CN113801462B - Resin composition, prepreg, circuit board and printed circuit board - Google Patents

Resin composition, prepreg, circuit board and printed circuit board Download PDF

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Publication number
CN113801462B
CN113801462B CN202111146456.5A CN202111146456A CN113801462B CN 113801462 B CN113801462 B CN 113801462B CN 202111146456 A CN202111146456 A CN 202111146456A CN 113801462 B CN113801462 B CN 113801462B
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carbon
resin composition
resin
parts
weight
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CN113801462A (en
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王亮
任英杰
董辉
俞高
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Hangzhou Wazam New Materials Co ltd
Zhuhai Huazheng New Material Co ltd
Zhejiang Huazheng New Material Group Co ltd
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Hangzhou Wazam New Materials Co ltd
Zhuhai Huazheng New Material Co ltd
Zhejiang Huazheng New Material Group Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Abstract

The invention relates to a resin composition, a prepreg, a circuit substrate and a printed circuit board. The resin composition comprises a polyphenyl ether resin capped by a carbon-carbon conjugated group, a hydrocarbon resin containing carbon-carbon double bonds, a polysiloxane curing agent and a solvent; wherein the structure of the polysiloxane curing agent is shown as a formula (I),in the formula (I), m is an integer of 1-20, R 1 Is a first hydrocarbon group of carbon chain length 1-12, R 2 Is hydrogen or a second hydrocarbon group of carbon chain length 1-12, R 1 Or R is 2 At least one of which contains an alkenyl-reactive functional group. The polysiloxane curing agent in the resin composition is not easy to volatilize, so that the stability of the performances of circuit substrates prepared from different batches can be ensured; and due to the inventionThe polysiloxane curing agent does not contain hydrophilic groups and cannot hydrolyze, so that the hygroscopicity of the circuit substrate can be effectively reduced in the use process of the circuit substrate, and the deterioration of the dielectric property of the circuit substrate due to moisture absorption can be avoided.

Description

Resin composition, prepreg, circuit board and printed circuit board
Technical Field
The invention relates to the technical field of electronic industry, in particular to a resin composition, a prepreg, a circuit substrate and a printed circuit board.
Background
In the 5G age, circuit substrates are required to have low dielectric constants and dielectric losses in order to maintain transmission rates and to maintain transmission signal integrity. However, the resin system of the conventional circuit board is a polyphenylene ether resin system, and the curing crosslinking agent used is triallyl isocyanurate (TAIC). On one hand, the inherent amide groups in the TAIC self molecular structure belong to hydrophilic groups and are easy to hydrolyze, so that the moisture absorption is high, the water absorption rate of the circuit substrate is high, the dielectric property moisture absorption degradation is serious, and the reliability of the board is influenced; on the other hand, TAIC is volatile, resulting in difficulty in meeting the requirement of the crosslinking density of the resin system, and thus poor thermal properties such as glass transition temperature (Tg) of the circuit substrate or poor batch stability.
Disclosure of Invention
Based on this, it is necessary to provide a resin composition, a prepreg, a circuit board and a printed circuit board in view of the above-mentioned problems; the circuit substrate prepared by the resin composition has excellent dielectric property and thermal property, and the dielectric property of the circuit substrate is not degraded due to moisture absorption when the circuit substrate is used.
The invention provides a resin composition, which comprises polyphenyl ether resin capped by carbon-carbon conjugated groups, hydrocarbon resin containing carbon-carbon double bonds, polysiloxane curing agent and solvent; wherein the structure of the polysiloxane curing agent is shown as a formula (I),
in the formula (I), m is an integer of 1-20, R 1 Is a first hydrocarbon group of carbon chain length 1-12, R 2 Is hydrogen or a second hydrocarbon group of carbon chain length 1-12, R 1 Or R is 2 At least one of which contains an alkenyl-reactive functional group.
In one embodiment, m is an integer from 1 to 5, R 1 Is a first hydrocarbon group of carbon chain length 2-8, R 2 Is a second hydrocarbon group of carbon chain length 2-8, R 1 Or R is 2 At least one of which contains an alkenyl-reactive functional group.
