CN109777123B - Resin composition, prepreg for printed circuit, and metal-clad laminate - Google Patents
Resin composition, prepreg for printed circuit, and metal-clad laminate Download PDFInfo
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- CN109777123B CN109777123B CN201811596062.8A CN201811596062A CN109777123B CN 109777123 B CN109777123 B CN 109777123B CN 201811596062 A CN201811596062 A CN 201811596062A CN 109777123 B CN109777123 B CN 109777123B
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Abstract
The present disclosure provides a resin composition, a prepreg for a printed circuit, and a metal-clad laminate. The resin composition comprises: a silicon aryne resin; polyphenylene ether resin containing unsaturated bond; and a butadiene polymer. By using the resin composition, the metal-clad laminate can be produced that has at least one of characteristics of low dielectric loss tangent, high heat resistance, low thermal expansion coefficient, and the like.
Description
Technical Field
The present disclosure relates to the field of printed circuit board technology. In particular, the present disclosure relates to a resin composition, a prepreg for a printed circuit, and a metal-clad laminate.
Background
The metal-Clad Laminate is a plate-like material obtained by immersing electronic glass fiber cloth or other reinforcing materials in a resin solution, coating one or both surfaces with a metal foil, and hot-pressing, and is called a metal-Clad Laminate, which is simply referred to as a metal-Clad Laminate or a metal-Clad plate, such as a Copper-Clad Laminate or a Copper-Clad Laminate (CCL). Metal clad laminates such as copper clad laminates are base laminates for manufacturing Printed Circuit boards (PCBs for short), which are one of the important parts in the electronics industry. Almost every kind of electronic equipment, as small as electronic watches, calculators, as large as computers, communication electronics, military weaponry systems, requires printed boards for electrical interconnection as long as there are electronic components such as integrated circuits. The metal clad laminate is provided on the entire printed circuit board and mainly performs three functions of conduction, insulation and support.
With the rapid development of electronic devices in miniaturization, multi-functionalization, high performance, and high reliability, printed circuit boards are required to be developed more and more rapidly in directions of high precision, high density, high performance, microvoiding, and thinning. While the CCL determines the performance of the PCB to a large extent.
The development trend of printed circuit boards, such as high precision, high density, high performance, microporosity, thinning and multilayering, requires metal-clad plates, such as copper-clad plates, to have higher thermal and mechanical properties. For example, electronic products are increasingly applied to multilayer boards, and in order to ensure stable and reliable performance of multilayer circuit boards, it is necessary to laminate the multilayer boards with characteristics of low dielectric loss factor, high heat resistance, low thermal expansion coefficient, and the like.
Disclosure of Invention
An object of the present disclosure is to provide a resin composition, a prepreg for a printed circuit obtained by impregnating the resin composition with a reinforcing material such as glass fiber cloth (abbreviated as glass fiber cloth), and a metal-clad laminate including the prepreg for a printed circuit, such that the metal-clad laminate has at least one of characteristics of low dielectric loss factor, high heat resistance, low thermal expansion coefficient, and the like.
Another object of the present disclosure is to provide an insulating board including the prepreg for a printed circuit and a printed circuit board including the prepreg for a printed circuit, the insulating board or the metal clad laminate, wherein the insulating board or the metal clad laminate has one of characteristics of a low dielectric loss factor, high heat resistance, a low thermal expansion coefficient, and the like.
Accordingly, in one aspect, the present disclosure provides a resin composition comprising:
a silicon aryne resin;
polyphenylene ether resin containing unsaturated bond; and
a butadiene polymer, a butadiene-based polymer,
wherein the weight ratio of the silicon aryne resin, the polyphenylene ether resin containing unsaturated bonds and the butadiene polymer is ((1-95): (5-70)).
According to one embodiment of the present disclosure, the silicon aryne resin is represented by the formula:
wherein
n is an integer between 1 and 5; and is
R1And R2Each independently is a group selected from the group consisting of: hydrogen, C1-6Alkyl or C3-6A cycloalkyl group.
According to another embodiment of the present disclosure, the number average molecular weight of the silicon aryne resin is 250 to 10000.
According to another embodiment of the present disclosure, the polyphenylene ether resin containing an unsaturated bond is a polyphenylene ether resin containing an unsaturated double bond at a terminal group or a side chain, and has a molecular main chain structure as shown below:
wherein n is an integer so that the unsaturated bond-containing polyphenylene ether resin has a number average molecular weight of 1000 to 7000.
