Peel carrier structure and copper foil composite structure

Abstract

A release carrier structure that allows the copper foil to be easily separated from the corresponding release layer, and a copper foil composite structure including the release carrier structure are provided. [Solution] A release carrier structure (100) includes a carrier layer (170), a first release layer (110), and a second release layer (120), where the weight ratio of the organic material in the second release layer is greater than the weight ratio of the organic material in the first release layer. The second release layer is made of a film-forming composition, and the film-forming composition includes an azole compound. A copper foil composite structure (200) includes the release carrier structure and a copper foil (280) disposed on the second release layer of the release carrier structure.

Description

[Technical Field]

[0001] The present invention relates to a release carrier structure and a copper foil composite structure, and more particularly to a release carrier structure and a copper foil composite structure including an organic release layer. [Background technology]

[0002] The copper foil manufacturing method generally involves forming a corresponding copper foil on a corresponding carrier structure, and then removing or separating the copper foil formed on the carrier structure by peeling or peeling.

[0003] As electronic devices become more compact, thin copper foils with thicknesses of approximately 10 micrometers (μm) and even thinner ultra-thin copper foils are commonly used in the manufacture of fine or thin printed wiring boards. However, in the manufacturing process of thin or ultra-thin copper foils (especially the removal / separation method by peeling or peeling described above), if the adhesive strength between the copper foil and the carrier structure is too strong, a greater force is often required to peel or separate the copper foil. If a greater force is applied or if the force is applied unevenly, scratches, wrinkles, or patterns may appear on the copper foil.

[0004] Therefore, how to improve the quality of copper foil by improving the carrier structure is an issue to be studied in the art. Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a release carrier structure that allows the copper foil to be easily separated from the corresponding release layer, and a copper foil composite structure including the release carrier structure. [Means for solving the problem]

[0006] The release carrier structure of the present invention includes a carrier layer, a first release layer, and a second release layer, wherein the weight ratio of the organic material in the second release layer is greater than the weight ratio of the organic material in the first release layer.

[0007] The copper foil composite structure of the present invention includes a release carrier structure according to the present invention and a copper foil, the copper foil being disposed on the second release layer of the release carrier structure. [Effects of the Invention]

[0008] Based on the above, in the release carrier structure and the copper foil composite structure including the release carrier structure of the present invention, the copper foil can be easily separated from the corresponding organic release layer (eg, second release layer). [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic cross-sectional view of a peeling carrier structure according to an embodiment of the present invention; [Figure 2] 1 is a schematic cross-sectional view of a copper foil composite structure according to an embodiment of the present invention; [Figure 3] 1 is a schematic cross-sectional view illustrating an application method of a copper foil composite structure according to an embodiment of the present invention. [Figure 4] 1 is a schematic cross-sectional view of a copper foil composite structure according to a comparative example of the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0010] In the following detailed description, by way of example and not limitation, exemplary embodiments disclosing specific details are described to provide a thorough understanding of the various principles of the present invention. However, it will be apparent to those skilled in the art that the present invention may be practiced in other embodiments that depart from the specific details disclosed herein while still benefiting from the present invention. Moreover, descriptions of commonly known devices, methods, and materials may be omitted so as not to distract from the description of the various principles of the present invention.

[0011] Ranges may be expressed herein as from "about" one particular value to "about" another particular value, which may be expressed directly as the one particular value and / or the other particular value. When a range is expressed, another embodiment includes up to the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by using the preceding word "about," it is understood that the particular value forms another embodiment. It is further understood that the endpoints of each range may or may not be related to the other endpoint.

[0012] In the context of this specification, non-limiting terms (e.g., "may," "can," "for example," or other similar terms) indicate non-required or optional implementation, inclusion, addition, or presence.

[0013] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It is also understood that terms (such as those defined in commonly used dictionaries) should be interpreted to have a meaning consistent with the meaning in the relevant technical context, and should not be interpreted in an idealized or overly formal sense unless explicitly defined as such.

[0014] In the drawings, the thickness of some of the film layers may be exaggerated for clarity.

[0015] FIG. 1 is a schematic cross-sectional view of a peeling carrier structure according to an embodiment of the present invention.

[0016] Referring to FIG. 1, a release carrier structure 100 includes a carrier layer 170 , a first release layer 110 , and a second release layer 120 .

