CN109825039B - Cyanate ester resin composition and use thereof - Google Patents
Cyanate ester resin composition and use thereof Download PDFInfo
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- CN109825039B CN109825039B CN201811621233.8A CN201811621233A CN109825039B CN 109825039 B CN109825039 B CN 109825039B CN 201811621233 A CN201811621233 A CN 201811621233A CN 109825039 B CN109825039 B CN 109825039B
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Abstract
The invention provides a cyanate ester resin composition, and a prepreg, a laminated board, a metal foil-clad laminated board and a printed wiring board comprising the cyanate ester resin composition. The cyanate ester resin composition comprises: a cyanate ester resin (A) represented by the following formula (I); and an epoxy resin (B). The cyanate ester resin composition, and the prepreg, the laminated board and the metal foil-clad laminated board prepared by using the cyanate ester resin composition have good heat resistance, humidity resistance, mechanical property, flame retardance and reliability, and low in-plane thermal expansion coefficient, and are suitable for being used as substrate materials for manufacturing high-density printed circuit boards.
Description
Technical Field
The present invention relates to a resin composition, and more particularly, to a cyanate ester resin composition, and a prepreg, a laminate, a metal foil-clad laminate, and a printed wiring board prepared using the same.
Background
With the development of miniaturization, high performance and high functionality of computers, electronic and information communication equipment, higher requirements are also put forward on printed circuit boards: miniaturization, thinning, high integration and high reliability. This requires that metal-clad laminates used for manufacturing printed wiring boards have more excellent moisture resistance, heat resistance, reliability, and the like.
Meanwhile, due to the increase in the packing density of semiconductors, in order to reduce the problem of warpage generated during the packaging process, it has been strongly demanded in recent years to reduce the in-plane thermal expansion coefficient of the laminate.
Cyanate ester resin has excellent dielectric properties, heat resistance, mechanical properties and process processability, and is a commonly used matrix resin in the preparation of metal foil-clad laminates for high-end printed circuit boards. However, cyanate ester resins are generally used after being modified with epoxy resins or the like because of their poor wet heat resistance after curing.
In order to obtain better properties such as heat resistance, wet heat resistance, mechanical properties, flame retardancy and reliability, low in-plane thermal expansion coefficient, etc., it is still desired in the art to develop a novel cyanate ester resin composition having excellent properties.
Disclosure of Invention
In view of the technical problems set forth above, it is an object of the present invention to provide a cyanate ester resin composition, and a prepreg, a laminate, a metal-foil-clad laminate and a printed wiring board comprising the same. The cyanate ester resin composition, and the prepreg, the laminated board and the metal foil-clad laminated board prepared by using the cyanate ester resin composition have good heat resistance, humidity resistance, mechanical property, flame retardance and reliability, and low in-plane thermal expansion coefficient, and are suitable for being used as substrate materials for manufacturing high-density printed circuit boards.
The present inventors have made intensive studies and completed the present invention.
According to an aspect of the present invention, there is provided a cyanate ester resin composition comprising:
a cyanate ester resin (a) represented by the following formula (I):
wherein R is an arylene group having 6 to 18 carbon atoms, R1、R2Each independently is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 19 carbon atoms; and n is an integer from 1 to 20; and
an epoxy resin (B).
According to certain embodiments of the invention, n is an integer from 1 to 15, and n is preferably an integer from 1 to 10.
According to certain embodiments of the invention, R is phenylene, naphthylene or biphenylene, preferably phenylene.
According to certain embodiments of the invention, R1、R2Each independently a hydrogen atom or a methyl group, preferably a hydrogen atom.
According to certain embodiments of the present invention, the cyanate ester resin (a) has the structure represented by the following formula (Γ):
wherein R is an arylene group having 6 to 18 carbon atoms; and n is an integer of 1 to 20.
According to certain embodiments of the present invention, the cyanate ester resin (a) constitutes 10 to 90 wt%, preferably 20 to 80 wt%, and more preferably 30 to 70 wt% of the total weight of the cyanate ester resin (a) and the epoxy resin (B).
According to certain embodiments of the present invention, the epoxy resin (B) is selected from epoxy resins containing at least two epoxy groups.