According to another embodiment of the present disclosure, the butadiene polymer is selected from the group consisting of: a butadiene homopolymer, a butadiene copolymer, or a combination thereof.
According to another embodiment of the present disclosure, the butadiene copolymer is selected from the group consisting of: polybutadiene homopolymer, styrene-butadiene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleic anhydride diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer and maleic anhydride styrene-butadiene copolymer, or a mixture of at least two thereof.
According to another embodiment of the present disclosure, the content of the 1, 2-vinyl group on the side chain of the butadiene copolymer is 18% by weight or more.
According to another embodiment of the present disclosure, the butadiene polymer has a number average molecular weight ranging from 1000 to 10000.
According to another embodiment of the present disclosure, the resin composition further comprises an accelerator, wherein the accelerator is present in the resin composition in an amount of 0.01 to 5 wt.%.
According to another embodiment of the present disclosure, the accelerator is selected from the group consisting of: any one or a mixture of at least two of peroxide, acetylacetone metal salt, naphthenic acid metal salt, vanadium pentoxide, amine, quaternary ammonium salt, imidazole and triphenylphosphine.
According to another embodiment of the present disclosure, the resin composition further comprises a filler.
According to another embodiment of the present disclosure, the filler is selected from: any one or a mixture of at least two of clay such as alumina, titanium oxide, mica, silica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, and silicon carbide.
According to another embodiment of the present disclosure, the resin composition further comprises a flame retardant.
According to another embodiment of the present disclosure, the resin composition further comprises a solvent.
In another aspect, the present disclosure provides a prepreg for a printed circuit, comprising a reinforcing material and a resin composition as described in any one of the above attached thereto by wet-drying.
In a further aspect, the present disclosure provides an insulating board comprising at least one prepreg sheet for printed circuits as described above.
In yet another aspect, the present disclosure provides a metal clad laminate comprising at least one prepreg sheet for printed circuits as described above and a metal foil.
In yet another aspect, the present disclosure provides a printed circuit board comprising: at least one prepreg sheet for printed circuits as described above, or at least one insulating sheet as described above, or at least one metal-clad laminate as described above.
According to the present disclosure, a resin composition, a prepreg for a printed circuit obtained by impregnating the resin composition with a reinforcing material, a metal-clad laminate or an insulating board including the prepreg for a printed circuit, and a printed circuit board including the prepreg for a printed circuit, the insulating board, or the metal-clad laminate can be provided so that the metal-clad laminate can have at least one of characteristics such as a low dielectric loss factor, a high heat resistance, a low thermal expansion coefficient, and the like.
Detailed Description
The technical solutions in the examples of the present disclosure will be clearly and completely described below in connection with the specific embodiments of the present disclosure, and it is obvious that the described embodiments and/or examples are only a part of the embodiments and/or examples of the present disclosure, and not all embodiments and/or examples. All other embodiments and/or all other examples that can be obtained by one of ordinary skill in the art without making any inventive step based on the embodiments and/or examples in the present disclosure are within the scope of the present disclosure.
In the following description, layers and films may be used interchangeably. The resin composition is hereinafter sometimes also referred to as an adhesive.
In the present disclosure, all numerical features are meant to be within the error of measurement, for example within ± 10%, or within ± 5%, or within ± 1% of the defined numerical value.
The term "comprising", "including" or "containing" as used in this disclosure means that it may have, in addition to the recited components, other components which impart different properties to the prepreg sheet. In addition, references to "comprising," "including," or "containing" in this disclosure may also include references to "consisting essentially of … …," and may instead be "or" consist of.
In the present disclosure, amounts, ratios, etc., are by weight if not specifically indicated.
In the present disclosure, the resin composition including the solvent may also be referred to as a resin cement.
As described above, the present disclosure may provide a resin composition comprising:
a silicon aryne resin;
polyphenylene ether resin containing unsaturated bond; and
a butadiene polymer, a butadiene-based polymer,
wherein the weight ratio of the silicon aryne resin, the polyphenylene oxide resin containing unsaturated bonds and the butadiene polymer is (1-95) to (5-70).
Silicon aryne resin
The silicon aryne resin can be a resin with a molecular main chain containing silicon element, benzene ring and alkyne structure.
The silicon aryne resin may be represented by the formula:
wherein
n is an integer between 1 and 5;
r' and R "are each independently a group selected from the group consisting of: hydrogen, C1-6Alkyl or C3-6A cycloalkyl group.
