CN115847952A - Circuit material and printed circuit board - Google Patents
Circuit material and printed circuit board Download PDFInfo
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- CN115847952A CN115847952A CN202211615725.2A CN202211615725A CN115847952A CN 115847952 A CN115847952 A CN 115847952A CN 202211615725 A CN202211615725 A CN 202211615725A CN 115847952 A CN115847952 A CN 115847952A
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Abstract
The invention provides a circuit material and a printed circuit board. The circuit material includes a dielectric substrate layer, a conductive metal layer, and a resin layer disposed between the dielectric substrate layer and the conductive metal layer; the dielectric substrate layer includes a reinforcement material and a resin composition overlying the reinforcement material, the resin composition including the following components: (A) a 1, 2-polybutadiene resin; (B) Thermosetting resin with unsaturated double bond of macromolecular chain; (C) an inorganic filler; (D) a flame retardant; (E) a radical initiator. The circuit material provided by the invention has high peel strength after high-temperature aging, and the resonant ring Dk and insertion loss change values after high-temperature aging and high-temperature and high-humidity treatment are small.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to a circuit material and a printed circuit board.
Background
The application scenes of the high-frequency copper-clad plate are more and more, including application scenes of an antenna, a radio frequency, a power amplifier, a filter, a radar and the like, the application scenes are more and more complex, the requirements of terminal customers on the high-frequency copper-clad plate are more and more high, the high-temperature aging is still required to have high peel strength, and the resonant ring Dk and the insertion loss change value after the high-temperature aging and the high-temperature and high-humidity treatment are required to be small.
CN113597088A discloses a circuit material, a preparation method and a circuit board thereof. The circuit material comprises a flexible conductive metal layer, a PET film and an adhesive layer arranged between the flexible conductive metal layer and the PET film, wherein the thickness of the adhesive layer is 0.4-1 mm; the adhesive layer is made of an adhesive, and the adhesive is made of the following raw materials in parts by weight: 80-120 parts of hydroxyl-terminated polydimethylsiloxane, 2-7 parts of ethyl orthosilicate, 2-7 parts of catalyst and 5-15 parts of coated titanium dioxide; the preparation method comprises the following steps: the adhesive is coated between the flexible conductive metal layer and the PET film and is solidified to form an adhesive layer under the condition of 40-55 ℃ to obtain the finished circuit material. The circuit board prepared by the technical scheme has good flexibility, processability and appearance performance, but has poor comprehensive performance after high-temperature aging.
CN111393724A discloses a resin composition and a prepreg and a circuit material using the same. The resin composition comprises unsaturated polyphenyl ether resin, polyolefin resin, rosin resin and an initiator; the content of the rosin resin is 3-40 parts by weight based on 100 parts by weight of the total weight of the unsaturated polyphenylene oxide resin, the polyolefin resin and the rosin resin; the polyolefin resin is selected from one or a combination of at least two of unsaturated polybutadiene resin, SBS resin and styrene-butadiene resin. According to the technical scheme, the unsaturated polyphenyl ether resin, the polyolefin resin and the rosin resin are matched with one another, so that the obtained resin composition has good film forming property, cohesiveness and dielectric property, and a circuit board adopting the resin composition has high interlayer peeling strength and low dielectric loss, but the peeling strength after high-temperature aging is poor, and the resonant ring Dk and insertion loss change value after high-temperature aging and high-temperature high-humidity treatment are also large.
In the prior art, 1, 2-polybutadiene resin is excellent in dielectric property after being cured, highly crosslinked and has very high glass transition temperature, and raw materials are cheap and easy to obtain, so that the 1, 2-polybutadiene resin is often used as a main resin for preparing a high-frequency copper-clad plate, but the carbon-hydrogen high-frequency copper-clad plate in the prior art is seriously deteriorated in electrical property after being aged at high temperature and treated at high temperature and high humidity, and cannot meet the increasingly complex application scene requirements of terminal customers.
Therefore, it is an urgent technical problem to provide a circuit board material having high peel strength after high-temperature aging, a resonant ring Dk after high-temperature aging and high-temperature and high-humidity processing, and a small insertion loss variation value.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a circuit material and a printed circuit board. According to the invention, through designing the structure of the circuit material and the specific composition of the resin composition, and further selecting the 1, 2-polybutadiene resin with specific performance, the prepared circuit material has high peel strength after high-temperature aging, and the resonant ring Dk and insertion loss change value after high-temperature aging and high-temperature high-humidity treatment are small.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a circuit material comprising a dielectric substrate layer, a conductive metal layer, and a resin layer disposed between the dielectric substrate layer and the conductive metal layer;
the dielectric substrate layer includes a reinforcement material and a resin composition overlying the reinforcement material, the resin composition including the following components:
(A) 1, 2-polybutadiene resin, wherein the content of 1, 2-vinyl in the 1, 2-polybutadiene resin is more than or equal to 90%, the number average molecular weight (Mn) is 3000-6000g/mol, and the ratio PDI of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.02-1.08;
(B) The number average molecular weight Mn of the thermosetting resin with the unsaturated double bonds of the macromolecular chains is more than or equal to 50000g/mol;
(C) An inorganic filler;
(D) A flame retardant;
(E) A free radical initiator.