According to certain embodiments of the present invention, the epoxy resin (B) comprises 10 to 90 weight percent, preferably 20 to 80 weight percent, and more preferably 30 to 70 weight percent of the total weight of the cyanate ester resin (a) and the epoxy resin (B).
According to certain embodiments of the present invention, the cyanate ester resin composition further comprises a maleimide compound (C).
According to certain embodiments of the present invention, the amount of the maleimide compound (C) is 5 to 80 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the total weight of the cyanate ester resin (a) and the maleimide compound (C).
According to certain embodiments of the present invention, the cyanate ester resin composition further comprises an inorganic filler (D).
According to certain embodiments of the present invention, the amount of the inorganic filler (D) is 10 to 300 parts by weight, preferably 30 to 270 parts by weight, and more preferably 50 to 250 parts by weight, based on 100 parts by weight of the total weight of the cyanate ester resin (a) and the epoxy resin (B) or 100 parts by weight of the total weight of the cyanate ester resin (a), the epoxy resin (B), and the maleimide compound (C).
According to another aspect of the present invention, there is provided a prepreg comprising a substrate and the cyanate ester resin composition as described above attached to the substrate after drying by impregnation.
According to a further aspect of the present invention there is provided a laminate comprising at least one prepreg as described above.
According to a further aspect of the present invention, there is provided a metal-clad laminate comprising at least one prepreg as described above and a metal foil clad to one or both sides of the prepreg.
According to a further aspect of the present invention there is provided a printed wiring board comprising at least one prepreg as described above.
Compared with the prior art in the field, the invention has the advantages that:
by using the specific cyanate ester resin (a) having the structure of formula (I) as a curing agent together with the epoxy resin (B) or with the epoxy resin (B) and the maleimide compound (C), a resin composition having good heat resistance, moist heat resistance, mechanical properties, flame retardancy and reliability and a low coefficient of thermal expansion in the plane direction can be obtained, which can be used for producing a prepreg, a laminate, a metal foil-clad laminate and a printed wiring board having desired properties. In other words, the cyanate ester resin composition provided by the invention has good heat resistance, humidity resistance, mechanical property, flame retardance and reliability, and low in-plane thermal expansion coefficient. The prepreg, the laminated board and the metal foil-clad laminated board prepared by using the cyanate resin composition also have good heat resistance, humidity resistance, mechanical property, flame retardance and reliability, and low in-plane thermal expansion coefficient, and are suitable for manufacturing substrate materials of high-density printed circuit boards.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It will be appreciated that other embodiments are contemplated and may be made without departing from the scope or spirit of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense.
Unless otherwise indicated, all numbers expressing feature sizes, quantities, and physical and chemical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
The inventors of the present invention have found that the use of the cyanate ester resin (a) having the structure of formula (I) as a curing agent together with the epoxy resin (B) or with the epoxy resin (B) and the maleimide compound (C) can significantly improve the heat resistance, moist heat resistance, mechanical properties, flame retardancy and reliability of the cyanate ester resin composition and reduce the in-plane thermal expansion coefficient. Based on the above findings, the inventors have completed the present invention.
According to an aspect of the present invention, there is provided a cyanate ester resin composition comprising:
a cyanate ester resin (a) represented by the following formula (I):
wherein R is an arylene group having 6 to 18 carbon atoms, R1、R2Each independently is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 19 carbon atoms; and n is an integer from 1 to 20; and
an epoxy resin (B).
The cyanate ester resin (a) having the structure of formula (I) of the present invention is not particularly limited, and may be selected from cyanate ester resins or cyanate ester prepolymers having at least four cyanate groups in the molecular structure and having the structure of formula (I). The cyanate ester resin (a) may be used alone, or at least two cyanate ester resins (a) may be used in combination as needed.
The position of the cyanate group is not particularly limited as long as each naphthalene group in the formula (I) has two cyanate groups. Preferably, the two cyanate groups of the naphthyl group are located on different phenyl rings. For example, the cyanate ester resin (a) may have a structure represented by the following formula (I'):
preferably, in the cyanate ester resin (a) represented by formula (I), n is an integer of 1 to 15, and n is preferably an integer of 1 to 10. When the molecular weight is too large, too fast reaction is caused by too many cyanate groups, so that the gummosis window becomes small and the lamination process is difficult.