Preferably, the silicon aryne resin may be represented by the following formula
Wherein
n is an integer between 1 and 5; and is
R1And R2Each independently is a group selected from the group consisting of: hydrogen, C1-6Alkyl or C3-6A cycloalkyl group.
In the above formula, the two alkynyl groups on the benzene ring may be in ortho, meta or para positions. The silicon aryne resin can be obtained by polymerizing diethynylbenzene with dichlorosilane. For example, it can be obtained by polymerizing diethynylbenzene with dichlorosilane by a Grignard reaction.
Examples of the diacetylene-benzenes may include 1, 2-diacetylene-benzene, 1, 3-diacetylene-benzene, and 1, 4-diacetylene-benzene.
Examples of dichlorosilanes may include R' SiCl2Or R is1R2SiCl2Wherein R ', R', R1And R2Each independently is a group selected from the group consisting of: hydrogen, C1-6Alkyl or C3-6A cycloalkyl group.
Specific examples of dichlorosilane may include methyldichlorosilane and dichlorodimethylsilane.
C1-6Examples of the alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, various pentyl groups and various hexyl groups. C3-6Examples of the cycloalkyl group may include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The number average molecular weight of the silaaryne resin may be about 250 to 10000, preferably about 500 to 2000. The low molecular weight silicon aryne resin is easier to dissolve in a solvent, has better compatibility with polyphenylene oxide resin containing unsaturated bonds, can reduce the risk of resin separation and phase separation, and is favorable for better forming an interpenetrating network structure. However, the reaction time of the silicon aryne resin with the excessively low molecular weight is too long, which is unfavorable for the curing process of the resin system.
The weight ratio of the silicon aryne resin in the resin composition has a significant influence on the flame retardant property of the resin composition. When the weight ratio of the silicon aryne resin to the sum of the silicon aryne resin, the polyphenylene ether resin containing unsaturated bonds and the butadiene polymer is more than 75 percent, the system can achieve V-0 flame retardance without using a flame retardant.
Polyphenylene ether resin containing unsaturated bond
The polyphenylene ether resin having an unsaturated bond may be a polyphenylene ether resin having an unsaturated double bond at a terminal group or a side chain, and has a molecular main chain structure shown below:
wherein n is an integer so that the unsaturated bond-containing polyphenylene ether resin has a number average molecular weight of 1000 to 7000.
Unsaturated double bonds contained in the terminal groups or side chains in the polyphenylene ether resin containing unsaturated bonds can be cured and crosslinked, and thus a crosslinked cured product can be formed.
Polyphenylene ether resins containing unsaturated bonds are generally prepared by substituting hydrogen atoms on the terminal groups or side chains of polyphenylene ether resins such as low molecular weight polyphenylene ether resins with compounds containing unsaturated double bonds. The polyphenylene ether resin containing an unsaturated bond may be liquid or solid at room temperature. The size of the molecular weight of the polyphenylene ether resin containing unsaturated bonds affects the processing technology and the performance of the final crosslinking cured product, and the larger the molecular weight is, the larger the viscosity of the polyphenylene ether resin liquid containing unsaturated bonds or the viscosity of the solution of the polyphenylene ether resin liquid containing unsaturated bonds or solid in a solvent is, the fewer the reactive groups are, and the poorer the compatibility with other components is; the smaller the molecular weight, the smaller the viscosity of the unsaturated bond-containing polyphenylene ether resin liquid or the viscosity of a solution of the unsaturated bond-containing polyphenylene ether resin liquid or solid in a solvent, the more reactive groups and the better the compatibility with other components, but too small a molecular weight causes a loss in dielectric properties and toughness of the crosslinked cured product. Therefore, the number average molecular weight of the polyphenylene ether resin containing an unsaturated double bond is about 1000 to 7000, and preferably the number average molecular weight of the polyphenylene ether resin containing an unsaturated double bond is about 1000 to 4000.
The polyphenylene ether resin containing an unsaturated bond plays a main role in improving the adhesion and toughness of the resin composition in the resin composition. Too small an amount is insufficient for improving the peel strength and interlayer adhesion of a metal-clad plate such as a copper-clad plate, but too much polyphenylene ether resin containing an unsaturated bond lowers the glass transition temperature. And the dielectric property of the polyphenylene oxide resin containing unsaturated bonds is inferior to that of silicon aryne resin and butadiene polymer, so that the dielectric constant and the dielectric loss of a metal-clad plate such as a copper-clad plate can be improved when the dosage is excessive.