In one embodiment, the polysiloxane curing agent is selected from one or a combination of at least two of the compounds represented by the formulas (II-1) - (II-6), (III-1) - (III-6), (IV-1) - (IV-6), (V-1) - (V-6), (VI-1) - (VI-6), (VII-1) - (VII-6), (VIII-1) - (VIII-6),
wherein, m is an integer of 1 to 5 in the compounds shown in (II-1) - (II-6), (III-1) - (III-6), (IV-1) - (IV-6), (V-1) - (V-6), (VI-1) - (VI-6), (VII-1) - (VII-6) and (VIII-1) - (VIII-6).
In one embodiment, the hydrocarbon resin containing carbon-carbon double bonds has a relative molecular mass of 1000-9000;
and/or the relative molecular mass of the carbon-carbon conjugated group end-capped polyphenyl ether resin is 600-6000.
In one embodiment, the mass of the hydrocarbon resin containing carbon-carbon double bonds is 40 to 90 parts by weight and the mass of the polysiloxane curing agent is 70 to 100 parts by weight based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenylene ether resin in the resin composition.
In one embodiment, the resin composition further comprises a halogen-free flame retardant.
In an embodiment, the halogen-free flame retardant includes one or a combination of at least two of a phosphorus flame retardant, a nitrogen flame retardant, or a silicon flame retardant.
In one embodiment, the halogen-free flame retardant is 20 to 60 parts by weight based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenylene ether resin.
In one embodiment, the resin composition further comprises an accelerator, the accelerator having a mass of 0.1 parts by weight or less based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenylene ether resin;
and/or, the resin composition further comprises a dielectric filler, wherein the mass of the dielectric filler is less than or equal to 150 parts by weight based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenyl ether resin.
A prepreg comprising a reinforcing material and a dried resin composition as described above attached to the reinforcing material.
The circuit substrate comprises a dielectric layer and a conductive layer arranged on at least one surface of the dielectric layer, wherein the dielectric layer is formed by solidifying a prepreg layer, and the prepreg layer comprises one prepreg or is formed by overlapping more than two prepregs.
A printed circuit board is made of the circuit substrate.
The curing agent used in the resin composition is a polysiloxane curing agent shown in the formula (I), the polysiloxane curing agent has an organic and inorganic hybrid structure, a main framework is of a cyclic inorganic structure, the heat resistance is excellent, the resin composition is not easy to volatilize, and the polysiloxane curing agent has a plurality of alkenyl active functional groups, so that the polysiloxane curing agent has high retention amount in a system and enough crosslinking reaction activity in the process of processing the resin composition into a circuit substrate, various components in the resin composition can fully react, the crosslinking density of the resin system is high, and the heat resistance such as Tg (glass transition temperature) of the prepared circuit substrate can be improved. In addition, the low volatility of the polysiloxane curing agent enables the preparation process to be easier to control, and the performances of the circuit substrates prepared in different batches can be guaranteed to be the same or similar, so that the circuit substrates can be produced in a large scale.
Because the polysiloxane curing agent does not contain hydrophilic groups, the hygroscopicity of the circuit substrate can be effectively reduced in the use process of the circuit substrate, the polysiloxane curing agent cannot be hydrolyzed, the deterioration of the dielectric property of the circuit substrate due to moisture absorption can be avoided, and the stability and the use reliability of the dielectric property of the circuit substrate are ensured. Therefore, the circuit substrate provided by the invention can be better suitable for the use environment of high temperature and high humidity.
Detailed Description
The resin composition, prepreg, circuit board and printed circuit board provided by the present invention will be further described below.
The resin composition provided by the invention comprises a polyphenyl ether resin capped by a carbon-carbon conjugated group, hydrocarbon resin containing carbon-carbon double bonds, a polysiloxane curing agent and a solvent; wherein the structure of the polysiloxane curing agent is shown as a formula (I),
in the polysiloxane curing agent shown in the formula (I), the alkenyl active functional group increases with the number of m times. However, if m >20, the cyclic structure of the polysiloxane curing agent is liable to undergo molecular entanglement during the preparation of the resin composition into a circuit substrate, resulting in a great increase in the viscosity of the resin composition; meanwhile, the excessive molecular weight of the polysiloxane curing agent can lead to the increase of steric hindrance of alkenyl active functional groups, so that the number of alkenyl active functional groups participating in the crosslinking reaction is reduced, the reactivity of the polysiloxane curing agent is reduced, and finally, the crosslinking density of a resin system is reduced, and the heat resistance such as Tg of a circuit substrate is reduced. In the formula (I), m is an integer of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, and m is more preferably an integer of 1 to 5 in order to further reduce steric hindrance of the reactive group.
