Most preferably, the thickness of the finally formed protective coating may be, for example, about 2 μm to about 3 μm.

Laminate Including Circuit Board and Protective Coating

[0035] By the above-described method of forming a protective coating of the present disclosure, a protective coating including a polyketone may be laminated on at least a portion of a surface of a circuit board on which an electrical/electronic component is mounted. Accordingly, provided according to another aspect of the present disclosure is a laminate including: a circuit board on which an electrical/electronic component is mounted; and a protective coating formed on at least a portion of a surface of the circuit board, the protective coating including a polyketone.

Removal of Protective Coating

[0036] In the present disclosure, removal of at least a portion of the protective coating from a laminate including “a circuit board on which an electrical/electronic component is mounted” and “a protective coating including a polyketone” in order to replace a defective electrical/electronic component may be performed in an extremely convenient manner. That is, by contacting an area of the protective coating sought to be removed, with a solvent capable of dissolving a polyketone, the protective coating may be removed in an extremely simple manner. The solvent may be brought in contact with the protective coating by, for example, a spray method, a painting method, or a combination thereof. Examples of the solvent capable of dissolving a polyketone may include ethyl alcohol, isopropyl alcohol, methyl isobutyl ketone, normal butyl alcohol, propylene glycol monomethyl ether, xylene, toluene, methyl ethyl ketone, acetone, hexanone, or a combination thereof. The solvent used for removal of the protective coating may be the same solvent used in the preparation of the protective coating composition, or may be different therefrom.

MODE OF DISCLOSURE

Examples

Preparation of Protective Coating Composition

[0037] According to compositions shown in Table 1, the protective coating composition of Examples 1 to 4 and Comparative Examples 1 to 4 were prepared at room temperature.

TABLE-US-00001 TABLE 1 Composition (wt %) Comparative Comparative Comparative Comparative Material name Example 1 Example 2 Example 3 Example 4 Example 1 Example 2 Example 3 Example 4 Polyketone (Germany, TEGO, 5 5 Product name: VariPlus CA) Polyurethane (Germany, TEGO, 5 Product name: VariPlus SK) Polyketone (Korea, Hyundai 5 5 2.5 Chemical, SN-206) Acrylic lacquer resin (Korea, 5 Aekyung Chemical Co., Ltd., 52-204) Polyvinyl butyral (Japan, 5 2.5 Kuraray Korea Co., Ltd., PVB) Acrylic leveling agent 0.5 0.5 0.5 (Korea, FTC Korea, LA-45) Fluorine wax 0.5 (USA, SHAMROCK, SST-3) Ethanol (Korea, SYT 95 94 94.5 55 39 39 39 94.5 ETHANOL Co. Ltd., ETOH99) Propylene Glycol Monomethyl 40 Ether (Korea, SAMYUNG TRADING Co. Ltd., PM) Isopropyl Alcohol (Korea, 23 23 23 SAMYUNG TRADING Co. Ltd., IPA) Methyl Isobutyl Ketone (Korea, 33 33 33 SAMYUNG TRADING Co. Ltd., MIBK) Total 100 100 100 100 100 100 100 100

Corrosion Protection Performance Test

[0038] Each of the protective coating compositions of Examples 1 to 4 and Comparative Examples 1 to 4 was applied onto the entire surface of a copper sample by a spray method, and dried at room temperature for 1 minute. Such application and drying processes were repeated until the thickness of the formed protective coating reached 2 μm.

[0039] Sulfur was introduced under a desiccator. Then, a tray was installed in the middle of the desiccator. Next, on the tray inside the desiccator, the copper samples having a protective coating were arranged. Next, the lid of the desiccator was closed. Next, the desiccator was placed in an oven at 105° C.

[0040] Next, over 30 days, the presence or absence of discoloration in the respective copper samples inside the desiccator was observed with naked eyes. Since, for all of the copper samples with a discoloration, the discoloration occurred over the entire surface of the corresponding copper sample, observing for discoloration of the copper samples with naked eyes was extremely apparent and easy. The time points at which such discolorations occurred were summarized in Table 2.

TABLE-US-00002 TABLE 2 Example No. Number of days until discoloration Example 1 No discoloration even after 30 days Example 2 No discoloration even after 30 days Example 3 No discoloration even after 30 days Example 4 No discoloration even after 30 days Comparative Example 1 Discoloration after 1 day Comparative Example 2 Discoloration after 1 day Comparative Example 3 Discoloration after 1 day Comparative Example 4 Discoloration after 1 day

Ag Corrosion Protection Performance Test

[0041] Resistor, which is a representative example of electrical/electronic components, contains silver (Ag). When a resistor is exposed to hydrogen sulfide, silver inside the resistor reacts with hydrogen sulfide and forms silver sulfide. Since silver sulfide is a nonconductor, a resistor exposed to hydrogen sulfide comes to have an increased resistance value. Therefore, through changes in resistance value of the resistor covered with a protective coating, hydrogen sulfide protection performance of the protective coating can be evaluated.