Butadiene polymers
The butadiene polymer may be selected from: a butadiene homopolymer, a butadiene copolymer, or a combination thereof.
Examples of the butadiene co-copolymer may include any one of or a mixture of at least two of a styrene-butadiene copolymer, a hydrogenated diene-butadiene-styrene copolymer, a maleic anhydride-diene-butadiene-styrene copolymer, a styrene-isoprene-styrene copolymer, a styrene-butadiene-divinylbenzene copolymer and a maleic anhydride-styrene-butadiene copolymer.
In order to secure the curability of the resin composition, the content of the 1, 2-vinyl group in the side chain of the polymer is preferably about 18% by weight or more, more preferably 30% by weight or more.
In order to secure the curability of the resin composition and the dielectric properties of the cured product, and the fluidity of the prepreg or prepreg, etc., the number average molecular weight of the butadiene polymer may be in the range of about 1000 to 10000.
The butadiene polymer has good dielectric properties but poor adhesion and flame retardancy, and functions in the resin composition to increase the fluidity of the silicon aryne resin and to weaken the crystallinity of the silicon aryne resin. When the amount is too small, the effect is not sufficiently exhibited, but when the amount is too large, the peel strength of a metal-clad plate such as a copper-clad plate is lowered, and the flame retardancy is deteriorated.
Accelerator
Optionally, the resin composition further comprises an accelerator to cope with the requirements of different curing conditions.
In the case of containing an accelerator, the content of the accelerator in the above resin composition may be about 0.01 to 5% by weight.
The accelerator may be selected from: any one or a mixture of at least two of peroxide, acetylacetone metal salt, naphthenic acid metal salt, vanadium pentoxide, amine, quaternary ammonium salt, imidazole and triphenylphosphine.
Examples of the peroxide may include: dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyisopropylcarbonate, 2, 5-dimethyl-2, 5-di-tert-butyl cumyl peroxy hexyne-3, 2, 5-dimethyl 2, 5-di-tert-butyl peroxy hexane, p-menthane peroxide, 1, 1-bis (tert-amylperoxy) cyclohexane, diisopropylbenzene hydroperoxide, benzoyl peroxide or benzoyl peroxide derivatives. Examples of the amine may include aniline.
The metals in the metal salts of acetylacetone and naphthenic acid can be, independently, alkali metals, alkaline earth metals, or transition metals, e.g., potassium, calcium, sodium, magnesium, aluminum, zinc, iron, cobalt, and the like.
In order to better adapt to processing technologies such as impregnation, a solvent can be added into the resin composition to reduce the viscosity of the resin during impregnation.
Such a solvent is not particularly limited, and is preferably at least one solvent containing an aromatic hydrocarbon. Specific examples of the aromatic hydrocarbon solvent include toluene, xylene, mesitylene, and the like. These aromatic hydrocarbon solvents may be used alone or in combination of two or more.
Further, if the aromatic hydrocarbon-based solvent is contained, other solvents may be used in combination, and the solvent used in combination is not particularly limited, and specific examples thereof include: alcohols such as methanol, ethanol, and butanol; ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, and ethyl acetate; nitrogen-containing solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone, and these solvents may be used singly or in combination. In addition, when the aromatic hydrocarbon solvent is mixed with another solvent to form a mixed solvent, the aromatic hydrocarbon solvent is preferably 50% by weight or more of the total solvent.
In the case of containing a solvent, the content of the solvent in the resin composition may be 10 to 99.5% by weight, preferably about 20 to 99% by weight.
In order to obtain a metal-clad laminate having better modulus and heat resistance from the resin composition, a filler such as an inorganic filler may be added to the resin composition.
Specific examples of the inorganic filler include, but are not particularly limited to, alumina, titanium oxide, mica, silica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate, and silicon carbide. These may be used alone or in combination of two or more. The shape is not particularly limited, but a spherical shape is preferable. There is a certain limit to the particle diameter of the filler, and the particle diameter is preferably 0.01 to 30 μm, more preferably 0.1 to 15 μm.
When the particle size of the filler is 0.01 μm or less, the flowability of the resin composition is lowered, and therefore, moldability in producing a prepreg sheet or a metal-clad laminate is deteriorated, voids and the like are likely to occur, or the surface area is increased, and therefore, the bonding area between the metal and the resin is reduced, which is not preferable, and the peel strength of the printed wiring board is lowered. On the other hand, a particle size of more than 30 μm is not preferable because it causes a decrease in insulation reliability between wirings of a printed wiring board and an insulating layer.