In addition, R 1 Is a first hydrocarbon group of carbon chain length 1-12, R 2 Is hydrogen or a second hydrocarbon group of carbon chain length 1-12, R 1 Or R is 2 At least one of which contains an alkenyl active functional group to react a polysiloxane curing agent represented by the formula (I) with a polyphenylene ether resin capable of being terminated with the carbon-carbon conjugated group and a hydrocarbon resin containing carbon-carbon double bonds.
It will be appreciated that the first hydrocarbyl group having a carbon chain length of 1 to 12 and the second hydrocarbyl group having a carbon chain length of 1 to 12 each comprise C 1 Hydrocarbon radicals, C 2 Hydrocarbon radicals, C 3 Hydrocarbon radicals, C 4 Hydrocarbon radicals, C 5 Hydrocarbon radicals, C 6 Hydrocarbon radicals, C 7 Hydrocarbon radicals, C 8 Hydrocarbon radicals, C 9 Hydrocarbon radicals, C 10 Hydrocarbon radicals, C 11 Hydrocarbyl and C 12 A hydrocarbon group. In one embodiment, the first hydrocarbyl group having a carbon chain length of 1-12 and the second hydrocarbyl group having a carbon chain length of 1-12 each include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, isobutyl, (cyclohexyl) methyl, cyclopropylmethyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, 2-propenyl, butenyl, crotyl, 2-isopentenyl, 2- (butadienyl), 4-one of pentenyl, 2, 4-pentadienyl, 3- (1, 4-pentadienyl), 5-hexenyl or 6-heptenyl.
In order to further increase the reactivity of the polysiloxane curing agent and thereby further increase the crosslink density of the resin system and the heat resistance such as Tg of the circuit substrate, in one embodiment, the R 1 Is a first hydrocarbon group of carbon chain length 2-8, R 2 Is a second hydrocarbon group of carbon chain length 2-8, R 1 Or R is 2 At least one of which contains an alkenyl-reactive functional group.
It should be noted that R is 1 And R is R 2 May be the same or different, and in one embodiment R 1 And R is R 2 All contain alkenyl reactive functional groups.
In one embodiment, the polysiloxane curing agent is selected from one or a combination of at least two of the compounds represented by the formulas (II-1) - (II-6), (III-1) - (III-6), (IV-1) - (IV-6), (V-1) - (V-6), (VI-1) - (VI-6), (VII-1) - (VII-6), (VIII-1) - (VIII-6),
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wherein, m is an integer of 1 to 5 in the compounds shown in (II-1) - (II-6), (III-1) - (III-6), (IV-1) - (IV-6), (V-1) - (V-6), (VI-1) - (VI-6), (VII-1) - (VII-6) and (VIII-1) - (VIII-6).
If the relative molecular mass of the hydrocarbon resin containing carbon-carbon double bonds is too large, the linear structure of the hydrocarbon resin containing carbon-carbon double bonds is easy to wind so as to lead the reactive groups to be wrapped, the reaction degree between the hydrocarbon resin containing carbon-carbon double bonds and the polyphenyl ether resin capped by the carbon-carbon conjugated groups is reduced, and the Tg of the circuit substrate is lower; however, when the relative molecular mass of the hydrocarbon resin containing carbon-carbon double bonds is too small, the relative molecular weight difference between the hydrocarbon resin containing carbon-carbon double bonds and the rest of components in the resin composition is too large, so that the hydrocarbon resin containing carbon-carbon double bonds is easy to preferentially self-react in the process of preparing the resin composition into the circuit substrate, the compatibility between the hydrocarbon resin containing carbon-carbon double bonds and the polyphenyl ether resin capped by the carbon-carbon conjugated groups is reduced, the reaction uniformity is reduced, the copolymerization structure is built incompletely, and further the heat resistance such as Tg of the circuit substrate is greatly reduced. Thus, in one embodiment, the hydrocarbon resin containing carbon-carbon double bonds preferably has a relative molecular mass of 1000-9000, more preferably 3000-9000.