[0017] [Peel carrier structure carrier layer]

[0018] In the present invention, the material of the carrier layer 170 is not particularly limited as long as the carrier layer 170 is suitable for carrying a film, layer, and / or component thereon and is suitable for subsequent use. In one embodiment, the carrier layer 170 may be a sheet, plate, or block of metal material. In a preferred embodiment, the carrier layer 170 may be a copper material (e.g., a copper sheet, copper plate, or copper block), which is considered preferable because the copper material may have the same or similar coefficient of thermal expansion (CTE) and / or the same or similar physical or chemical properties as a copper layer (e.g., a copper plating layer or copper foil) subsequently formed thereon.

[0019] In one embodiment, the thickness of the carrier layer 170 can be from about 18 micrometers (μm) to about 35 μm. [First release layer of release carrier structure]

[0020] In one embodiment, the weight ratio of the inorganic material in the first release layer 110 is greater than the weight ratio of the inorganic material in the second release layer 120. In one embodiment, the first release layer 110 is also referred to as an inorganic release layer. In one embodiment, the first release layer 110 is essentially free of organic material.

[0021] In a preferred embodiment, the first release layer 110 may be formed of an inorganic metal salt, which is considered preferable because the first release layer 110 formed of an inorganic metal salt has a stronger bond between a film layer (e.g., second release layer 120) formed of an organic material and a metal (e.g., copper) than between the film layer (e.g., second release layer 120) and the metal (e.g., copper). That is, the bond between the first release layer 110 and the metal (e.g., copper) carrier layer 170 may be stronger than the bond between the film layer (e.g., second release layer 120) and the metal (e.g., copper). Conversely, the bond between the first release layer 110 and the film layer (e.g., second release layer 120) and the organic material may be stronger than the bond between the film layer (e.g., second release layer 120) and the metal (e.g., copper).

[0022] In one embodiment, the first release layer 110 can be formed on the carrier layer 170 by electroplating. The electrolyte used for electroplating can be an electrolyte compound containing nickel, cobalt, molybdenum, manganese, iron, and / or tungsten, such as sulfates, nitrates, phosphates, or chlorides of nickel, cobalt, molybdenum, manganese, iron, and / or tungsten, salts derived from oxides of these metals, and / or hydrates of the salts.

[0023] In one embodiment, before forming the first release layer 110 on the carrier layer 170, the carrier layer 170 may be subjected to a suitable pre-treatment. The pre-treatment may include, but is not limited to, acid cleaning, alkaline cleaning, degreasing, and / or electrolytic cleaning to make the outer surface of the carrier layer 170 cleaner and / or more amenable to adhesion of the first release layer 110.

[0024] In one embodiment, the nickel-containing compound may include, for example, nickel sulfate, nickel ammonium sulfate, nickel nitrate, or nickel chloride.

[0025] In one embodiment, the cobalt-containing compound may include, for example, cobalt sulfate, cobalt nitrate, cobalt phosphate, or cobalt chloride.

[0026] In one embodiment, the molybdenum-containing compound may include, for example, sodium molybdate, potassium molybdate, molybdenum disulfide, molybdenum nitrate, molybdenum phosphate, or molybdenum chloride.

[0027] In one embodiment, the manganese-containing compound may include, for example, manganese sulfate, manganese nitrate, manganese phosphate, manganese chloride.

[0028] In one embodiment, the iron-containing compound may include, for example, iron sulfate, iron nitrate, iron phosphate, or iron chloride.

[0029] In one embodiment, the tungsten-containing compound may include, for example, sodium tungstate or potassium tungstate.

[0030] In one embodiment, the solvent for the electrolyte may be water.

[0031] The pH of the electrolyte can be adjusted by adding an acidic or alkaline agent. In one embodiment, the pH of the electrolyte may be about 2.5 to 4.5. In one embodiment, the added acidic agent may include sulfuric acid, nitric acid, hydrochloric acid, or phosphoric acid.

[0032] In one embodiment, the temperature of the electrolysis may be in the range of about 20° C. to 60° C. In one embodiment, the current density of the electrolysis is about 0.1 A / dm 2 from 50A / dm 2 It may be within the range.

[0033] In one embodiment, the concentration of plating metal ions in the electrolyte may be between about 0.005M (molar concentration, mol / L) and 0.5M.

[0034] In one embodiment, the conductivity of the electrolyte can be adjusted by adding a separate non-plating electrolyte, where the metal contained in the "non-plating electrolyte" is essentially not reduced and is plated onto the carrier layer 170. The "non-plating electrolyte" can include, for example, the corresponding potassium or sodium salt.

[0035] In one embodiment, the electroplating time can be adjusted according to the requirements (e.g., corresponding thickness) or corresponding conditions (e.g., current density, electroplating temperature, and / or concentration of plating metal ions).

[0036] In one embodiment, the electroplated layer formed on the carrier layer 170 essentially serves as the first release layer 110 .