According to the invention, through designing the structure of the circuit material and the specific composition of the resin composition, and further selecting the 1, 2-polybutadiene resin with specific performance, the prepared circuit material has high peel strength after high-temperature aging, and the resonant ring Dk and insertion loss change value after high-temperature aging and high-temperature high-humidity treatment are small.
In the invention, the 1, 2-polybutadiene resin with specific performance is selected, and when the content of 1, 2-vinyl in the 1, 2-polybutadiene resin is more than or equal to 90%, the number average molecular weight (Mn) is 3000-6000g/mol, the circuit material has narrow molecular weight distribution, and the ratio PDI of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.02-1.08, the prepared circuit material has better comprehensive performance.
If the content of 1, 2-vinyl in 1, 2-polybutadiene resin is less than 90%, the curing crosslinking density of the circuit material (also called plate) is deteriorated, so that the aging performance is affected, and finally the resonant ring Dk and the insertion loss change value of the circuit material after aging for 28 days at 188 ℃ are out of limits.
If the number average molecular weight (Mn) of the 1, 2-polybutadiene resin is less than 3000g/mol, the molecular weight is too small, and when the plate is pressed, glue easily flows to generate gully, so that the internal structure of the plate is not compact, and finally the resonant ring Dk and the insertion loss change value of the circuit material after being processed for 1000 hours at 85 ℃ are out of limits; if the number average molecular weight (Mn) of the 1, 2-polybutadiene resin is more than 6000g/mol, the molecular weight is too large, and the resin is not easily flowed when pressed into a plate to cause dry-out, resulting in voids in the internal structure of the plate, and finally, the resonance ring Dk and the insertion loss variation of the circuit material after processing at 85% RH and 85 ℃ for 1000 hours are out of limits.
Meanwhile, when the ratio PDI of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the 1, 2-polybutadiene resin is controlled to be 1.02-1.08, the requirements that the resonance ring Dk and the insertion loss change value of the high-frequency electronic circuit substrate are small after aging and high temperature and high humidity are met. When PDI is less than 1.02, it is difficult for raw material suppliers to synthesize a high molecular weight polymer having an almost complete single molecular weight distribution; when the PDI is more than 1.08, the molecular weight distribution of the resin is wider, the fluctuation value of the resonance ring Dk and the insertion loss data tested by the circuit material is larger, and finally the resonance ring Dk and the insertion loss change value after the circuit material is aged for 28 days at 188 ℃ and treated for 1000 hours at 85 ℃ are higher than the standard.
In the present invention, the 1, 2-polybutadiene resin has a 1, 2-vinyl group content of 90% or more (for example, 90%, 91%, 92%, 93%, 94%, or 95%, etc.), a number-average molecular weight (Mn) of 3000 to 6000g/mol (for example, 3000g/mol, 3300g/mol, 3500g/mol, 3700g/mol, 4000g/mol, 4200g/mol, 4600g/mol, 5000g/mol, 5200g/mol, 5500g/mol, 5700g/mol, or 6000g/mol, etc.), and a PDI ratio of a weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of 1.02 to 1.08 (for example, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, or 1.08, etc.).
The number average molecular weight of the high molecular weight unsaturated double bond-bearing thermosetting resin may be 50000g/mol, 60000g/mol, 65000g/mol, 70000g/mol, 80000g/mol, 90000g/mol, 100000g/mol, 110000g/mol, 120000g/mol, or the like.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferred technical scheme of the invention, the resin layer is an unmodified polyarylether layer.
Preferably, the raw materials for preparing the unmodified polyarylether layer comprise the unmodified polyarylether, metal salt containing unsaturated bonds and a co-curable monomer.
The specific proportion of the raw materials for preparing the unmodified polyarylether layer and the preparation method refer to CN113072885A.
The thickness of the resin layer is preferably 5 to 20 μm, and may be, for example, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 13 μm, 14 μm, 15 μm, 18 μm, or 20 μm.