In the case where the filler is contained, the content of the filler in the resin composition may be about 1 to 90% by weight, preferably about 5 to 80% by weight.
In order to better meet the requirements of flame retardance and the like, a flame retardant can be added into the resin composition.
As the flame retardant, a flame retardant such as bromine, phosphorus, or metal hydroxide is preferably used.
Examples of bromine-based flame retardants are: brominated additive flame retardants such as brominated epoxy resins including brominated bisphenol a type epoxy resins and brominated phenol novolac type epoxy resins, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1, 2-dibromo-4- (1, 2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene oxide, brominated polystyrene, and 2, 4, 6-tris (tribromophenoxy) -1, 3, 5-triazine; brominated flame retardants containing unsaturated double bond groups, such as tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A-type dimethacrylate, pentabromobenzyl acrylate, and brominated styrene.
Examples of phosphorus-based flame retardants are: aromatic phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyldi2, 6-dimethylphenyl phosphate, and resorcinol bis (diphenyl phosphate); phosphonates such as divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate; phosphates such as phenyl diphenylphosphate, methyl diphenylphosphate, and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives; phosphazene compounds such as bis (2-allylphenoxy) phosphazene and xylenol phosphazene; phosphorus flame retardants such as melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds, red phosphorus and the like.
Examples of metal hydroxide flame retardants are magnesium hydroxide or aluminum hydroxide.
The flame retardant may be used alone or in combination of two or more.
In the case of containing a flame retardant, the content of the flame retardant in the resin composition may be about 1 to 60% by weight, preferably about 2 to 40% by weight.
The resin composition may further contain various auxiliaries. Specific examples of the auxiliary include a filler dispersant, an antifoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, and a lubricant. These auxiliaries may be used alone or in admixture of any two or more.
The resin composition of the present disclosure can be prepared by a known method such as compounding, stirring, mixing a silicon aryne resin, a polyphenylene ether resin containing an unsaturated bond and a butadiene polymer, and optionally any one or a mixture of at least two of an accelerator, a solvent, a filler, a flame retardant, a dispersant, an antifoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant and a lubricant.
The resin composition is prepared into resin glue solution by mechanical stirring, emulsification or ball milling dispersion, then the resin glue solution is adopted to soak the reinforcing material, and the pre-soaking sheet is obtained by drying. The metal-clad laminate can be prepared by hot-pressing the prepreg sheet and a metal foil such as a copper foil or an aluminum foil in a vacuum press.
Examples of the reinforcing material may include: glass fiber cloth, glass fiber non-woven fabric, organic non-woven fabric and the like.
In order to reduce the viscosity of the resin dope, the impregnation may be performed under heating. Heating to make the resin glue solution temperature less than the boiling point of the solvent, preferably the resin glue solution temperature is about 20-90 deg.C, more preferably about 25-55 deg.C.
In another aspect, the present disclosure may also provide a prepreg for a printed circuit, including a reinforcing material and the resin composition according to any one of the above attached thereto by wet-drying.
In yet another aspect, the present disclosure may also provide an insulating board or a metal-clad laminate containing at least one prepreg sheet for a printed circuit as described above.
In yet another aspect, the present disclosure may also provide a printed circuit board including: at least one prepreg sheet for printed circuits as described above, or at least one insulating sheet as described above, or at least one metal-clad laminate as described above.
According to the present disclosure, a resin composition, a prepreg for a printed circuit obtained by impregnating the resin composition with a reinforcing material, a metal-clad laminate or an insulating board including the prepreg for a printed circuit, and a printed circuit board including the prepreg for a printed circuit, the insulating board, or the metal-clad laminate can be provided so that the metal-clad laminate can have at least one of characteristics such as a low dielectric loss factor, a high heat resistance, a low thermal expansion coefficient, and the like.
Examples
The technical solution of the present disclosure is further explained by the following embodiments. However, these examples are intended to illustrate the disclosure and should not be construed as limiting the disclosure.
Preparation example
The silicon aryne resins used in the examples and comparative examples were prepared as follows.