Preferably, in the cyanate ester resin (a) represented by the formula (I), R is phenylene, naphthylene or biphenylene, and R is preferably phenylene.
Preferably, in the cyanate ester resin (A) represented by the formula (I), R1、R2Each independently is a hydrogen atom or a methyl group, and R1、R2Preferably a hydrogen atom.
The method for synthesizing the cyanate ester resin (a) represented by the formula (I) is not particularly limited, and those skilled in the art can select the cyanate ester resin (a) according to the prior art in combination with their own expertise. Specifically, the cyanate ester resin (a) represented by the formula (I) can be obtained, for example, by: reacting a phenolic resin with a structure shown as a formula (II) with cyanogen halide in an inert organic solvent in the presence of a basic compound to obtain a cyanate ester resin (A) shown as a formula (I).
Wherein, R, R1、R2And n is as defined above for formula (I).
According to the technical scheme of the invention, the dosage of the cyanate ester resin (a) is not particularly limited. In order to achieve a good effect of the cyanate ester resin (a) in the cyanate ester resin composition, it preferably accounts for 10 to 90 wt%, for example, 12%, 15%, 21%, 26%, 32%, 36%, 45%, 52%, 58%, 63%, 67%, 72%, 77%, 85%, 88%, further preferably 20 to 80 wt%, and particularly preferably 30 to 70 wt% of the total weight of the cyanate ester resin (a) having the structure of formula (I) and the epoxy resin (B).
The epoxy resin (B) of the present invention is not particularly limited, and is selected from epoxy resins having at least two epoxy groups, and examples thereof include bisphenol A type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, tetramethylbisphenol F type epoxy resins, bisphenol M type epoxy resins, bisphenol P type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, trifunctional phenol type epoxy resins, tetrafunctional phenol type epoxy resins, naphthalene type epoxy resins, naphthol novolac type epoxy resins, anthracene type epoxy resins, phenolphthalein type epoxy resins, phenoxy type epoxy resins, norbornene type epoxy resins, adamantane type epoxy resins, fluorene type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, Dicyclopentadiene phenol type epoxy resin, aralkyl phenol type epoxy resin, epoxy resin containing an arylene ether structure in the molecule, alicyclic epoxy resin, polyhydric alcohol type epoxy resin, silicon-containing epoxy resin, nitrogen-containing epoxy resin, phosphorus-containing epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, and the like. In order to improve the heat resistance and flame retardancy of the cyanate ester resin composition, the epoxy resin (B) of the present invention is preferably any one of or a mixture of at least two of a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol novolac type epoxy resin, an anthracene type epoxy resin, a phenolphthalein type epoxy resin, a biphenyl type epoxy resin, an aralkyl novolac type epoxy resin, and an epoxy resin containing an arylene ether structure in a molecule, and is preferably any one of or a mixture of at least two of a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol novolac type epoxy resin, an anthracene type epoxy resin, a phenolphthalein type epoxy resin, an aralkyl novolac type epoxy resin, and an epoxy resin containing an arylene ether structure in a molecule. The epoxy resins (B) may be used alone, or at least two epoxy resins (B) may be mixed and used as necessary.
The amount of the epoxy resin (B) used is not particularly limited, and it is preferably 10 to 90% by weight, for example, 12%, 15%, 21%, 26%, 32%, 36%, 45%, 52%, 58%, 63%, 67%, 72%, 77%, 85%, 88%, further preferably 20 to 80% by weight, particularly preferably 30 to 70% by weight, based on the total weight of the cyanate ester resin (a) and the epoxy resin (B) represented by formula (I).