In the invention, the unmodified polyarylether layer is arranged between the dielectric substrate layer and the conductive metal layer, so that the dielectric substrate layer and the conductive metal layer can be ensured to have higher peel strength after being aged for 10 days at 188 ℃, and finally, the change value of a resonant ring Dk and the insertion loss change value of the circuit material after being aged for 28 days at 188 ℃ are smaller through the synergistic effect of the unmodified polyarylether layer and the resin composition; the change in the ring Dk and the change in the insertion loss were small even after the circuit material was treated at 85% rh for 1000 hours at 85 ℃. The reason is that the crosslinking density of hydrocarbon resin (including 1, 2-polybutadiene resin and thermosetting resin with unsaturated double bonds of high molecular chains) is higher, the molecular chains are easy to age, if no unmodified polyarylether layer is arranged, the surface of the hydrocarbon resin is carbonized and contracted after high-temperature aging, and micro gaps are finally formed between the surface of the hydrocarbon resin and copper foil, so that the peel strength is greatly reduced, the aged resonant ring Dk and the insertion loss change value exceed standards due to carbonization, and the resonant ring Dk and the insertion loss change value exceed standards due to carbonization and the micro gaps after high-temperature and high-humidity treatment.
In a preferred embodiment of the present invention, the sum of the parts by weight of the component (a) and the component (B) is 15 to 25 parts, for example, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, or the like, based on 100 parts by weight of the resin composition.
Preferably, the mass ratio of the component (a) to the component (B) is 2.
In the present invention, the resin proportion and the filler proportion are such that the formulation combines the dielectric properties and the production processability of the product, based on 100 parts by weight of the total amount of the resin composition, 15 to 25 parts by weight of the total amount of the components (A) and (B), and 60 to 78 parts by weight of the total amount of the component (C). If the proportion of the resin is too small, the resin does not fill the voids between the fillers, voids are easily formed, eventually resulting in the circuit material being treated at 85% RH, the resonance ring Dk after 1000 hours of treatment at 85 ℃ and the insertion loss variation exceeding the limits; if the resin ratio is too high, particularly 1, 2-polybutadiene hydrocarbon resin is used, the occurrence of defects such as seizing of the bonding sheet, which affects the production manufacturability and the sheet appearance, and ravines of the resin are likely to occur, eventually leading to the excessive occurrence of the change in the resonant ring Dk and insertion loss after the circuit material is processed at 85% rh,85 ℃ for 1000 hours.
In the invention, the high-molecular-weight thermosetting resin with unsaturated double bonds is added into the formula of the resin composition, so that the high-frequency substrate can be ensured to have better thickness consistency, and the resonance ring Dk and the insertion loss change value are ensured to have smaller fluctuation. Since 1, 2-polybutadiene resin with a number average molecular weight (Mn) of 3000-6000g/mol flows after being heated and pressurized, defects such as gully are easily generated, the thickness of the plate edge is too thin, the thickness of the plate is unstable, and the resonance ring Dk and insertion loss fluctuation are large. The best effect is achieved when the proportion of the 1, 2-polybutadiene resin and the high molecular weight thermosetting resin with unsaturated double bonds is 2; if the proportion of the high molecular weight thermosetting resin having unsaturated double bonds is too high, no bleeding is liable to occur, so that dry streaks are liable to occur, resulting in voids in the internal structure of the board, and finally, in the case where the circuit material is processed at 85% RH at 85 ℃ for 1000 hours, the resonance ring Dk and the insertion loss variation value are out of limits.
As a preferred technical scheme of the invention, the component (B) is selected from any one or a combination of at least two of elastomer block copolymer, ethylene propylene rubber or polybutadiene rubber.
Preferably, the elastomeric block copolymer is selected from any one of or a combination of at least two of a styrene-butadiene diblock copolymer, a styrene-butadiene-styrene triblock copolymer, a styrene- (ethylene-butylene) -styrene triblock copolymer, a styrene-isoprene diblock copolymer, a styrene-isoprene-styrene triblock copolymer, a styrene- (ethylene-propylene) -styrene triblock copolymer, or a styrene- (ethylene-butylene) diblock copolymer.
In a preferred embodiment of the present invention, the inorganic filler is 60 to 78 parts by weight, for example, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, or the like, based on 100 parts by weight of the resin composition.
Preferably, the inorganic filler has a D50 particle diameter of 2 to 20 μm, and may be, for example, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, 12 μm, 13 μm, 14 μm, 15 μm, 18 μm, or 20 μm.
Preferably, the inorganic filler is selected from any one of silica, titanium dioxide, hollow glass beads, alumina, boron nitride, aluminum nitride, silicon carbide, magnesium oxide, zinc oxide, barium titanate, strontium titanate, magnesium titanate, calcium titanate, potassium titanate, barium strontium titanate, lead titanate, glass powder, magnesium hydroxide, mica powder, talc, hydrotalcite, mullite, boehmite, kaolin, montmorillonite, calcium silicate or calcium carbonate, or a combination of at least two thereof.
Preferably, the silica comprises fused silica and/or crystalline silica, more preferably fused silica.
Preferably, the titanium dioxide comprises rutile titanium dioxide and/or anatase titanium dioxide, further preferably rutile titanium dioxide.