[0042] First, a test circuit board was prepared by mounting 40 resistors (Samsung Electro-Mechanics, 5 kΩ) on a test PCB. 10 of such test circuit boards were prepared. Each of the protective coating compositions of Examples 1 to 4, Comparative Examples 1 to 4, and Comparative Example 5 (Novec 2704, 3M) was applied on the entire surface of the test circuit board by a spraying method, and dried at room temperature for 1 minute. Such application and drying processes were repeated until the thickness of the formed protective coating reached 2 μm.

[0043] Sulfur was introduced under a desiccator. Then, a tray was installed in the middle of the desiccator. Next, on the tray inside the desiccator, the test circuit boards having a protective coating were arranged. Next, the lid of the desiccator was placed. Next, the desiccator was placed in an oven at 105° C.

[0044] Next, for 30 days, resistance values of 40 resistors on each of the test circuit boards in the desiccator were measured daily. If a resistor has a resistance value that is increased by 10% or more of the original resistance value, said resistor was determined as defective. However, in practice, all of defective resistors had infinitely increased resistance values, and thereby, it was extremely clear and easy to determine whether a resistor was defective. Defective rate was calculated by determining how many of the 40 resistors mounted on each of the test circuit boards were defective. The results are summarized in Table 3.

TABLE-US-00003 TABLE 3 Defective Defective Defective rate after rate after rate after Example No. 10 days 20 days 30 days Example 1  0%  0%   3% Example 2  0%  0%   3%     Example 3  0%  0%   3%       Example 4  0%  0%   3% Comparative  8% 40%  58% Example 1 Comparative 60% 80% 100% Example 2 Comparative  3%  3%  8% Example 3   Comparative  0% 15% — Example 4 Comparative 24% 80%  91% Example 5 (Novec 2704, 3M) Comparative 96% (100% after 15 — Example 6 days) (Uncoated circuit board)

Ag Corrosion Protection Performance Test According to Coating Thickness

[0045] 6 of the test circuit boards described above were prepared. The respective protective coating compositions of Example 1 and Comparative Example 5 (Novec 2704, 3M) were applied onto the entire surface of the respective test circuit boards by a spraying method, and dried at room temperature for 1 minute. The above application and drying processes were repeated until the thickness of the formed protective coating reached thicknesses shown in Table 4. The Ag corrosion protection performance test, as described above, was performed on the respective test circuit boards having the protective coatings prepared above. The results are summarized in Table 4.

TABLE-US-00004 TABLE 4 Protective coating Comparative composition Example 5 Example 1 Example 1 Example 1 Example 1 Example 1 Protective coating thickness (μm) 20 2 4 12 16 20 Defective rate (%) after 8 days 0 0 0 0 0 0 Defective rate (%) after 9 days 1 1 0 0 0 0 Defective rate (%) after 20 days 18 1 0 0 0 0 Defective rate (%) after 30 days 24 2 1 3 0 3 Defective rate (%) after 40 days 31 8 5 5 1 11 Defective rate (%) after 50 days 35 11 8 8 6 14 Defective rate (%) 35 15 8 12 10 15 after 60 days

Reliability Test

[0046] On the protective coating (thickness 2 μm) formed of the protective coating composition of Example 1, a contact angle measurement test, a saline spray test, and an insulation resistance measurement test were performed. The results are summarized in Table 5.

TABLE-US-00005 TABLE 5 Protective coating of Comparative Protective Example 5 coating of (Novec 2704, Test item Test method Example 1 3M) Water Contact Initial 112.5° 109.1° angle High temperature, 109.8° — high humidity (85° C., 85%, 120 h) Heat shock 104.0° — (−40° C.~85° C., 72 h) UV light 105.0° — (UV-B(313 nm), 72 h) Saline spray Test circuit board No change in — test (resistor mounted), resistance 10 days value Insulation 500 V 99.9 GΩm 11.9 GΩm resistance test

INDUSTRIAL APPLICABILITY

[0047] As shown in Table 5, the protective coating formed from the protective coating composition according to the present disclosure exhibits highly effective moisture protection performance as well as highly effective insulation performance, and thus may be highly suitable as a protective coating for a circuit board. In addition, a protective coating formed from the protective coating composition according to the present disclosure can achieve, at an extremely reduced thickness, highly improved protection performance against corrosive gas (hydrogen sulfide in particular) compared to a conventional conformal coating.