In addition, in one embodiment, the carbon-carbon conjugated group-terminated polyphenylene ether resin includes an allyl-terminated polyphenylene ether resin, an acrylate-terminated polyphenylene ether resin, a methyl methacrylate group-terminated polyphenylene ether resin, or a vinyl-terminated polyphenylene ether resin; if the relative molecular mass of the carbon-carbon conjugated group-terminated polyphenylene ether resin is too large, the processability of the resin composition is lowered due to poor solubility of the carbon-carbon conjugated group-terminated polyphenylene ether resin, and heat resistance such as Tg of the circuit substrate is greatly lowered; however, the carbon-carbon conjugated group-terminated polyphenylene ether resin having a relatively small molecular mass may have a relatively large end group occupation to lower the dielectric properties, and thus the carbon-carbon conjugated group-terminated polyphenylene ether resin has a relative molecular mass of 600 to 6000; further preferably 2000 to 3000.
The polysiloxane curing agent shown in the formula (I) has longer silica bond length and larger flexibility than carbon bond length, and can generate a bridging effect, so that the compatibility of the polyphenyl ether resin capped by the carbon-carbon conjugated group and the hydrocarbon resin containing carbon-carbon double bonds in the resin composition can be improved, meanwhile, the polysiloxane curing agent shown in the formula (I), the polyphenyl ether resin capped by the carbon-carbon conjugated group and the hydrocarbon resin containing carbon-carbon double bonds can generate copolymerization reaction, and further, more hydrocarbon resin containing carbon-carbon double bonds can be added into the resin composition to form a firmer soft and hard block skeleton structure, so that the dielectric property of a circuit substrate prepared by using the resin composition is further improved, the adjustable range of the dielectric property of the circuit substrate is wider, and lower dielectric constant and dielectric loss can be obtained.
In one embodiment, the mass of the hydrocarbon resin containing carbon-carbon double bonds is 40 to 90 parts by weight, more preferably 50 to 90 parts by weight, based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenylene ether resin in the resin composition.
In one embodiment, the polysiloxane curing agent is present in the resin composition in an amount of 70 to 100 parts by weight, more preferably 70 to 80 parts by weight, based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenylene ether resin.
In order to improve the flame retardant property of the circuit substrate, the resin composition also comprises a halogen-free flame retardant, wherein the mass of the halogen-free flame retardant is 20-60 parts by weight based on 100 parts by weight of the polyphenyl ether resin capped by the carbon-carbon conjugated group. Wherein the halogen-free flame retardant comprises one or a combination of a plurality of phosphorus flame retardants, nitrogen flame retardants and silicon flame retardants, and can also comprise other auxiliary flame retardants which can produce synergistic action with the selected phosphorus flame retardants, nitrogen flame retardants and silicon flame retardants.
Since the polysiloxane curing agent of formula (I) of the present invention can form a silicon-phosphorus synergistic flame retardant system with a phosphorus flame retardant, not only can the flame retardant effect be improved, but also the problem of poor compatibility of the phosphorus flame retardant in the resin composition can be improved, in one embodiment, the halogen-free flame retardant is preferably a phosphorus flame retardant, including a phosphate flame retardant, a phosphazene flame retardant, a hypophosphite flame retardant, a bisdiphenyloxy phosphorus flame retardant, and the like. At this time, the mass of the phosphorus-based flame retardant is 30 to 60 parts by weight based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenylene ether resin, so that the circuit substrate has more excellent flame retardant property.
In order to catalyze free radical reaction in the process of processing the resin composition to prepare the circuit substrate, the resin composition also comprises an accelerator which is a peroxide accelerator and comprises dicumyl peroxide, tert-butyl cumyl peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide and dicumyl hydroperoxide. The accelerator is less than or equal to 0.1 part by weight based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenylene ether resin.
In order to further improve the dielectric properties of the circuit board prepared by the resin composition, the resin composition further comprises a dielectric filler, wherein the dielectric filler comprises one or more than two of titanium dioxide, barium titanate, strontium titanate, crystalline silicon dioxide, fused silicon dioxide, corundum, wollastonite, solid glass microspheres, hollow silica microspheres, hollow titanium dioxide microspheres, synthetic glass, quartz, boron nitride, aluminum carbide, beryllium oxide, aluminum hydroxide, magnesium oxide, mica, talcum and magnesium hydroxide. The dielectric filler has a mass of 150 parts by weight or less based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenylene ether resin.