3.5 parts of magnesium powder (chemical purity, Shanghai pharmaceutical group chemical Co., Ltd.) and 40 parts of Tetrahydrofuran (THF) solvent were charged into a reaction vessel filled with nitrogen, stirred at room temperature and added dropwise with a mixed solution of 13.5 parts of bromoethane (chemical purity, Shanghai pharmaceutical group chemical Co., Ltd.) and 40 parts of THF, and the temperature was maintained at 50 ℃ for 1 hour after completion of the dropwise addition. Then, a mixture of 7.5 parts of 1, 3-diacetylene benzene (Fine chemical Co., Ltd., Shandong, Guzhou) and 40 parts of THF solvent was added dropwise in an ice water bath, and the mixture was kept at 65 ℃ for 1 hour after the addition. Then cooling again, adding dropwise a mixture of 5.5 parts of dichlorodimethylsilane (chemical purity, used after distillation by Xinan chemical group Co., Ltd., Zhejiang) and 40ml of THF under ice water cooling bath, and keeping the temperature at 40 ℃ and 70 ℃ for 1h respectively after dropwise addition. After the reaction was completed, THF in the reaction product was distilled off, and a mixture of 7.2 parts of glacial acetic acid and 50 parts of toluene solvent was added dropwise under ice-water cooling bath conditions, followed by stirring thoroughly, then 140 parts of 2.0% dilute aqueous hydrochloric acid solution was added dropwise, and after stirring thoroughly, the upper organic phase was separated. The organic phase was sufficiently washed with water to neutrality, then dried, filtered, and the toluene was evaporated to obtain a silylyne resin (i.e., a silylyne resin (number average molecular weight 1200, mobile phase in GPC test is THF) used in examples and comparative examples, hereinafter referred to as PSA 1200).
Examples 1 to 8 and comparative examples 1 to 4
According to the amounts (parts by weight) shown in table 1 or table 2, a silicon aryne resin, a polyphenylene ether resin containing an unsaturated bond, a butadiene polymer, and an accelerator were sufficiently dissolved in a solvent and mixed uniformly, and then an inorganic filler and/or a flame retardant was added and mixed uniformly to obtain a glue solution. Uniformly soaking the E-type glass fiber cloth (produced by Ridong textile) with the model of 1080 into the above glue solution, and baking in a forced air oven at 155 deg.C for 3min to obtain the prepreg. Each of 4 or 8 sheets of the prepreg was stacked, covered with 18 μm reverse copper foil (manufactured by suzhou fuda metal limited), and pressed in a vacuum hot press at a pressure of 3MPa and a temperature of 210 ℃ for 90 minutes to obtain two thickness samples of a laminate (hereinafter, sometimes referred to as a copper-clad laminate or a copper-clad laminate) (i.e., 8 × 1080HH samples of the laminate and 4 × 1080HH samples of the laminate).
The amounts of the components in the resin composition and the test results of the resin composition are shown in tables 1 and 2 below, in which the thermal expansion coefficient, the thermal expansion ratio, and the thermal stress were tested using the sample of the laminate of 8 x 1080HH, and the other samples of the laminate using 4 x 1080 HH.
TABLE 1
TABLE 2
PSA 1200: the silicon aryne resin obtained in the preparation example;
SA 9000: allyl modified polyphenylene ether resin, manufactured by SABIC;
ricon 100: a butadiene-styrene copolymer having a number average molecular weight of 4500 and a side chain vinyl content of 70% by weight, produced at CRAYVALLEY;
ricon 181: a butadiene-styrene copolymer having a number average molecular weight of 3200 and a side chain vinyl content of 20 to 40% by weight, produced at CRAYVALLEY;
ricon 257: a butadiene-styrene-divinylbenzene branched terpolymer having a number average molecular weight of 5300 and a pendant vinyl group content of 30 to 50% by weight, produced at CRAYVALLEY;
b1000: butadiene homopolymer, number average molecular weight about 1200, side chain vinyl content 85% by weight, manufactured by NISSO, Japan;
b3000: butadiene homopolymer having a number average molecular weight of about 3200 and a side chain vinyl content of 92% by weight, produced by NISSO of Japan;
DCP: dicumyl peroxide, reagent;
a solution of 1 part cobalt acetylacetonate and 1.5 parts triphenylphosphine in 100 parts ethanol: the amounts in the table refer to the amounts of cobalt acetylacetonate and triphenylphosphine, i.e. 0.5 parts by weight of 0.2 parts by weight of cobalt acetylacetonate and 0.3 parts by weight of triphenylphosphine;
DQ 1028L: spherical silicon dioxide, D50 about 3.0 μm, produced by Jiangsu Union;
SC 2050: spherical silica, D50 about 0.5 μm, available from Toyota, Japan;
BT-93 w: an additive bromine flame retardant produced by American Yabao;
XP 7866: adding type phosphorus flame retardant, and producing American Yabao;
aluminum hydroxide: OL-104, Yabao, USA;
toluene: industrial products, commercially available.
