Glass cloth impregnated with resin composition, and copper-clad laminate using glass cloth impregnated with resin composition, and printed substrate
Patent Information
- Authority / Receiving Office
- TW · TW
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-02-22
- Publication Date
- 2023-09-16
Smart Images
Figure TWG2TA000925483_001 
Figure TWG2TA000925483_002 
Figure TWG2TA000925483_003
Abstract
Description
[Technical Field]
[0001] This invention relates to a resin-impregnated glass cloth for high-frequency conductive printed circuit boards. Furthermore, it relates to a copper-clad laminate and a printed circuit board using the resin-impregnated glass cloth. [Previous Technology]
[0002] In recent years, in order to achieve excellent performance such as high-speed and high-capacity communication in electronic devices, a high-frequency response substrate has been sought. High-frequency response substrates require characteristics of low dielectric properties and low dielectric loss tangent. Therefore, substrates using materials with excellent dielectric properties, such as fluorinated resins, polyphenylene ether (PPE), liquid crystal polymers (LCP), polyphenylene sulfide (PPS), cycloolefin polymers (COP), and modified polyimide (MPI), are being developed.
[0003] Fluoropolymer resins have excellent dielectric properties, but they are expensive or have poor adhesion, making lamination or close-fitting of copper wiring difficult. LCPs also have excellent dielectric properties, but they are expensive or have poor adhesion. COPs also have poor adhesion. MPIs are hygroscopic, resulting in poor dielectric properties at high humidity.
[0004] It is known that substrates using polyphenylene sulfide resin (PPS) have excellent dielectric properties, heat resistance or flame retardancy, and low moisture absorption.
[0005] On the other hand, the PPS film monomer undergoes dimensional changes due to thermal shrinkage, which can easily lead to circuit misalignment during the manufacture of laminated circuit boards. To solve this problem, a method for fixing the PPS film monomer to a fiber sheet, such as glass cloth, is known (Patent Document 1). Additionally, a method for providing a low-melting-point copolymerized PPS layer between the fiber sheet and a copper layer is known because the adhesion between the PPS-impregnated sheet and a metal layer, such as copper for wiring, is insufficient (Patent Document 2). [Prior Art Documents] [Patent Documents]
[0006] [Patent Document 1] Japanese Patent Application Publication No. 4-224941 [Patent Document 2] Japanese Patent Application Publication No. 6-45714 [Summary of the Invention]
[0007] [Problems to be Solved by the Invention] However, in the method described in Patent Document 1, since the fiber sheet, such as glass cloth, is impregnated at a temperature below 270°C (lower than the melting point of PPS), the impregnation into the fiber interior is insufficient. Furthermore, since the PPS crystallization in the obtained PPS-impregnated fiber sheet is insufficient, crystallization occurs during the thermal process in subsequent steps. This leads to dimensional changes, and circuit misalignment during lamination may occur. In Patent Document 2, PPS is impregnated at a temperature above the melting point, but the adhesion to the copper foil is insufficient. Therefore, a copolymer PPS layer needs to be separately placed between the PPS-impregnated fiber sheet and the copper foil, complicating the process. Additionally, since low-melting-point copolymer PPS is used, the solder heat resistance is reduced compared to the case where copolymer PPS is not used.
[0008] Therefore, an object of the present invention relates to a glass cloth impregnated with a resin composition for a printed circuit board, and to a sheet material in which the resin is sufficiently crystallized and has good adhesion to a metal layer without the addition of a new layer of other components. Furthermore, an object of the present invention is also to provide a copper-clad laminate and a printed circuit board using the same. [Means for Solving the Problem]
[0009] The inventors conducted intensive research to solve the aforementioned problem. As a result, they discovered that the problem could be solved by impregnating a resin composition in which polyphenylene sulfide resin is dispersed in a glass cloth at a temperature of 290°C to 315°C, thus completing the present invention.
[0010] That is, the present invention relates to the following (1) to (7).