In one embodiment, the solvent comprises at least one of N, N-dimethylformamide, ethylene glycol methyl ether, propylene glycol methyl ether acetate, toluene, xylene, acetone, butanone, or cyclohexanone. The mass of the solvent is 25 to 400 parts by weight based on 100 parts by weight of the resin.
The invention also provides a prepreg which comprises a reinforcing material and the dried resin composition attached to the reinforcing material.
In an embodiment, the reinforcing material includes one or a combination of at least two of glass fiber cloth, carbon fiber cloth, or aramid fiber cloth.
The prepreg can be prepared by the following steps: the resin composition is uniformly coated on the reinforcing material and is prepared after baking.
The invention also provides a circuit substrate, which comprises a dielectric layer and a conductive layer arranged on at least one surface of the dielectric layer, wherein the dielectric layer is formed by solidifying a prepreg layer, and the prepreg layer comprises one prepreg or is formed by overlapping more than two prepregs.
The number of prepregs in the prepreg layer is selected by the thickness of the circuit substrate.
In an embodiment, the conductive layer is preferably copper foil, so that the circuit substrate is a copper-clad plate.
Since the polysiloxane curing agent used in the invention improves the compatibility of the carbon-carbon conjugated group-terminated polyphenyl ether resin and the hydrocarbon resin containing carbon-carbon double bonds, more hydrocarbon resin containing carbon-carbon double bonds can be used in the resin composition, in one embodiment, the dielectric constant of the circuit substrate prepared by using the resin composition is kept between 3.0 and 4.0, further kept between 3.0 and 3.8, the dielectric loss is less than 0.005, further less than 0.004, and the circuit substrate has excellent dielectric properties and wider adjustable range.
In addition, since the polysiloxane curing agent shown in the formula (I) has an organic and inorganic hybrid structure and a main framework is of a cyclic inorganic structure, the polysiloxane curing agent has excellent heat resistance and is not easy to volatilize, and a plurality of alkenyl active functional groups exist in the polysiloxane curing agent, so that the polysiloxane curing agent has high retention amount in a system and enough crosslinking reaction activity in the process of processing the resin composition to prepare the circuit substrate, various components in the resin composition can fully react, the crosslinking density of the resin system is high, and the heat resistance such as Tg (glass transition temperature) of the prepared circuit substrate can be improved. In addition, the low volatility of the polysiloxane curing agent enables the preparation process to be easier to control, and the performances of the circuit substrates prepared in different batches can be guaranteed to be the same or similar, so that the circuit substrates can be produced in a large scale.
In one embodiment, the Tg of the circuit substrate can be 200 ℃ or higher.
Because the polysiloxane curing agent does not contain hydrophilic groups, the hygroscopicity of the circuit substrate can be effectively reduced in the use process of the circuit substrate, the polysiloxane curing agent cannot be hydrolyzed, the deterioration of the dielectric property of the circuit substrate due to moisture absorption can be avoided, and the stability and the use reliability of the dielectric property of the circuit substrate are ensured. Therefore, the circuit substrate provided by the invention can be better suitable for the use environment of high temperature and high humidity.
Based on the above, the invention also provides a printed circuit board manufactured by the circuit substrate. The specific preparation process mainly comprises the processes of drilling a hole plate, finishing the hole, microetching, presoaking, activating, accelerating, thickening chemical copper and copper, and the like.
The printed circuit board can still maintain a good transmission rate and maintain the integrity of transmission signals in a high-temperature and high-humidity environment.
Hereinafter, the resin composition, the prepreg, the circuit substrate and the printed circuit board will be further described by the following specific examples.