The method for testing the properties described in the table is as follows:
1) glass transition temperature Tg: using a dynamic thermomechanical analysis (DMA) test, following the DMA test method specified by IPC-TM-6502.4.24;
2) thermal decomposition temperature (Td): using thermogravimetric analysis (TGA) testing, according to standard IPC-TM-6502.4.24.6;
3) peel Strength (PS): the tensile force required for peeling each millimeter of copper foil from the copper-clad plate at room temperature;
4) dielectric constant (Dk) and dielectric loss tangent (Df): 10GHz was measured by the resonance cavity method (SPDR) according to the standard IPC-TM-6502.5.5.5.
5) Flame retardancy: according to UL94 "50W (20mm) vertical burning test: v-0, V-1 and V-2' test methods, and V-0 is determined to be flame retardant.
6) Coefficient of Thermal Expansion (CTE) and proportion of thermal expansion between 50 ℃ and 260 ℃: the test was carried out using a static thermal analyzer (TMA) according to the IPC-TM-6502.4.24 standard. The Coefficient of Thermal Expansion (CTE) and the 50-260 ℃ thermal expansion ratio are values measured in the length direction of the laminate sample.
7) Thermal stress: the copper clad laminate was floated on the surface of molten tin at 288 ℃ for delamination or bubbling time as a test result.
8) D50: the term "average particle diameter" means a particle diameter corresponding to a point of 50% by volume when a cumulative power distribution curve based on the particle diameter is obtained with the total volume of the particles as 100%, and is measured by a particle size distribution measurement using a laser diffraction scattering method.
As can be seen from the test results of the above examples and comparative examples, the Tg and Td of the sample of this example are both higher than those of the printed circuit board commonly found in the industry. The dielectric loss factor results of the copper clad laminate show that the copper clad laminate has good application performance in high-frequency and high-speed laminates, and the CTE, the thermal expansion ratio of 50-260 ℃ and the thermal stress are excellent.
In contrast to the examples, comparative example 1, which has no butadiene copolymer resin, has relatively low dielectric loss and a large expansion coefficient; the polyphenyl ether resin containing unsaturated double bonds is not contained in the comparative example 2, the peel strength is obviously too low, and the use requirement of the copper-clad plate is not met; comparative example 3 does not contain silicon aryne resin, the dielectric loss is relatively large, and the expansion coefficient is also large; comparative example 4 is a silarylyne single resin system, which has a smaller coefficient of expansion but a larger dielectric constant.
As described above, a resin composition, a prepreg for a printed circuit obtained by impregnating the resin composition with a glass cloth, a metal-clad laminate or an insulating board comprising the prepreg for a printed circuit, and a printed wiring board comprising the prepreg for a printed circuit, the insulating board or the metal-clad laminate can be provided, so that the metal-clad laminate can have at least one of characteristics such as a low dielectric loss factor, a high heat resistance, and a low thermal expansion coefficient, and preferably has a low dielectric loss factor, a high heat resistance, and a low thermal expansion coefficient at the same time. Meanwhile, the V-0 level flame retardant performance can be achieved by adding the flame retardant, so that the flame retardant is suitable for application needing flame retardance.
It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments of the disclosure without departing from the spirit and scope of the disclosure. Thus, if such modifications and variations of the present disclosure fall within the scope of the claims of the present disclosure and their equivalents, the present disclosure is intended to include such modifications and variations as well.
Claims (17)
1. A resin composition, the resin composition comprising:
a silicon aryne resin;
polyphenylene ether resin containing unsaturated bond; and
a butadiene polymer, a butadiene-based polymer,
wherein the weight ratio of the silicon aryne resin, the polyphenylene ether resin containing unsaturated bonds and the butadiene polymer is (1-95) to (5-70),
wherein the silicon aryne resin is represented by the formula:
wherein
n is an integer between 1 and 5; and is
R1And R2Each independently is a group selected from the group consisting of: hydrogen, C1-6Alkyl or C3-6A cycloalkyl group,
the weight ratio of the silicon aryne resin to the sum of the silicon aryne resin, the polyphenylene ether resin containing unsaturated bonds and the butadiene polymer is more than 75 percent,
the unsaturated bond-containing polyphenylene ether resin has a number average molecular weight of 1000 to 7000, and
the butadiene polymer has a number average molecular weight ranging from 1000 to 10000.