[0011] (1) A glass cloth impregnated with a resin composition, the resin composition comprising polyphenylene sulfide resin (A) and polyphenylene sulfide resin (B), wherein the content of (A) in the resin composition is 55% to 97% by mass and the content of (B) is 3% to 45% by mass. (2) The glass cloth impregnated with a resin composition according to (1), wherein the resin composition further comprises 1% to 10% by mass of a modified elastomer (C). (3) The glass cloth impregnated with a resin composition according to (2), wherein the modified elastomer (C) comprises a copolymer of α-olefin and glycidyl ester of α,β-unsaturated carboxylic acid, or a copolymer of α-olefin and glycidyl ester of α,β-unsaturated carboxylic acid and (meth)acrylate. (4) The glass cloth impregnated with a resin composition according to (3), wherein the resin composition further comprises 1% to 10% by mass of a styrene-methacrylic acid copolymer. (5) A copper-clad laminate, wherein a copper-containing conductive layer is formed on the surface of a glass cloth impregnated with a resin composition according to any one of (1) to (4). (6) A single-sided, double-sided, and multilayer printed circuit board using the copper-clad laminate according to (5). (7) A method for manufacturing a glass cloth impregnated with a resin composition, comprising the steps of: heating the resin composition according to (1) to (4) to a temperature of 290°C or higher and 315°C or lower, and impregnating the resin composition heated to said temperature into a glass cloth. [Effects of the Invention]
[0012] In this invention, a glass cloth impregnated with a resin composition can be obtained, wherein the impregnation of the resin component in the glass cloth and the resulting material is sufficient, and the adhesion is sufficient even without a layer of other components between it and the metal layer, and it has a low dielectric loss tangent suitable for high-frequency applications. Furthermore, a copper-clad laminate and a printed circuit board using the glass cloth impregnated with the resin composition can be obtained.
Implementation Method
[0014] Hereinafter, the configuration for carrying out the present invention will be described in detail.
[0015] [Resin Composition] The resin composition uses at least polyphenylene sulfide resin (hereinafter sometimes referred to as "PPS" or "PPS resin") A and polyphenylene ether resin (hereinafter sometimes referred to as PPE resin) B as raw materials. The resin composition has a continuous phase and a dispersed phase, the continuous phase comprising PPS resin A and the dispersed phase comprising PPE resin B. Furthermore, to ensure good dispersion, a silane coupling agent is preferably added.
[0016] The average dispersion diameter of the dispersed phase is 5 μm or less, preferably 3 μm or less, and more preferably 0.5 μm to 3 μm. When the average dispersion diameter of the dispersed phase is 5 μm or less, a film as a uniform impregnation material can be obtained.
[0017] [PPS resin] The PPS resin used in this invention is the main component of the resin composition and is, in principle, contained in the continuous phase of the resin composition.
[0018] In order to exert heat resistance, PPS resin is preferably with a melting point of not less than 275°C.
[0019] As a PPS resin, a resin that uses the structural part represented by the following structural formula (1) as the main repeating unit can be listed.
[0020] [Chemical 1]
[0021] In the formula, R1 independently represents hydrogen atom, alkyl, nitro, amino, phenyl, methoxy, and ethoxy groups with 1 to 4 carbon atoms, and n is an integer from 1 to 4.
[0022] Here, in terms of the mechanical strength of the PPS resin, the structural part represented by the structural formula (1) is particularly preferably composed of hydrogen atoms in R1 of the formula.
[0023] As a manufacturing method, as listed in WO2019 / 220882, for example, a method of reacting sodium sulfide with p-dichlorobenzene in an amine solvent such as N-methylpyrrolidone or dimethylacetamide or an amine solvent such as cyclobutane can be listed.
[0024] From the viewpoint of heat resistance and chemical resistance, the content of PPS resin is preferably 55% to 97% by mass relative to the total mass of organic components in the resin composition, more preferably 60% to 95% by mass, and even more preferably 65% to 90% by mass.
[0025] [Polyphenylene ether resin] Since polyphenylene ether resin (PPE resin) is an amorphous polymer, it tends to have low viscosity even at temperatures below the melting point of PPS resin, even at temperatures above the glass transition temperature. Therefore, when bonding copper foil at high temperatures below the melting point of PPS resin, the resin composition containing PPE resin, which is an amorphous polymer, exhibits higher conformability to the unevenness of the copper foil compared to PPS resin, which is a crystalline polymer alone, thereby improving the adhesion strength between the resin and the copper foil. In addition, PPE resin has the characteristic of low dielectric loss tangent, and therefore also has the following characteristics: compared to polymers with poor dielectric loss tangent, such as polycarbonate, it is easier to obtain physical properties suitable for high-frequency applications. Furthermore, since PPE resin has aromatic rings or oxygen-containing functional groups, it also has the following characteristics: compared to aliphatic hydrocarbons such as polypropylene (PP), it has superior adhesion.