In the following examples, the polysiloxane curing agents were self-made and had the following structural formula:
wherein: a first polysiloxane curing agent: m=1, r 1 R is R 2 All are 7-octenyl groups; a second polysiloxane curing agent: m=5, r 1 R is R 2 All are vinyl groups; third polysiloxane curing agent: m=5, r 1 Is 7-octenyl, R 2 Is hydrogen; fourth polysiloxane curing agent: m=5, r 1 Is methyl, R 2 11-dodecenyl; fifth polysiloxane curing agent: m=20, r 1 R is R 2 All are 11-dodecenyl; sixth polysiloxane curing agent: m=25, r 1 R is R 2 All are 7-octenyl groups; seventh polysiloxane curing agent: m=0, r 1 R is R 2 All are 7-octenyl groups;
in the following examples, the cyanate ester curative is melamine isocyanurate;
the first polyphenyl ether resin is polyphenyl ether resin terminated by methyl methacrylate groups, and the molecular weight is 2500; the second polyphenyl ether resin is polyphenyl ether with hydroxyl end capped, and the molecular weight is 2500;
the first hydrocarbon resin is polybutadiene with a molecular weight of 3000; the second hydrocarbon resin is polybutadiene with a molecular weight of 1000; the third hydrocarbon resin is polybutadiene with a molecular weight of 9000; the fourth hydrocarbon resin is hydrogenated polybutadiene with a molecular weight of 3000; the fifth hydrocarbon resin is polybutadiene with a molecular weight of 15000; the sixth hydrocarbon resin is polybutadiene with a molecular weight of 800.
Example 1
Referring to table 1, 100 parts by weight of a first polyphenylene ether resin, 70 parts by weight of a first polysiloxane curing agent, 50 parts by weight of a first hydrocarbon resin, 40 parts by weight of hypophosphite, 0.086 parts by weight of dicumyl peroxide, 140 parts by weight of silica and 215 parts by weight of toluene solvent were taken and added to a vessel equipped with a stirrer and a condenser at room temperature to prepare a resin composition.
The resin composition is coated on E-type glass cloth, and is baked in an oven at 170 ℃ to obtain a prepreg, wherein the glue content in the prepreg is 50%, and the calculation formula of the glue content is as follows: glue content= (mass of prepreg-mass of E-glass cloth) ×100%/mass of prepreg.
And (3) superposing six prepregs to obtain a semi-cured layer, covering copper foils with the thickness of 1oz on two sides of the semi-cured layer, placing the semi-cured layer in a vacuum hot press, and pressing the semi-cured layer at the temperature of 200 ℃ for 2 hours under the pressure of 2MPa, so that the copper-clad plate is obtained.
Examples 2 to 9 and comparative examples 1 to 9 are shown below.
Reference is made to example 1, with the differences in the types and proportions of the components, see in particular tables 1-3.
TABLE 1
TABLE 2
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TABLE 3 Table 3
The copper-clad plates obtained in examples 1 to 9 and comparative examples 1 to 9 were subjected to performance test, and the specific test results are shown in tables 4 to 6.
The dielectric constant and dielectric loss are tested by using a vector net separator of rosenberg, and the test frequency is 10GHz according to the SPDR method of the resonant cavity of the separation medium column.
PCT water absorption: after etching copper foil on the surface of the copper-clad plate, the base material is dried and weighed to the original weight, then the base material is put into a pressure cooker, the base material is treated for two hours at the temperature of 120 ℃ and 150KPa, the base material is taken out and dried by a dry cloth, the weight of a sample after water absorption is weighed, and the PCT water absorption is (weight after cooking-weight before cooking)/weight before cooking.
Glass transition temperature (Tg): tg of the copper clad laminate was measured according to dynamic thermo-mechanical analysis (DMA) according to the DMA method specified in IPC-TM-6502.4.24.4.
Flame retardancy: measured according to the UL94 method.
TABLE 4 Table 4
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TABLE 5
TABLE 6
The procedure of example 1 was repeated to prepare copper clad laminate of different batches, and the glass transition temperatures of the copper clad laminate of different batches were tested, and the test results are shown in table 7.
TABLE 7
Batch of Glass transition temperature Tg (. Degree. C.)
1 220
2 216
3 215
4 223
5 221
The copper clad laminate prepared in example 1 was subjected to etching, and then stored in an environment with a humidity of 95%, and dielectric properties were measured after storage for 2 days and 4 days, and specific test results are shown in table 8.