Preferably, the inorganic filler includes an unmodified inorganic filler and/or an inorganic filler surface-modified with ethylene, i.e., a coupling agent.
In a preferred embodiment of the present invention, the flame retardant is 5 to 15 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, or the like, based on 100 parts by weight of the resin composition.
Preferably, the flame retardant comprises a bromine-containing flame retardant and/or a phosphorus-containing flame retardant.
Preferably, the bromine-containing flame retardant comprises any one of decabromodiphenyl ether, decabromodiphenylethane or ethylenebistetrabromophthalimide or a combination of at least two of them.
Preferably, the phosphorus-containing flame retardant includes any one of tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene, or 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, or a combination of at least two thereof.
In a preferred embodiment of the present invention, the radical initiator is used in an amount of 0.5 to 1 part by weight, for example, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, or 1 part by weight, based on 100 parts by weight of the resin composition.
Preferably, the free radical initiator comprises an organic peroxide free radical initiator and/or a carbon-based free radical initiator.
Preferably, the organic peroxide free radical initiator comprises any one or a combination of at least two of dicumyl peroxide, 1, 3-bis (t-butylperoxyisopropyl) benzene, 2, 5-di-t-butylperoxy-2, 5-dimethylhexane, 2, 5-di-t-butylperoxy-2, 5-dimethylhexyne-3, di-t-butyl peroxide or t-butylcumyl peroxide.
Preferably, the carbon-based radical initiator is selected from any one of 2, 3-dimethyl-2, 3-diphenylbutane, 2, 3-dimethyl-2, 3-bis (4-methylphenyl) butane, 2, 3-dimethyl-2, 3-bis (4-isopropylphenyl) butane, 3, 4-dimethyl-3, 4-diphenylhexane, or a combination of at least two thereof.
In a preferred embodiment of the present invention, the resin composition further comprises 0.1 to 0.5 parts by weight of a coupling agent, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, or 0.5 part, based on 100 parts by weight of the resin composition.
Preferably, the coupling agent comprises a vinyl coupling agent.
Preferably, the resin composition further comprises 0.1 to 0.5 parts by weight of an auxiliary agent, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part or 0.5 part, based on 100 parts by weight of the resin composition.
Preferably, the auxiliary agent comprises any one or a combination of at least two of a cross-linking agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant or a lubricant.
Preferably, the crosslinking agent includes any one of triallyl cyanate (TAC), allyl isocyanate (TAIC), trimethallyl allyl isocyanate (TMAIC), or a combination of at least two thereof.
It is to be noted that the resin composition of the present invention may also be used in combination with other various high polymers, which illustratively include but are not limited to: liquid crystalline polymers, thermoplastic resins, different flame retardant compounds or additives, etc.; and may be used alone or in combination of plural kinds as required.
Meanwhile, it should be noted that the preparation method of the resin composition in the present invention is not limited in any way, and the preparation method commonly used in the art is applicable, and exemplary methods include, but are not limited to: stirring and mixing. In the invention, the method for testing the particle size of the spherical silicon dioxide adopts a Malvern 3000 laser particle size analyzer for testing; the molecular weight of the thermosetting resins of the present invention (including number average molecular weight Mn and weight average molecular weight Mw) was measured by gel permeation chromatography based on polystyrene calibration as described in GB/T21863-2008.
As a preferable technical scheme of the invention, the reinforcing material is electronic-grade glass fiber cloth.
Preferably, the conductive metal layer is a copper foil.
Preferably, the copper foil has a thickness of 9 to 150 μm, such as 9 μm, 12 μm, 20 μm, 30 μm, 40 μm, 50 μm, 70 μm, 90 μm, 110 μm, 120 μm, 130 μm, 140 μm, or the like.
It should be noted that, in the present invention, there is no particular limitation on the preparation method of the circuit material, and for example, the preparation method of the circuit material includes the following steps:
(1) Dissolving or dispersing the resin composition in a solvent to obtain a resin glue solution, impregnating the reinforcing material with the resin glue solution, drying, and removing the solvent to obtain a prepreg;
(2) Coating an unmodified polyarylether layer on the copper foil, and drying the solvent to obtain a copper foil (RCC) of the attached resin layer;
(3) And (3) stacking at least one prepreg together, placing the prepreg between two pieces of copper foil (RCC) with the resin layer in the step (2), and then placing the prepreg in a laminating machine to obtain the circuit material through hot-pressing and curing.
It should be noted that the present invention does not have any particular limitation on the solvent in step (1), and organic solvents commonly used in the art are applicable, and exemplary include but are not limited to: alcohols such as methanol, ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, diethylene glycol ethyl ether and diethylene glycol butyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and mesitylene, esters such as ethoxyethyl acetate and ethyl acetate, and nitrogen-containing solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone. The above solvents may be used singly or in combination of two or more.