[0026] PPE resin is a homopolymer and / or copolymer having the structural part represented by the following structural formula (2).
[0027] [Chemical 2]
[0028] In the formula, R2 is independently a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, a secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, an alkyl group, or a haloalkyl group having at least two carbon atoms separating the halogen atom from the oxygen atom, and m is independently an integer from 1 to 4.
[0029] Specific examples of PPE resins include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), and polyphenylene ether copolymers such as copolymers of 2,6-dimethylphenol with other phenols (e.g., 2,3,6-trimethylphenol or 2-methyl-6-butylphenol). Among these, copolymers of poly(2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol, and 2,3,6-trimethylphenol are preferred, and poly(2,6-dimethyl-1,4-phenylene ether) is even more preferred.
[0030] The content of PPE resin is preferably 3% to 45% by mass relative to the total amount of organic components in the resin composition, and more preferably 5% to 40% by mass from the viewpoint of uniform dispersion in the composition. Furthermore, in order to achieve uniform dispersion, it is preferably 10% to 35% by mass.
[0031] The average molecular weight of the PPE resin is preferably 1,000 or more, more preferably 1,500 to 50,000, and even more preferably 2,500 to 30,000.
[0032] Since PPE resin has low flowability when it is a monomer, the flowability decreases when modified polyphenylene ether resin (m-PPE) is prepared by alloying with styrene-based resins, which is therefore preferable. Furthermore, in terms of improving adhesion to the surface of glass cloth treated with aminosilanes, etc., and functioning as a compatibilizer in reaction with the modified elastomer described later, it is even more preferable that the styrene-based resin is a styrene-methacrylic acid copolymer. The styrene-methacrylic acid copolymer of the present invention is a copolymer of styrene monomers and methacrylic acid monomers, and does not have any functional groups such as glycidyl groups or oxazole groups. The styrene-based resin is preferably 1% to 10% relative to the total amount of organic components in the resin composition, and more preferably 2% to 5% from the viewpoint of homogenization of dispersion in the composition.
[0033] [Alkoxysilanes with amino groups] The resin composition may further contain alkoxysilanes with amino groups. By using alkoxysilanes with amino groups, the dispersibility of polyphenylene ether resin is significantly improved, thereby forming a good morphology.
[0034] Specific examples of alkoxysilanes having an amino group include: γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, etc.
[0035] The amount of the alkoxysilane having an amino group is preferably 0.01% to 5% by mass relative to the total weight of the organic components in the resin composition, more preferably 0.1% to 3% by mass.
[0036] [Modified Elastomer] The modified elastomer is an elastomer containing glycidyl groups or reactive groups such as amine groups or carboxyl groups. In principle, the modified elastomer is contained in the dispersed phase of the resin composition. The modified elastomer in the dispersed phase also functions as a compatibilizer between PPS resin and polyphenylene ether resin, and has the function of improving mechanical strength (tear strength, etc.) through micro-dispersion in the dispersed phase. Furthermore, by using it in combination with styrene-(meth)acrylic acid copolymer, the interfacial adhesion between PPS resin and PPE resin is further improved, and the mechanical strength (tear strength, etc.) is further improved via the modified elastomer.
[0037] Specific examples of modified elastomers include copolymers of α-olefins and α,β-unsaturated glycidyl esters, and copolymers of α-olefins with α,β-unsaturated glycidyl esters and acrylates. That is, in one embodiment, the modified elastomer comprises at least one selected from the group consisting of copolymers of α-olefins and α,β-unsaturated glycidyl esters, and copolymers of α-olefins with α,β-unsaturated glycidyl esters and acrylates.
[0038] Examples of α-olefins include ethylene, propylene, and 1-butene. Among these, ethylene is preferred.
[0039] There are no particular limitations on the α,β-unsaturated glycidyl esters mentioned above, and compounds represented by the following structural formula (3) can be listed.
[0040] [Chemical 3]
[0041] In the formula, R3 is an alkenyl group having 1 to 6 carbon atoms. There are no particular limitations on the alkenyl group having 1 to 6 carbon atoms, and examples include: vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-pentenyl, 1-methyl-3-pentenyl, 1,1-dimethyl-1-butenyl, 1-hexenyl, 3-hexenyl, etc.
[0042] In addition, R4 is independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.
[0043] As the halogen atom, examples include: fluorine atom, chlorine atom, bromine atom, and iodine atom.
[0044] The alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-methylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 2,4-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc.