The cyanate ester resin composition of the present invention may further contain a maleimide compound (C). By adding the maleimide compound (C) to the cyanate ester resin composition, a resin composition having more excellent mechanical properties, heat resistance and in-plane thermal expansion coefficient can be obtained. The maleimide compound (C) of the present invention is not particularly limited, and is selected from compounds having at least one maleimide group in the molecular structure, preferably compounds having at least two maleimide groups in the molecular structure. Specifically, the maleimide compound (C) may be selected from the group consisting of N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2, 6-dimethylphenyl) maleimide, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 4-methyl-1, 3-phenylenebismaleimide, m-phenylenebismaleimide, 1, 3-bis (3-maleimidophenoxy) benzene, 1, 3-bis (4-maleimidophenoxy) benzene, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, maleimide having a biphenyl structure in the molecule, polyphenylmethanemaleimide (Polyphenylmethane maleinimide), N-phenylmaleimide prepolymer, N- (2-methylphenyl) maleimide prepolymer, N- (4-methylphenyl) maleimide prepolymer, N- (2, 6-dimethylphenyl) maleimide prepolymer, bis (4-maleimidophenyl) methane prepolymer, bis (4-maleimidophenyl) ether prepolymer, bis (4-maleimidophenyl) sulfone prepolymer, and mixtures thereof, 4-methyl-1, 3-phenylenebismaleimide prepolymer, m-phenylenebismaleimide prepolymer, 1, 3-bis (3-maleimidophenoxy) benzene prepolymer, 1, 3-bis (4-maleimidophenoxy) benzene prepolymer, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane prepolymer, bis (3, 5-dimethyl-4-maleimidophenyl) methane prepolymer, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane prepolymer, bis (3, 5-diethyl-4-maleimidophenyl) methane prepolymer, maleimide prepolymer containing a biphenyl structure in the molecule, m-phenylenebismaleimide prepolymer, 1, 3-bis (3-maleimidophenoxy) benzene prepolymer, 1, 3-bis (4-maleimidophenoxy) -, Polyphenylmethanemaleimide prepolymer, prepolymer of N-phenylmaleimide and an amine compound, prepolymer of N- (2-methylphenyl) maleimide and an amine compound, prepolymer of N- (4-methylphenyl) maleimide and an amine compound, prepolymer of N- (2, 6-dimethylphenyl) maleimide and an amine compound, prepolymer of bis (4-maleimidophenyl) methane and an amine compound, prepolymer of bis (4-maleimidophenyl) ether and an amine compound, prepolymer of bis (4-maleimidophenyl) sulfone and an amine compound, prepolymer of 4-methyl-1, 3-phenylenebismaleimide and an amine compound, prepolymer of m-phenylenebismaleimide and an amine compound, prepolymer of N- (2-methylphenyl) maleimide and an amine compound, prepolymer of N-phenylenebismaleimide and an amine compound, and a mixture of N-methyl-1, 3-phenylenebismaleimide and an amine compound, Any of a prepolymer of 1, 3-bis (3-maleimidophenoxy) benzene and an amine compound, a prepolymer of 1, 3-bis (4-maleimidophenoxy) benzene and an amine compound, a prepolymer of 2, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane and an amine compound, a prepolymer of bis (3, 5-dimethyl-4-maleimidophenyl) methane and an amine compound, a prepolymer of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and an amine compound, a prepolymer of bis (3, 5-diethyl-4-maleimidophenyl) methane and an amine compound, a prepolymer of maleimide and an amine compound having a biphenyl structure in a molecule, or a prepolymer of polyphenylmethane maleimide and an amine compound One or a mixture of at least two thereof, preferably one or a mixture of at least two of bis (4-maleimidophenyl) methane, m-phenylene bismaleimide, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, maleimide or polyphenylmethane maleimide having a biphenyl structure in the molecule, a prepolymer thereof or a prepolymer with an amine compound.
The maleimide compound (C) may be used alone or in combination of plural kinds as required. The amount of the maleimide compound (C) to be used is not particularly limited. Preferably, the amount of the maleimide compound (C) is 5 to 80 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the total weight of the cyanate ester resin (a) and the maleimide compound (C).