The solvent is 40 to 80 parts by weight, for example, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, or 80 parts by weight based on 100 parts by weight of the resin composition.
In a second aspect, the present invention provides a printed circuit board comprising a circuit material as described in the first aspect.
Preferably, the printed circuit board is a high frequency substrate.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, by designing the structure of the circuit material and the specific composition of the resin composition, further by arranging an unmodified polyarylether layer and selecting 1, 2-polybutadiene resin with specific performance, the prepared circuit material has high peel strength after high-temperature aging, and small change values of the Dk and the insertion loss of the resonant ring after high-temperature aging and high-temperature and high-humidity treatment, wherein the peel strength of the circuit material after aging for 10 days at 188 ℃ is more than or equal to 1.25N/mm, the change value of the Dk of the resonant ring after aging for 28 days at 188 ℃ is less than or equal to 0.05 (2 GHz), and the insertion loss change value is less than or equal to 0.05dB/5inch (2 GHz); change in Dk of the resonance ring after 1000 hours of treatment at 85% RH and 85 ℃ was 0.05 (2 GHz) or less, and change in insertion loss was 0.05dB/5inch (2 GHz).
(2) In the invention, the content of each component in the resin composition is further set within a specific range, so that the change values of the Dk and the insertion loss of the resonant ring of the circuit material after high-temperature aging and high-temperature and high-humidity can be further reduced, and more excellent performance effects are obtained, wherein the change value of the Dk of the resonant ring of the circuit material after aging for 28 days at 188 ℃ is less than or equal to 0.042 (2 GHz), specifically 0.035-0.042, and the insertion loss change value is less than or equal to 0.045dB/5inch (2 GHz), specifically 0.038-0.045; the change in Dk of the resonant ring after 1000 hours of treatment at 85% RH and 85 ℃ is not more than 0.044 (2 GHz), specifically 0.033 to 0.044, and the change in insertion loss is not more than 0.046dB/5inch (2 GHz), specifically 0.036 to 0.046.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Some of the component sources in the examples and comparative examples are shown in table 1 below:
TABLE 1
Wherein, in the conductive metal layer, the RCC refers to the copper foil with the unmodified polyarylether layer, and the RCC-free copper foil without the unmodified polyarylether layer.
The raw materials for preparing the unmodified polyarylether layers in the following examples and comparative examples include 100 parts by weight of the unmodified polyarylether, 15 parts by weight of a metal salt having an unsaturated bond, 8 parts by weight of a co-curable monomer, 8 parts by weight of an elastomer block copolymer, and 4 parts by weight of an initiator.
Examples 1 to 9
Examples 1-9 provide, respectively, a circuit material and a method of making the same, the circuit material comprising a dielectric substrate layer, a conductive metal layer, and an unmodified polyarylether layer disposed between the dielectric substrate layer and the conductive metal layer;
the dielectric substrate layer comprises a reinforcing material and a resin composition coated on the reinforcing material, the specific composition of the resin composition is shown in the following tables 2 and 3, and the dosage units of the resin composition in the tables 2 and 3 are parts by weight.
The circuit material described in example 1 was prepared as follows:
(1) Dissolving or dispersing the resin composition in xylene to obtain a resin glue solution, impregnating the reinforcing material with the resin glue solution, drying, and removing the solvent to obtain a prepreg;
(2) Coating the unmodified polyarylether layer on the copper foil, and drying the solvent to obtain the copper foil (RCC) with the unmodified polyarylether layer;
(3) Laminating at least one prepreg between two copper foils (RCC) having an unmodified polyarylether layer in step (2), and laminating in a laminator at a temperature of 245 deg.C and a pressure of 60Kg/cm 2 And then, preparing the circuit material through hot-pressing solidification.
Comparative examples 1 to 5
Comparative examples 1 to 5 provide a circuit material and a method for preparing the same, respectively, and the specific composition of the resin composition and the specific composition material of the circuit material are shown in table 3 below, and the usage units of the resin compositions in table 3 are parts by weight.
The circuit materials described in comparative examples 1-5 can be prepared by the preparation method provided in example 1.