[0045] Specific examples of the α,β-unsaturated glycidyl ester include glycidyl acrylate, glycidyl methacrylate, etc. Among these, glycidyl methacrylate is preferred.
[0046] When the modified elastomer is a copolymer of α-olefin and α,β-unsaturated glycidyl ester, or a copolymer of α-olefin, α,β-unsaturated glycidyl ester, and acrylate, the content of α,β-unsaturated glycidyl ester in the modified elastomer is preferably 1% to 30% by mass, more preferably 2% to 20% by mass. When the content of α,β-unsaturated glycidyl ester is 1% by mass or more, the target improvement effect can be obtained, and therefore it is preferred. On the other hand, when it is 30% by mass or less, good extrusion stability can be obtained, and therefore it is preferred.
[0047] In addition, when the modified elastomer is a copolymer of α-olefin and α,β-unsaturated glycidyl ester, or a copolymer of α-olefin and α,β-unsaturated glycidyl ester and acrylate, the content of α-olefin in the modified elastomer is preferably 50% to 95% by mass, more preferably 50% to 80% by mass.
[0048] The modified elastomer content is preferably in the range of 1% to 10% by mass relative to the total mass of the resin composition, and more preferably 2% to 5% by mass. This can improve the copper foil adhesion without significantly impairing the excellent physical properties of PPS, such as flame retardancy.
[0049] [Inorganic filler] To further suppress dimensional changes during thermal processes, inorganic fillers may be added to the resin composition. When adding inorganic fillers, in order to produce a uniform film, it is preferable to add them at a concentration of 40% or less, preferably 30% or less, relative to the resin composition.
[0050] [Additives] Plasticizers, weathering agents, antioxidants, heat stabilizers, ultraviolet stabilizers, lubricants, antistatic agents, colorants, flame retardants, etc. may also be added to the resin composition as long as they do not impair the effects of the present invention.
[0051] [Method for Manufacturing the Resin Composition] There are no particular limitations on the method for manufacturing the resin composition. Examples include uniformly mixing the PPS resin, PPE resin, modified elastomer, and other desired formulation components using a rotary drum or Henschel mixer, and then feeding the mixture into a twin-screw extruder for melt mixing. In this case, the melt mixing is preferably carried out under conditions where the ratio of the resin component ejection rate (kg / hr) to the screw speed (rpm) (ejection rate / screw speed) is 0.02 to 0.2 (kg / hr·rpm). By this manufacturing method, a resin composition with an average dispersion diameter of 5 μm or less can be manufactured.
[0052] To further describe the manufacturing method in detail, a method in which the components are fed into a twin-screw extruder and melt-blended at a set temperature of approximately 300°C and a resin temperature of approximately 330°C can be described. In this case, the amount of resin component ejected is in the range of 5 kg / hr to 50 kg / hr at a rotational speed of 250 rpm. Of this, in terms of dispersibility, 20 kg / hr to 35 kg / hr is particularly preferred. Therefore, the ratio of the amount of resin component ejected (kg / hr) to the screw rotational speed (rpm) (ejection amount / screw rotational speed) is particularly more preferably 0.08 to 0.14 (kg / hr·rpm). Furthermore, in terms of improving the dispersibility of the polyphenylene ether resin, etc., the torque of the twin-screw extruder is preferably in the range of a maximum torque of 20 to 100 (Å), particularly 25 to 80 (Å).
[0053] [Film] In the impregnation of the resin composition into glass cloth, a film containing the resin composition can be used. The film can be a non-stretch film or a stretch film, but a non-stretch film that can be manufactured more inexpensively is preferred. There are no particular limitations on the manufacturing method of the non-stretch film or the stretch film, and known methods can be used. For example, after drying the resin composition at 140°C for more than 3 hours and under reduced pressure of 10 mmHg or less, it is fed into an extruder heated to 280°C to 320°C. Then, the molten resin passing through the extruder is sprayed out in sheet form using a T-die, and it is brought into close contact with a cooling roller with a surface temperature of 20°C to 50°C and cooled and solidified to obtain a non-oriented, non-stretch sheet. In addition, as a stretching method when using a stretch film, a sequential twin-screw stretching method, a simultaneous twin-screw stretching method, or a combination of these methods using known methods can be used.
[0054] [Glass cloth] Commercially available glass cloth can be used for resin impregnation. Among them, glass cloth with low dielectric properties and low dielectric loss tangent, such as NE-2116 manufactured by Nittobo, is preferred. However, depending on the target application, dielectric properties, glass fiber diameter or thickness, density, glass raw materials, and surface treatment agent can be appropriately selected.