[0037] In one embodiment, after electroplating, the carrier layer 170 and the electroplated layer thereon can be preferably heated appropriately to form a corresponding first release layer 110. One reason this may be preferred is that it may promote the formation of a corresponding eutectic mixture between the metal in the first release layer 110 and the metal in the carrier layer 170, thereby improving the bonding strength between the first release layer 110 and the carrier layer 170. Another reason this may be preferred is that it may promote oxidation and / or roughening of the outer surface of the first release layer 110 (i.e., the surface not in contact with the carrier layer 170 and exposed to the outside), thereby improving the bonding strength between the first release layer 110 and the subsequently formed second release layer 120.

[0038] In one embodiment, the thickness of the first release layer 110 may be between about 10 nanometers (nm) and 1 μm, and preferably between about 50 nm and 300 nm.

[0039] [Second release layer of release carrier structure]

[0040] After a corresponding first release layer 110 is formed on the carrier layer 170 , a second release layer 120 can be formed on the first release layer 110 .

[0041] In one embodiment, the weight ratio of organic material in second release layer 120 is greater than the weight ratio of organic material in first release layer 110. In one embodiment, the weight ratio of inorganic material in second release layer 120 is less than the weight ratio of inorganic material in first release layer 110. In one embodiment, second release layer 120 can be essentially free of inorganic material. In one embodiment, second release layer 120 is also referred to as an organic release layer.

[0042] In one embodiment, the corresponding film-forming composition may be formed on the first release layer 110 by spraying, roll coating, impregnation, sprinkling, or other suitable method. The film-forming composition on the first release layer 110 may then be selectively solidified or semi-solidified by a suitable method (e.g., heating and / or standing) to form the corresponding second release layer 120. In one embodiment, the step of forming the corresponding film-forming composition on the first release layer 110 may be performed in an environment of about 15°C to 70°C, and preferably in an environment of room temperature (about 25°C) to 70°C.

[0043] In one embodiment, the film-forming composition may include an azole compound.

[0044] In one embodiment, the concentration of the azole compound in the film-forming composition may be from about 0.1 grams / liter to about 50 grams / liter.

[0045] In one embodiment, the azole compound may include imidazole, triazole, tetrazole, a derivative thereof, or a mixture thereof. The "derivative" may refer to a compound in which a hydrogen atom bonded to a carbon atom of the azole ring is replaced with an electron-donating group, or a compound in which the azole ring is fused with an aromatic ring. The "electron-donating group" may include, for example, a dialkylamino group (-NRR'), an alkylamino group (-NHR), an amino group (-NH), a hydroxyl group (-OH), or an alkoxy (-OR). A nitrogen-containing electron-donating group is preferred, and an amino group is more preferred. The "aromatic ring" may include, for example, a benzene ring or a naphthalene ring, with a benzene ring being preferred.

[0046] In one embodiment, the film-forming composition can be made correspondingly basic by adding an alkaline agent. In one embodiment, the added alkaline agent can include sodium hydroxide, potassium hydroxide, or a mixture thereof. In one embodiment, the base equivalent of the film-forming composition is approximately equal to about 0.1% to about 20% by weight of sodium hydroxide.

[0047] In one embodiment, when the film-forming composition includes an azole compound having an azole ring fused with an aromatic ring, the corresponding conjugate base is stabilized by the benzene ring in an alkaline environment. In this way, the film-forming composition and / or the correspondingly formed film layer may be more stable. In one embodiment, the azole compound having an azole ring fused with an aromatic ring may include, for example, benzotriazole (CAS: 95-14-7).

[0048] In one embodiment, when the film-forming composition contains an azole compound in which the hydrogen atom of the azole ring is replaced with an amino group, the corresponding ammonium ion (-NH +) state. In this way, the film-forming composition and / or the correspondingly formed film layer may be more stable and / or may exhibit better bonding with the first release layer 110. In one embodiment, the azole compound in which the hydrogen of the carbon atom of the azole ring is replaced with an amino group may include aminotetrazole, aminotriazole, aminodiazole, etc. In one embodiment, the aminotetrazole may include 5-aminotetrazole (CAS: 4418-61-5) and 1,5-diaminotetrazole (CAS: 2165-21-1). In one embodiment, the aminodiazole may include 2-amino-1,3,4-thiadiazole (CAS: 4005-51-0). In one embodiment, the aminotriazole may include 3,5-diamino-1,2,4-triazole (CAS: 1455-77-2).