TABLE 2
TABLE 3
| Components | Example 6 | Example 7 | Example 8 | Example 9 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| A-1 | 17 | ||||||||
| A-2 | 17 | ||||||||
| A-3 | |||||||||
| A-4 | |||||||||
| A-5 | |||||||||
| A-6 | 10 | 20 | 19 | 15 | 17 | ||||
| A-7 | |||||||||
| A-8 | 17 | ||||||||
| A-9 | 17 | ||||||||
| B-1 | 4 | 9 | 5 | 9 | 7 | 7 | 7 | 7 | 7 |
| B-2 | |||||||||
| C-1 | 75 | 60 | 65 | 65 | 65 | 65 | 65 | 65 | 65 |
| C-2 | |||||||||
| C-3 | |||||||||
| C-4 | |||||||||
| C-5 | |||||||||
| D-1 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| D-2 | |||||||||
| E-1 | |||||||||
| E-2 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| F-1 | 6 | 6 | 6 | 6 | 6 | 6 | 6 | 6 | 6 |
| F-2 | |||||||||
| T-1 | 2 | ||||||||
| T-2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | |
| T-3 | |||||||||
| T-4 |
The circuit materials provided in examples 1-9 and comparative examples 1-5 were tested for their performance by the following specific test methods:
(1) Dielectric constant (Dk) and dielectric loss (Df): the dielectric constant (Dk) and dielectric loss (Df) of the panels were tested using the SPDR method at a frequency of 10 GHz.
(2) Peel Strength (PS): the plate was aged at 188 ℃ for 10 days, and then the peel strength in N/mm was measured according to IPC-TM-650.2.4.8.
(3) Resonance ring Dk: and testing according to a design drawing and a testing method provided by the terminal, wherein the testing frequency is 2GHz. The test conditions were divided into three conditions in the as received state, after aging at 188 degrees for 28 days, after treatment at 85% RH,85 ℃ for 1000 hours. The change in the ring Dk after aging at 188 ℃ for 28 days was the difference between the ring Dk after aging at 188 ℃ for 28 days and the ring Dk in the reception state, and the change in the ring Dk after processing at 85 ℃ for 1000 hours was 85% RH, and the difference between the ring Dk after processing at 85 ℃ for 1000 hours and the ring Dk in the reception state.
(4) Inserting loss: and testing according to a design drawing and a testing method provided by the terminal, wherein the testing frequency is 2GHz, and the unit of insertion loss is dB/5inch. The test conditions were divided into three conditions in the as received state, after aging at 188 degrees for 28 days, after treatment at 85% RH,85 ℃ for 1000 hours. The change in insertion loss after aging at 188 ℃ for 28 days is the difference between the insertion loss after aging at 188 degrees for 28 days and the insertion loss in the receiving state, 85% RH, the change in insertion loss after treatment at 85 ℃ for 1000 hours is the difference between the insertion loss after treatment at 85 ℃ for 1000 hours and the insertion loss in the receiving state.
The results of the tests on the laminates provided in the examples and comparative examples are shown in tables 4 and 5:
TABLE 4
TABLE 5
As can be seen from the data in tables 4 and 5, in the present invention, by designing the structure of the circuit material and the specific composition of the resin composition, further by setting the unmodified polyarylether layer and selecting the 1, 2-polybutadiene resin with specific properties, the prepared circuit material has high peel strength after high temperature aging, and the resonant ring Dk and the insertion loss change value after high temperature aging and high temperature and high humidity treatment are small, the peel strength of the circuit material after aging at 188 ℃ for 10 days is not less than 1.25N/mm, the change value of the resonant ring Dk after aging at 188 ℃ for 28 days is not more than 0.05 (2 GHz), and the insertion loss change value is not more than 0.05dB/5inch (2 GHz); change in Dk of the resonance ring after 1000 hours of treatment at 85% RH and 85 ℃ was 0.05 (2 GHz) or less, and change in insertion loss was 0.05dB/5inch (2 GHz).
In the invention, the content of each component in the resin composition is further set within a specific range, so that the change values of the Dk and the insertion loss of the resonant ring of the circuit material after high-temperature aging and high-temperature and high-humidity can be further reduced, and more excellent performance effects are obtained, wherein the change value of the Dk of the resonant ring of the circuit material after aging for 28 days at 188 ℃ is less than or equal to 0.042 (2 GHz), specifically 0.035-0.042, and the insertion loss change value is less than or equal to 0.045dB/5inch (2 GHz), specifically 0.038-0.045; the change in Dk of the resonant ring after 1000 hours of treatment at 85% RH and 85 ℃ is not more than 0.044 (2 GHz), specifically 0.033 to 0.044, and the change in insertion loss is not more than 0.046dB/5inch (2 GHz), specifically 0.036 to 0.046.
As is apparent from a comparison of example 4 and examples 6 to 7, if the addition amount of the resin (component (A) and component (B)) is too small (example 6), the resin does not fill the voids between the fillers, voids are easily formed, eventually resulting in the exceeding of the resonance ring Dk and the insertion loss variation value after the circuit material has been processed for 1000 hours at 85% RH,85 ℃; if the amount of resin added is too high (example 7), especially if 1, 2-polybutadiene resin is used, the adhesive sheet sticks to hands, which affects the production process and the appearance of the board, and the resin tends to cause defects such as ravines, eventually causing the resonant ring Dk and the insertion loss variation of the circuit material to exceed the values after processing the circuit material at 85% rh and 85 ℃ for 1000 hours.