[0055] [Glass cloth impregnated with a resin composition] To produce a glass cloth impregnated with a resin composition, heating and pressurization are performed while the glass cloth is held between films of the resin composition. The preferred ratio of resin composition to glass cloth is 35 wt% to 80 wt% resin composition and 65 wt% to 20 wt% glass cloth, but this can be appropriately varied depending on the thickness, mechanical properties, dielectric properties, etc., required for the intended application. To adjust the ratio of resin composition to glass cloth, the number of films of the resin composition can be adjusted, with one film on each side to hold the glass cloth, or more films can be used.
[0056] To ensure the resin composition is fully impregnated in the glass cloth, the impregnation temperature is preferably higher than the melting point of PPS and above 290°C. On the other hand, at 320°C, decomposition gases may be generated by the resin components, creating voids; therefore, impregnation is preferably performed at a temperature below 315°C. When the pressure is low, impregnation takes time; when the pressure is high, the resin tends to spread to the outside of the glass cloth. Therefore, impregnation is preferably performed at an appropriate pressure. For example, pressure conditions of 0.1 MPa to 5 MPa, preferably 0.5 MPa to 3 MPa, can be listed, but since the optimal pressure varies depending on the thickness or composition of the target sheet and the stamping temperature, it can be appropriately adjusted.
[0057] The impregnation of the resin composition into the glass cloth can be manufactured by continuously hot pressing while conveying the materials of each roller in an overlapping manner, or by stamping the resin composition cut into a rectangle with the glass cloth. In order to suppress the formation of voids, vacuuming can be performed, but since the device would become complicated, vacuuming may not be performed.
[0058] When PPS resin is rapidly cooled from its molten state, it becomes amorphous and thermally unstable, thus requiring a crystallization process for the resin composition. Therefore, it is necessary to crystallize the PPS resin by impregnating it in glass cloth and then slowly cooling it, or by rapidly cooling it and then heating it to a temperature above the Tg of the PPS resin but below its melting point, for example, any temperature between 150°C and 270°C. Of these, slow cooling is preferable for shortening the process.
[0059] [Layer of Resin-Impregnated Glass Cloth] To adjust the thickness of the target copper-clad laminate, multiple sheets of glass cloth impregnated with the resin composition can be hot-pressed and laminated. Lamination can be performed simultaneously with resin impregnation, or separately. In the case of separate lamination, it can be performed simultaneously with the manufacturing of the copper-clad laminate described later, or it can be performed before manufacturing. Regarding the hot-pressing temperature during separate lamination, if the temperature is too low, the laminated resins cannot fully melt together; if the temperature is too high, the resin seeps out of the glass cloth, making it difficult to control the thickness. Therefore, for example, lamination is preferably performed at 260°C to 275°C. When the stamping pressure is weak, the weld becomes insufficient; when the stamping pressure is strong, the resin expands, making it difficult to control the film thickness. Therefore, it is preferable to select an appropriate pressure for lamination. When the stamping time is short, the weld is insufficient; when the stamping time is long, production efficiency is poor. Therefore, for example, stamping for 15 seconds to 15 minutes is preferred, but stamping for longer periods is also possible. In addition, surface modification can be achieved by corona treatment to enhance adhesion with copper foil.
[0060] [Copper Clad Laminate] A copper clad laminate can be obtained by hot-pressing copper foil onto one or both sides of a resin-impregnated glass cloth or its laminate. Regarding the hot-pressing temperature, when the temperature is too low, the viscosity of the resin composition is high, thus the copper foil's conformity to surface irregularities decreases, resulting in weak adhesion. When the temperature is too high, the resin viscosity decreases excessively, causing the resin to seep out of the glass cloth, making it difficult to control the thickness. Therefore, it is preferable to perform the process at, for example, 260°C to 280°C. When the pressure is weak, the resin's conformity to the copper foil is poor, resulting in weak adhesion. When the pressure is too strong, the copper clad laminate expands, making it difficult to control the film thickness. Therefore, it is preferable to press at, for example, 2 MPa to 20 MPa, preferably 5 MPa to 15 MPa. When the pressing time is short, the adhesion between the copper foil and the resin is insufficient. When the pressing time is long, the production efficiency is poor. Therefore, it is preferable to press for, for example, 5 minutes to 60 minutes, but pressing can also be performed for longer periods.