[0049] In one embodiment, the film-forming composition may be an aqueous sodium hydroxide solution containing aminotetrazole and benzotriazole, wherein the aminotetrazole concentration is between about 0.1 grams per liter (g / L) and 10 g / L, the benzotriazole concentration is between about 0.1 g / L and 10 g / L, and the sodium hydroxide concentration is between about 0.1% and 5% by weight.

[0050] In one embodiment, the film-forming composition may be an aqueous sodium hydroxide solution containing 2-amino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, and benzotriazole. In one embodiment, the weight concentration ratio of 2-amino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, and benzotriazole in the film-forming composition is about 1:1:1 to 1:1:3. In one embodiment, the total weight concentration of 2-amino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, and benzotriazole in the film-forming composition is about 0.1 g / L to 10 g / L, and the concentration of sodium hydroxide is about 0.1 wt% to 5 wt%.

[0051] In one embodiment, the thickness of the second release layer 120 may be about 1 nm to 100 nm, more preferably 1 nm to 50 nm, and even more preferably 1 nm to 20 nm.

[0052] [Peeling carrier structure]

[0053] 1, in the release carrier structure 100, the first release layer 110 may be interposed between the carrier layer 170 and the second release layer 120. Two opposing sides of the first release layer 110 may contact the carrier layer 170 and the second release layer 120, respectively.

[0054] In one embodiment, the material and formation method of the first release layer 110 are different from the material and formation method of the second release layer 120, so that there may be corresponding contact interfaces between the first release layer 110 and the second release layer 120.

[0055] In one embodiment, a corresponding eutectic mixture may be formed at the contact point between the first release layer 110 and the carrier layer 170 .

[0056] [Copper foil composite structure]

[0057] FIG. 2 is a schematic cross-sectional view of a copper foil composite structure according to an embodiment of the present invention.

[0058] The copper foil composite structure 200 may be formed from the release carrier structure 100 of the above-described embodiments.

[0059] In one embodiment, a corresponding copper foil 280 may be formed on the second release layer 120 by sputtering, sputtering followed by electroplating, or other suitable or commonly employed methods.

[0060] In one embodiment, the thickness of the copper foil 280 may be approximately 1 μm to 5 μm.

[0061] [Application methods of copper foil composite structures]

[0062] The application method of the copper foil composite structure 200 can be adjusted as needed, and is not particularly limited in the present invention.

[0063] In one embodiment, the copper foil composite structure 200 shown in FIG. 2 can be appropriately cut.

[0064] In one embodiment, the copper foil composite structure 200 shown in FIG. 2 can be suitably wound.

[0065] In one embodiment, the copper foil 280 of the copper foil composite structure 200 shown in FIG. 2 can be patterned by any suitable method.

[0066] In one embodiment, another film layer can be formed by any suitable method on the copper foil 280 of the copper foil composite structure 200 shown in FIG.

[0067] In one embodiment, as shown in FIGS. 2-3, the copper foil 280 (which may include unpatterned copper foil or patterned copper foil) can be separated from the second release layer 120.

[0068] In one embodiment, the copper foil composite structure 200 is heated and pressed according to the requirements of the copper foil substrate manufacturing process, resulting in different degrees of peel force during the process of separating the copper foil 280 from the second release layer 120.

[0069] According to the second release layer 120 of the present invention, the copper foil 280 can be easily peeled from the second release layer 120. This reduces the risk of damage, wrinkles, or patterns due to uneven stress during the separation process of the copper foil 280 or on the separated copper foil 280.

[0070] [Examples and Comparative Examples]

[0071] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0072] [Example]

[0073] The copper foil composite structure of the example was formed using the method described in the above embodiment. The copper foil composite structure of the example includes a release carrier structure and a copper foil plated thereon. The cross section of the copper foil composite structure of the example may be the same as or similar to that shown in FIG. 2. That is, in the copper foil composite structure of the example, the release carrier structure may be the same as or similar to the release carrier structure 100 of the above-described embodiment. Furthermore, the materials, thicknesses, and formation methods of the copper foil, second release layer, first release layer, and / or carrier layer of the example may be the same as or similar to the materials, thicknesses, and formation methods of the copper foil 280, second release layer 120, first release layer 110, and / or carrier layer 170 of the above-described embodiment, respectively.

[0074] In the examples, the film-forming composition used to form the second release layer was an aqueous sodium hydroxide solution containing 2-amino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, and benzotriazole. The total concentration of 2-amino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, and benzotriazole was about 0.1 g / L to 10 g / L, the weight ratio was 1:1:1 to 1:1:3, and the sodium hydroxide concentration was about 0.1 wt% to 5 wt%.