2. The resin composition according to claim 1, wherein the number average molecular weight of the silarylyne resin is 250 to 10000.
3. The resin composition according to claim 1, wherein the polyphenylene ether resin having an unsaturated bond is a polyphenylene ether resin having an unsaturated double bond at a terminal group or a side chain, and has a molecular main chain structure shown as follows:
wherein n is an integer so that the unsaturated bond-containing polyphenylene ether resin has a number average molecular weight of 1000 to 7000.
4. The resin composition of claim 1, wherein the butadiene polymer is selected from the group consisting of: a butadiene homopolymer, a butadiene copolymer, or a combination thereof.
5. The resin composition according to claim 4, wherein the butadiene copolymer is selected from any one of a styrene-butadiene copolymer, a hydrogenated diene-butadiene-styrene copolymer, a maleinated diene-butadiene-styrene copolymer, a styrene-isoprene-styrene copolymer, a styrene-butadiene-divinylbenzene copolymer and a maleinated styrene-butadiene copolymer or a mixture of at least two thereof.
6. The resin composition according to claim 1, wherein the content of the 1, 2-vinyl group in the side chain of the butadiene polymer is 18% by weight or more.
7. The resin composition according to claim 1, further comprising an accelerator, wherein the accelerator is contained in an amount of 0.01 to 5% by weight in the resin composition.
8. The resin composition of claim 7, wherein the accelerator is selected from the group consisting of: any one or a mixture of at least two of peroxide, acetylacetone metal salt, naphthenic acid metal salt, vanadium pentoxide, amine, quaternary ammonium salt, imidazole and triphenylphosphine.
9. The resin composition of claim 1, further comprising a filler.
10. The resin composition of claim 9, wherein the filler is selected from the group consisting of: any one or a mixture of at least two of alumina, titanium oxide, mica, silica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, and silicon carbide.
11. The resin composition of claim 10 wherein the clay is calcined clay.
12. The resin composition of claim 1, further comprising a flame retardant.
13. The resin composition of claim 1, further comprising a solvent.
14. A prepreg for printed circuits comprising a reinforcing material and the resin composition according to any one of claims 1 to 12 attached thereto by wet-drying.
15. An insulating board comprising at least one prepreg for printed circuits according to claim 14.
16. A metal clad laminate comprising at least one prepreg for printed circuits according to claim 14 and a metal foil.
17. A printed circuit board, the printed circuit board comprising: at least one prepreg sheet for printed circuits according to claim 14, or at least one insulating sheet according to claim 15, or at least one metal-clad laminate according to claim 16.
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| CN201811596062.8A CN109777123B (en) | 2018-12-25 | 2018-12-25 | Resin composition, prepreg for printed circuit, and metal-clad laminate |
| TW108119392A TWI704185B (en) | 2018-12-25 | 2019-06-04 | Resin composition, prepreg for printed circuit and metal-clad laminate |
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| CN110845853B (en) * | 2019-12-09 | 2021-11-26 | 苏州生益科技有限公司 | Resin composition, and prepreg, laminated board, insulating board, circuit board and coverlay film comprising same |
| CN110922764B (en) * | 2019-12-09 | 2021-10-08 | 苏州生益科技有限公司 | Silicon-containing resin composition and prepreg and laminated board manufactured by using same |
| CN110950901B (en) * | 2019-12-09 | 2023-07-07 | 苏州生益科技有限公司 | Silicone resin, method for producing the same, resin composition, prepreg, laminated board, insulating board, circuit board, and coverlay film |
| CN114634713B (en) * | 2020-12-16 | 2023-07-14 | 广东生益科技股份有限公司 | Resin composition, prepreg and metal-clad laminate |
| CN112795169B (en) * | 2020-12-31 | 2022-07-19 | 广东生益科技股份有限公司 | Resin composition, resin film containing resin composition, prepreg, laminated board, copper-clad plate and printed circuit board |
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| CN103467967A (en) * | 2013-09-16 | 2013-12-25 | 广东生益科技股份有限公司 | Thermosetting resin composition and use thereof |
| CN106480735B (en) * | 2015-08-28 | 2019-06-14 | 广东生益科技股份有限公司 | Circuit substrate and preparation method thereof |
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| TWI704185B (en) | 2020-09-11 |
| CN109777123A (en) | 2019-05-21 |
| TW202024234A (en) | 2020-07-01 |
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