[0061] To avoid air remaining between the copper foil and the resin during stamping, it is preferable to perform stamping while vacuuming. By preventing air from remaining between the copper foil and the resin, expansion or peeling is less likely to occur, for example, when heating the copper-clad laminate.
[0062] [Copper Foil] The copper foil used can be rolled copper foil or electrolytic copper foil. Electrolytic copper foil is preferred to reduce costs, but it can be selected appropriately depending on the intended application. Furthermore, when the surface roughness of the copper foil is large, the adhesion to the resin-impregnated glass cloth becomes stronger, but the high-frequency transmission characteristics deteriorate. Therefore, the roughness of the copper foil is preferably Rz of 3 μm or less, but a copper foil with suitable roughness can be selected according to the application. In addition, to improve adhesion, copper foil with known surface treatments such as silane coupling agent treatment can also be used.
[0063] [Printed Circuit Board] A printed wiring board can be obtained by using the aforementioned copper-clad laminate and forming wiring patterns using known methods. Furthermore, by connecting electronic components to operate as an electronic circuit, a printed circuit board can be obtained. [Example]
[0064] Next, examples will be given to illustrate the present invention in more detail, but the present invention is not limited thereto.
[0065] (Example 1) A mixture was obtained by uniformly mixing 79.5 parts by weight of MA520 (linear PPS, manufactured by DIC Corporation) as polyphenylene sulfide resin (PPS resin), 15 parts by weight of PX-100 (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) as polyphenylene sulfide resin (PPE resin), 2.5 parts by weight of Ryulex A-14P (methacrylic acid content: 14% by mass, manufactured by DIC Corporation) as styrene-methyl methacrylate copolymer (SMAA), and 3 parts by weight of Bondfast 7L (ethylene / glycidyl methacrylate / methyl acrylate = 70 / 3 / 27 (by mass), manufactured by Sumitomo Chemical Co., Ltd.) as modified elastomer using a rotary drum mixer.
[0066] The obtained mixture is then fed into a twin-screw extruder "TEX-30α" with venting holes manufactured by Nippon Steel Co., Ltd. It is melt-extruded at a flow rate of 20 kg / hr, a screw speed of 300 rpm, and a set temperature of 300°C to produce a filament. After cooling with water at 30°C, it is cut to manufacture a resin composition.
[0067] The resin composition is fed into a single-screw extruder with a fully threaded screw and melted at 280°C to 300°C. After the molten resin composition is extruded from a T-die, it is closely cooled using a cooling roller set to 40°C to produce a 0.05 mm thick unstretched PPS resin film.
[0068] Next, a 30 cm square glass cloth NE-2116 (manufactured by Nitto Boshoku Co., Ltd.) was clamped between two of the aforementioned films (30 cm square), and then clamped with a mirror-finished stainless steel plate. The cloth was then pressed for 15 minutes at a temperature of 300°C and a pressure of 2 MPa. After cooling to below 50°C and pressing again, a 0.12 mm thick resin-impregnated glass cloth was manufactured. The results of differential scanning calorimetry (DSC) measurements on the obtained resin-impregnated glass cloth are shown in Figure 1. No crystallization peak appeared at 190°C during heating, indicating sufficient crystallization.
[0069] Next, six pieces of the resin-impregnated glass cloth were stacked and pressed at a temperature of 270°C and a pressure of 2 Ma for 5 minutes, thereby producing a 0.7 mm thick laminated resin-impregnated glass cloth. The laminated resin-impregnated glass cloth was then surface-treated using a corona surface treatment machine (A3SW-FLNW, manufactured by Wedge Co., Ltd.).
[0070] Next, the laminated resin-impregnated glass cloth is clamped using 18 μm thick copper foil HA-V2 (manufactured by JX Metal Co., Ltd.) and stamped at a temperature of 275°C and a pressure of 10 MPa to manufacture a copper-clad laminate.
[0071] (Example 2) MA520 was set to 60 parts by weight, PX-100 to 33 parts by weight, A-14P to 5 parts by weight, 7L to 2 parts by weight, the impregnation temperature was set to 290°C, and the copper cladding stamping temperature was set to 270°C. Otherwise, the copper clad laminate was manufactured using the same method as in Example 1.