As is clear from a comparison between examples 4 and 8 to 9, if the proportion of the high molecular weight thermosetting resin having unsaturated double bonds is too low (the amount of the 1, 2-polybutadiene resin added is too large) to achieve the object of improving the thickness uniformity and the defects such as ravines, the resonant ring Dk and the insertion loss change after the circuit material is processed at 85% RH and 85 ℃ for 1000 hours are out of the limits; if the proportion of the high molecular weight thermosetting resin having unsaturated double bonds is too high (the amount of the 1, 2-polybutadiene resin added is too small), no flow occurs easily, so that dry flowers are generated, resulting in voids in the internal structure of the board, and finally, the resonant ring Dk and the insertion loss variation of the circuit material after processing at 85% RH and 85 ℃ for 1000 hours are out of limits.
As is apparent from a comparison between example 4 and comparative examples 1-2, when the number average molecular weight (Mn) of the 1, 2-polybutadiene resin is less than 3000g/mol, the molecular weight is too small, and flow of the resin easily causes gullies when pressing the plate, resulting in an inner structure of the plate being not dense, and finally, the resonant ring Dk and the insertion loss variation of the circuit material after processing at 85 ℃ RH and 85 ℃ for 1000 hours are out of the limits; when the number average molecular weight (Mn) of the 1, 2-polybutadiene resin is more than 6000g/mol, the molecular weight is too large, and the flow of the resin is not easy at the time of pressing the plate to cause dry-out, resulting in occurrence of voids in the internal structure of the plate, eventually leading to the occurrence of an excessive level of change in the resonance ring Dk and insertion loss after the circuit material has been processed at 85% RH for 1000 hours at 85 ℃.
As is apparent from comparison of example 4 and comparative examples 3 to 4, when PDI is greater than 1.08, the molecular weight distribution of the resin is relatively broad, and the fluctuation values of the resonance ring Dk and the insertion loss data in the circuit material test are relatively large, eventually leading to the exceeding of the resonance ring Dk and the insertion loss variation values after the circuit material is aged at 188 ℃ for 28 days and treated at 85 ℃ RH and 85 ℃ for 1000 hours; when the content of 1, 2-vinyl in 1, 2-polybutadiene resin is less than 90%, the curing crosslinking density of the board is deteriorated, so that the aging performance is influenced, and finally the resonant ring Dk and the insertion loss change value of the circuit material after aging for 28 days at 188 ℃ exceed the standard.
As can be seen from the comparison between example 4 and comparative example 5, the conductive metal layer and the unmodified polyarylether layer disposed between the dielectric substrate layer and the conductive metal layer can not only ensure that the peel strength of the dielectric substrate layer and the conductive metal layer after aging at 188 ℃ for 10 days is more than or equal to 1.20N/mm, but also can finally realize that the change value of Dk of the resonant ring of the circuit material after aging at 188 ℃ for 28 days is less than or equal to 0.05 (2 GHz), and the insertion loss change value is less than or equal to 0.05dB/5inch (2 GHz) through the synergistic effect between the unmodified polyarylether layer and the resin composition; the change in Dk of the resonance ring after the circuit material was treated at 85% RH for 1000 hours at 85 ℃ was 0.05 (2 GHz) or less, and the change in insertion loss was 0.05dB/5inch (2 GHz) or less. If no unmodified polyarylether layer exists, after high-temperature aging, the surface of the hydrocarbon resin (the component (A) and the component (B)) can be carbonized and shrunk to finally form a micro gap with the copper foil, so that not only is the peel strength greatly reduced, but also the aged resonant ring Dk and the insertion loss change value exceed the standard due to carbonization, and the aged resonant ring Dk and the insertion loss change value exceed the standard due to carbonization and the micro gap.
In summary, in the invention, by designing the structure of the circuit material and the specific composition of the resin composition, and further by arranging the unmodified polyarylether layer and selecting the 1, 2-polybutadiene resin with specific performance, the prepared circuit material has high peel strength after high-temperature aging, and the resonant ring Dk and insertion loss change value after high-temperature aging and high-temperature and high-humidity treatment are small.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims.
Claims (10)
1. A circuit material, comprising a dielectric substrate layer, a conductive metal layer, and a resin layer disposed between the dielectric substrate layer and the conductive metal layer;
the dielectric substrate layer includes a reinforcement material and a resin composition overlying the reinforcement material, the resin composition including the following components:
(A) 1, 2-polybutadiene resin, wherein the content of 1, 2-vinyl in the 1, 2-polybutadiene resin is more than or equal to 90%, the number average molecular weight is 3000-6000g/mol, and the ratio PDI of the weight average molecular weight to the number average molecular weight is 1.02-1.08;
(B) The number average molecular weight Mn of the thermosetting resin with the unsaturated double bonds of the macromolecular chains is more than or equal to 50000g/mol;
(C) An inorganic filler;
(D) A flame retardant;
(E) A free radical initiator.