[0075] [Comparative Example 1]

[0076] The copper foil composite structure of Comparative Example 1 is similar to the copper foil composite structure of the Examples, except that the copper foil composite structure of Comparative Example 1 does not have a film layer that is the same as or similar to the second release layer.

[0077] 4, the copper foil composite structure 200c of Comparative Example 1 includes a release carrier structure 100c and a copper foil 280c plated thereon. The release carrier structure 100c includes a carrier layer 170c and a release layer 110c.

[0078] In the copper foil composite structure 200c of Comparative Example 1, the material, thickness, or formation method of the copper foil 280c, release layer 110c, and / or carrier layer 170c may be the same as or similar to the material, thickness, or formation method of the copper foil, first release layer, and / or carrier layer in the embodiments, respectively.

[0079] [Evaluation of Examples and Comparative Example 1]

[0080] Copper foils were peeled at various temperatures using common or standard peel test methods (e.g., ASTM D1000, ASTM D3330, or similar tests). Ten sets of experiments were repeated under the same test conditions, and the average value (unit: gf / cm) of the minimum peel force required to peel the copper foil and its standard deviation (unit: gf / cm) were recorded. The test results are shown in Table 1.

[0081] [Table 1]

[0082] In the above tests, an environment of approximately 390°C can be used to simulate the temperature range that may be present in the manufacturing process of a flexible circuit board, and an environment of approximately 200°C can be used to simulate the temperature range that may be present in the manufacturing process of a rigid board.

[0083] As shown in Table 1, the copper foil of the copper foil composite structure of the example was easier to peel off than that of Comparative Example 1. Thus, in multiple experiments, the copper foil peeled off from the copper foil composite structure of the example was not damaged, and hardly any wrinkles or patterns due to uneven stress visible to the naked eye were observed.

[0084] Comparative Example 2

[0085] The appearance of the copper foil composite structure of Comparative Example 2 was essentially the same as that of the copper foil composite structure of the Examples, with the difference being the film-forming composition used to form the second release layer. Specifically, in Comparative Example 2, the film-forming composition used to form the second release layer was an aqueous sodium hydroxide solution containing benzotriazole. That is, in Comparative Example 2, the film-forming composition used to form the second release layer did not contain any azole compounds other than benzotriazole (e.g., aminodiazole, aminotriazole, aminotetrazole). Furthermore, the concentration of benzotriazole in the film-forming composition of Comparative Example 2 was essentially the same as the combined concentration of aminotetrazole and benzotriazole in the film-forming composition of the Examples.

[0086] The peel force required to peel the copper foil from the copper foil composite structure of Comparative Example 2 was greater than the peel force required to peel the copper foil from the copper foil composite structure of the Example.

[0087] The peel force required to peel the copper foil from the copper foil composite structure of Comparative Example 2 was slightly smaller than the peel force required to peel the copper foil from the copper foil composite structure of Comparative Example 1.

[0088] In summary, the release carrier structure of the present invention can be adapted to form the copper foil composite structure of the present invention, and further, in the copper foil composite structure of the present invention, the copper foil can be easily peeled from the corresponding release layer (e.g., the second release layer). [Industrial Applicability]

[0089] The release carrier structure of the present invention can be adapted to form the copper foil composite structure of the present invention, which can be adapted for subsequent processing to serve as a material for manufacturing electronic products (e.g., circuit boards). [Explanation of symbols]

[0090] 100, 100c: Peel-off carrier structure 200, 200c: Copper foil composite structure 280, 280c: copper foil 120: Second peel layer 110: First release layer 110c: peel layer 170, 170c: Carrier layer

Claims

1. The carrier layer and a first release layer formed on the carrier layer; a second release layer formed on the first release layer; a release carrier structure for releasing a copper foil formed on the second release layer, comprising: a weight ratio of the organic substance in the first release layer to the total composition of the first release layer is a first weight ratio, a weight ratio of the organic substance in the second release layer to the total composition of the second release layer is a second weight ratio, and the second weight ratio is greater than the first weight ratio; the second release layer comprises a film-forming composition; the film-forming composition is an alkaline solution containing aminodiazole, aminotriazole, and aminotetrazole, the base equivalent of the alkaline solution being equivalent to 0.1% to 20% by weight of sodium hydroxide; A release carrier structure, wherein the thickness of the second release layer is 1-20 nm, and the thickness of the copper foil is 1-5 μm.

2. The release carrier structure of claim 1 , wherein the first release layer and the second release layer contact each other and there is a contact interface therebetween.

3. A peeling carrier structure according to claim 1; the copper foil disposed on the second release layer of the release carrier structure.

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