[0072] (Example 3) MA520 was set to 93 parts by weight, PX-100 to 5 parts by weight, A-14P to 1 part by weight, 7L to 1 part by weight, the impregnation temperature was set to 310°C, and the copper cladding stamping temperature was set to 280°C. Otherwise, the copper clad laminate was manufactured using the same method as in Example 1.
[0073] (Example 4) MA520 was set to 85 parts by weight, PX-100 was set to 11 parts by weight, A-14P was set to 2 parts by weight, and 7L was set to 2 parts by weight. Otherwise, the copper-clad laminate was manufactured using the same method as in Example 1.
[0074] (Example 5) MA520 was set to 78 parts by weight, PX-100 to 15 parts by weight, A-14P to 5 parts by weight, and 7L to 2 parts by weight. Otherwise, the copper-clad laminate was manufactured using the same method as in Example 1.
[0075] (Example 6) MA520 was set to 80 parts by weight, PX-100 was set to 20 parts by weight, A-14P was not added, 7L was not added, and the copper-clad laminate was manufactured using the same method as in Example 1.
[0076] (Example 7) A copper-clad laminate was manufactured using a resin composition film stretched by a twin-screw extruder, except that the same method as in Example 1 was used. The twin-screw extrusion was performed using the method shown in Japanese Patent Application 2019-538278.
[0077] (Example 8) The glass cloth used is the common E-2116, and the copper-clad laminate is manufactured using the same method as in Example 1.
[0078] [Comparative Example 1] MA520 was set to 100 parts by weight, PX-100 was not used, A-14P was not used, 7L was not used, and the copper-clad laminate was manufactured using the same method as in Example 1.
[0079] [Comparative Example 2] The immersion temperature was set to 275°C, and the copper-clad laminate was manufactured using the same method as in Comparative Example 1.
[0080] [Comparative Example 3] The immersion temperature was set to 320°C, and the copper-clad laminate was manufactured using the same method as in Comparative Example 1.
[0081] [Comparative Example 4] MA520 was set to 82 parts by weight, PX-100 was not used, polycarbonate (PC) (Iupilon, manufactured by Mitsubishi Chemical Corporation) was set to 15 parts by weight, A-14P was not used, and the copper-clad laminate was manufactured using the same method as in Example 1.
[0082] [Comparative Example 5] MA520 was set at 82 parts by weight, PX-100 was not used, polypropylene (PP) (Sumitomo Noblen, manufactured by Sumitomo Chemical Co., Ltd.) was set at 15 parts by weight, A-14P was not used, and the copper-clad laminate was manufactured using the same method as in Example 1.
[0083] The materials and forming conditions of the copper-clad laminates manufactured in Examples 1 to 8 and Comparative Examples 1 to 5 are shown in Table 1.
[0084] [Table 1] MA520 (PPS) [wt%] PX-100 (PPE) [wt%] Norblen (PP) [wt%] Eupirum (PC) [wt%] A-14P (SMAA) [wt%] 7L (Modified elastomer) [wt%] With or without membrane stretching Fiberglass cloth Immersion temperature Copper plating temperature Example 1 79.5 15 0 0 2.5 3 none NE-2116 300℃ 275℃ Example 2 60 33 0 0 5 2 none NE-2116 290℃ 270℃ Example 3 93 5 0 0 1 1 none NE-2116 310℃ 280℃ Example 4 85 11 0 0 2 2 none NE-2116 300℃ 275℃ Example 5 78 15 0 0 5 2 none NE-2116 300℃ 275℃ Example 6 80 20 0 0 0 0 none NE-2116 300℃ 275℃ Example 7 79.5 15 0 0 2.5 3 have NE-2116 300℃ 275℃ Example 8 79.5 15 0 0 2.5 3 none E-2116 300℃ 275℃ Comparative Example 1 100 0 0 0 0 0 none NE-2116 300℃ 275℃ Comparative Example 2 100 0 0 0 0 0 none NE-2116 275℃ 275℃ Comparative Example 3 100 0 0 0 0 0 none NE-2116 320℃ 275℃ Comparative Example 4 82 0 0 15 0 3 none NE-2116 300℃ 275℃ Comparative Example 5 82 0 15 0 0 3 none NE-2116 300℃ 275℃
[0085] [Impregnation] The impregnation of the glass cloth impregnated with the resin composition was evaluated by observation using an optical microscope (MX51 industrial inspection microscope, manufactured by Olympus Corporation). If there were no voids in the center of the glass cloth's gaps, it was marked as 0; if the impregnation was insufficient, it was marked as X. Figure 2 is a diagram of the resin-impregnated glass cloth of Example 1 observed using an optical microscope. Figure 3 is a diagram of the resin-impregnated glass cloth of Comparative Example 2 observed using an optical microscope. Figure 4 is a diagram of the resin-impregnated glass cloth of Comparative Example 3 observed using an optical microscope.