TABLE 8
Storage conditions/days Dielectric constant (10 GHz) Dielectric loss
0 3.71 0.0040
1 3.71 0.0050
2 3.71 0.0055
3 3.70 0.0055
4 3.70 0.0055
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (12)

1. A resin composition comprising a carbon-carbon conjugated group-terminated polyphenylene ether resin, a hydrocarbon resin containing carbon-carbon double bonds, a polysiloxane curing agent, and a solvent; wherein the structure of the polysiloxane curing agent is shown as a formula (I),
；
in the formula (I), m is an integer of 1-20, R 1 Is a first hydrocarbon group of carbon chain length 1-12, R 2 Is hydrogen or a second hydrocarbon group of carbon chain length 1-12, R 1 Or R is 2 At least one of which contains an alkenyl-reactive functional group;
the carbon-carbon conjugated group-terminated polyphenyl ether resin is selected from allyl-terminated polyphenyl ether resin, acrylic ester-terminated polyphenyl ether resin, methyl methacrylate group-terminated polyphenyl ether resin or vinyl-terminated polyphenyl ether resin, and the relative molecular mass of the carbon-carbon conjugated group-terminated polyphenyl ether resin is 600-6000;
the relative molecular mass of the hydrocarbon resin containing carbon-carbon double bonds is 1000-9000;
in the resin composition, the mass of the hydrocarbon resin containing carbon-carbon double bonds is 40-90 parts by weight, and the mass of the polysiloxane curing agent is 70-100 parts by weight based on 100 parts by weight of the polyphenyl ether resin capped by the carbon-carbon conjugated groups.
2. The resin composition according to claim 1, wherein m is an integer of 1 to 5, R 1 Is a first hydrocarbon group of carbon chain length 2-8, R 2 Is a second hydrocarbon group of carbon chain length 2-8, R 1 Or R is 2 At least one of which contains an alkenyl-reactive functional group.
3. The resin composition according to claim 2, wherein the polysiloxane curing agent is selected from one or a combination of at least two of the compounds represented by the formulas (II-1) to (II-6), (III-1) to (III-6), (IV-1) to (IV-6), (V-1) to (V-6), (VI-1) to (VI-6), (VII-1) to (VII-6), (VIII-1) to (VIII-6),
，
wherein, m is an integer of 1 to 5 in the compounds shown in (II-1) - (II-6), (III-1) - (III-6), (IV-1) - (IV-6), (V-1) - (V-6), (VI-1) - (VI-6), (VII-1) - (VII-6) and (VIII-1) - (VIII-6).
4. A resin composition according to any one of claims 1 to 3, wherein the hydrocarbon resin containing carbon-carbon double bonds has a relative molecular mass of 3000 to 9000;
and/or the relative molecular mass of the carbon-carbon conjugated group end-capped polyphenyl ether resin is 2000-3000.
5. A resin composition according to any one of claims 1 to 3, wherein the mass of the hydrocarbon resin containing carbon-carbon double bonds is 50 to 90 parts by weight and the mass of the polysiloxane curing agent is 70 to 80 parts by weight based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenylene ether resin in the resin composition.
6. A resin composition according to any one of claims 1 to 3, wherein the resin composition further comprises a halogen-free flame retardant.
7. The resin composition according to claim 6, wherein the halogen-free flame retardant comprises one or a combination of at least two or more of a phosphorus-based flame retardant, a nitrogen-based flame retardant, or a silicon-based flame retardant.
8. The resin composition according to claim 6, wherein the halogen-free flame retardant is 20 to 60 parts by weight based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenylene ether resin.
9. A resin composition according to any one of claims 1 to 3, further comprising an accelerator in an amount of 0.1 parts by weight or less based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenylene ether resin;
and/or, the resin composition further comprises a dielectric filler, wherein the mass of the dielectric filler is less than or equal to 150 parts by weight based on 100 parts by weight of the carbon-carbon conjugated group-terminated polyphenyl ether resin.
10. A prepreg comprising a reinforcing material and a dried resin composition according to any one of claims 1 to 9 attached to the reinforcing material.
11. A circuit substrate, comprising a dielectric layer and a conductive layer disposed on at least one surface of the dielectric layer, wherein the dielectric layer is formed by curing a prepreg layer, and the prepreg layer comprises one prepreg according to claim 10 or is formed by laminating more than two prepregs according to claim 10.
12. A printed circuit board made from the circuit substrate of claim 11.
CN202111146456.5A 2021-09-28 2021-09-28 Resin composition, prepreg, circuit board and printed circuit board Active CN113801462B (en)

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