2. The circuit material of claim 1, wherein the resin layer is an unmodified polyarylether layer.
3. The circuit material according to claim 1 or 2, wherein the sum of the parts by weight of the component (a) and the component (B) is 15 to 25 parts based on 100 parts by weight of the resin composition;
preferably, the mass ratio of the component (A) to the component (B) is 2.
4. A circuit material according to any of claims 1-3, wherein component (B) is selected from any one of or a combination of at least two of elastomeric block copolymers, ethylene propylene rubber or polybutadiene rubber;
preferably, the elastomeric block copolymer is selected from any one of or a combination of at least two of a styrene-butadiene diblock copolymer, a styrene-butadiene-styrene triblock copolymer, a styrene- (ethylene-butylene) -styrene triblock copolymer, a styrene-isoprene diblock copolymer, a styrene-isoprene-styrene triblock copolymer, a styrene- (ethylene-propylene) -styrene triblock copolymer, or a styrene- (ethylene-butylene) diblock copolymer.
5. The circuit material according to any one of claims 1 to 4, wherein the inorganic filler is present in an amount of 60 to 78 parts by weight based on 100 parts by weight of the resin composition;
preferably, the inorganic filler has a D50 particle diameter of 2 to 20 μm;
preferably, the inorganic filler is selected from any one of silica, titanium dioxide, hollow glass beads, alumina, boron nitride, aluminum nitride, silicon carbide, magnesium oxide, zinc oxide, barium titanate, strontium titanate, magnesium titanate, calcium titanate, potassium titanate, barium strontium titanate, lead titanate, glass powder, magnesium hydroxide, mica powder, talc, hydrotalcite, mullite, boehmite, kaolin, montmorillonite, calcium silicate or calcium carbonate, or a combination of at least two thereof.
6. The circuit material according to any one of claims 1 to 5, wherein the flame retardant is 5 to 15 parts by weight based on 100 parts by weight of the resin composition;
preferably, the flame retardant comprises a bromine-containing flame retardant and/or a phosphorus-containing flame retardant.
7. The circuit material of any of claims 1-6, wherein the free radical initiator is present in an amount of 0.5 to 1 part by weight based on 100 parts by weight of the resin composition;
preferably, the free radical initiator comprises an organic peroxide free radical initiator and/or a carbon-based free radical initiator;
preferably, the organic peroxide free radical initiator comprises any one or at least two combinations of dicumyl peroxide, 1, 3-bis (t-butylperoxyisopropyl) benzene, 2, 5-di-t-butylperoxy-2, 5-dimethylhexane, 2, 5-di-t-butylperoxy-2, 5-dimethylhexyne-3, di-t-butyl peroxide or t-butylcumyl peroxide;
preferably, the carbon-based radical initiator is any one selected from 2, 3-dimethyl-2, 3-diphenylbutane, 2, 3-dimethyl-2, 3-di (4-methylphenyl) butane, 2, 3-dimethyl-2, 3-di (4-isopropylphenyl) butane, 3, 4-dimethyl-3, 4-diphenylhexane, or a combination of at least two thereof.
8. The circuit material according to any one of claims 1 to 7, wherein the resin composition further comprises 0.1 to 0.5 parts by weight of a coupling agent, based on 100 parts by weight of the resin composition;
preferably, the coupling agent comprises a vinyl coupling agent;
preferably, the resin composition further comprises 0.1 to 0.5 part by weight of an auxiliary agent, based on 100 parts by weight of the resin composition;
preferably, the auxiliary agent comprises any one of or a combination of at least two of a cross-linking agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant or a lubricant.
9. The circuit material of any of claims 1-8, wherein the reinforcing material is an electronic grade fiberglass cloth;
preferably, the conductive metal layer is a copper foil;
preferably, the copper foil has a thickness of 9 to 150 μm.
10. A printed circuit board comprising the circuit material of any one of claims 1-9;
preferably, the printed circuit board is a high frequency substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211615725.2A CN115847952A (en) | 2022-12-15 | 2022-12-15 | Circuit material and printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211615725.2A CN115847952A (en) | 2022-12-15 | 2022-12-15 | Circuit material and printed circuit board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115847952A true CN115847952A (en) | 2023-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211615725.2A Pending CN115847952A (en) | 2022-12-15 | 2022-12-15 | Circuit material and printed circuit board |
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| Country | Link |
|---|---|
| CN (1) | CN115847952A (en) |
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2022
- 2022-12-15 CN CN202211615725.2A patent/CN115847952A/en active Pending
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