[0086] [Placement or absence of voids] If no voids are generated in the resin portion of the glass cloth impregnated with the resin composition, it is set to 0; if voids are generated, it is set to X.
[0087] [Peel Strength Test] A 1 cm strip of copper foil from the copper-clad laminate was peeled off the substrate. The tensile strength in the 180° direction was determined using a strograph V1-C tensile and compression testing machine (manufactured by Toyo Seiki Co., Ltd.). The peel strength was then measured. If the peel strength is 0.7 kN / m or higher, it can withstand the heat treatment during the manufacturing of the printed circuit board.
[0088] [280℃ heat resistance] After heating a 5 cm square copper-clad laminate at 280℃ for 30 minutes using a hot air dryer, let it stand at room temperature for more than 30 minutes. Then, the case where the copper foil does not expand or peel off is set as 0, and the case where it expands or peels off is set as X.
[0089] [Dielectric Loss Tangent] A strip 2 mm wide and 150 mm long was made from resin-impregnated glass cloth. The strip was then left to stand for 24 hours at 23°C and 50% Rh. The dielectric loss tangent at a frequency of 1 GHz was measured using the cavity resonance method with an ADMS010c series (manufactured by AET Corporation). The results are shown in Table 2 below.
[0090] [Table 2] Infiltrative gap suppression Peel strength (kN / m) 280℃ heat resistance Dielectric loss tangent Example 1 〇 〇 0.9 〇 0.002 Example 2 〇 〇 1.0 〇 0.002 Example 3 〇 〇 0.8 〇 0.002 Example 4 〇 〇 0.9 〇 0.002 Example 5 〇 〇 1.1 〇 0.002 Example 6 〇 〇 1.0 〇 0.002 Example 7 〇 〇 0.9 〇 0.002 Example 8 〇 〇 0.9 〇 0.002 Comparative Example 1 〇 〇 0.2 X 0.002 Comparative Example 2 X 〇 0.2 X 0.002 Comparative Example 3 〇 X 0.2 X 0.002 Comparative Example 4 〇 〇 0.5 X 0.003 Comparative Example 5 〇 X 0.4 X 0.002
[0091] As is also shown in Table 2, it can be seen that the copper foil adhesion and dielectric properties of the copper-clad laminate obtained by using the resin-impregnated glass cloth are excellent. [Simplified Explanation of the Diagram]
[0013] Figure 1 is a DSC chart of the PPS resin composition. Figure 2 is an optical microscope image of the resin-impregnated glass cloth of Example 1. Figure 3 is an optical microscope image of the resin-impregnated glass cloth of Comparative Example 2. Figure 4 is an optical microscope image of the resin-impregnated glass cloth of Comparative Example 3.
Claims
1. A glass cloth impregnated with a resin composition, the resin composition comprising polyphenylene sulfide resin (A) and polyphenylene ether resin (B), wherein the content of (A) in the resin composition is 55% to 97% by mass, and the content of (B) is 3% to 45% by mass.
2. The glass cloth impregnated with the resin composition as described in claim 1, wherein, The resin composition also contains 1% to 10% by mass of a modified elastomer (C).
3. The glass cloth impregnated with the resin composition as described in claim 2, wherein, The modified elastomer (C) comprises a copolymer of α-olefin and glycidyl ester of α,β-unsaturated carboxylic acid, or a copolymer of α-olefin and glycidyl ester of α,β-unsaturated carboxylic acid and (meth)acrylate.
4. The glass cloth impregnated with the resin composition as described in claim 3, wherein, The resin composition also contains 1% to 10% by mass of a styrene-methacrylic acid copolymer.
5. A copper-clad laminate, wherein a copper-containing conductive layer is formed on the surface of a glass cloth impregnated with a resin composition as described in any one of claims 1 to 4.
6. A single-sided, double-sided, and multilayer printed circuit board using a copper-clad laminate as described in claim 5.
7. A method for manufacturing a glass cloth impregnated with a resin composition, comprising the steps of: heating the resin composition as described in claims 1 to 4 to a temperature of 290°C or higher and 315°C or lower, and impregnating the resin composition heated to said temperature into the glass cloth.