The cyanate ester resin composition of the present invention may further contain an inorganic filler (D). The halogen-free flame-retardant resin composition with better mechanical property, humidity resistance, flame retardance and plane direction thermal expansion coefficient can be obtained by adding the inorganic filler (D) into the cyanate ester resin composition. In particular, different types of inorganic fillers (D) may be added in order to achieve different technical purposes. The inorganic filler (D) according to the present invention is not particularly limited, and is selected from any one or a mixture of at least two of silica, metal hydrate, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium sulfate, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, zinc borate, zinc stannate, clay, kaolin, talc, mica, composite fine silica powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, Q glass powder, quartz glass powder, short glass fiber, or hollow glass, preferably crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, aluminum hydroxide, boehmite, magnesium hydroxide, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, magnesium hydroxide, molybdenum oxide, zinc oxide, molybdenum molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, and magnesium oxide, Barium sulfate, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, zinc borate, zinc stannate, clay, kaolin, talc, mica, composite silica fume, E glass frit, D glass frit, L glass frit, M glass frit, S glass frit, T glass frit, NE glass frit, Q glass frit, quartz glass frit, short glass fiber, or hollow glass, or a mixture of at least two thereof, such as a mixture of crystalline silica and fused silica, a mixture of amorphous silica and spherical silica, a mixture of hollow silica and aluminum hydroxide, a mixture of boehmite and magnesium hydroxide, a mixture of molybdenum oxide and zinc molybdate, a mixture of titanium oxide, zinc oxide, strontium titanate, and barium titanate, a mixture of barium sulfate, boron nitride, and aluminum nitride, a mixture of silicon carbide, aluminum oxide, zinc borate, and zinc stannate, a mixture of composite silica micropowder, E glass powder, D glass powder, L glass powder and M glass powder, a mixture of S glass powder, T glass powder, NE glass powder and quartz glass powder, a mixture of clay, kaolin, talc and mica, a mixture of short glass fibers and hollow glass, and further preferably fused silica or/and boehmite. Among them, fused silica is preferable because it has a characteristic of low thermal expansion coefficient and boehmite is excellent in flame retardancy and heat resistance. The inorganic filler (D) is more preferably spherical fused silica, and spherical fused silica is preferable because it has characteristics such as a low thermal expansion coefficient and good dielectric properties and also has good dispersibility and fluidity.
Average particle diameter (D) of inorganic filler (D)50) The average particle diameter (d) is not particularly limited, but is determined from the viewpoint of dispersibility50) Preferably 0.1 to 10 microns, such as 0.2 microns, 0.8 microns, 1.5 microns, 2.1 microns, 2.6 microns, 3.5 microns, 4.5 microns, 5.2 microns, 5.5 microns, 6 microns, 6.5 microns, 7 microns, 7.5 microns, 8 microns, 8.5 microns, 9 microns, 9.5 microns, more preferably 0.2 to 5 microns. Can be used as requiredThe inorganic fillers (D) of different types, different particle size distributions or different average particle diameters are used alone or in combination of plural kinds.
The amount of the inorganic filler (D) used in the present invention is not particularly limited. The amount of the inorganic filler (D) may be 10 to 300 parts by weight, for example, 20 parts by weight, 40 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 140 parts by weight, 160 parts by weight, 180 parts by weight, 200 parts by weight, 220 parts by weight, 240 parts by weight, 260 parts by weight, 280 parts by weight, 290 parts by weight, preferably 30 to 270 parts by weight, and more preferably 50 to 250 parts by weight, based on 100 parts by weight of the total weight of the cyanate ester resin (a) and the epoxy resin (B) having the structure of formula (I) or based on 100 parts by weight of the total weight of the cyanate ester resin (a), the epoxy resin (B), and the maleimide compound (C).
The inorganic filler (D) of the present invention may be used in combination with a surface treating agent or wetting agent, a dispersant. The surface treatment agent is not particularly limited, and may be selected from surface treatment agents commonly used for surface treatment of inorganic substances. The organic silicon/organic silicon. The silane coupling agent is not particularly limited and is selected from silane coupling agents commonly used for surface treatment of inorganic substances, and specifically, aminosilane coupling agents, epoxy silane coupling agents, vinyl silane coupling agents, phenyl silane coupling agents, cationic silane coupling agents, mercapto silane coupling agents, and the like. The wetting agent and the dispersing agent are not particularly limited and are selected from the wetting agents and the dispersing agents generally used for coating materials. The present invention can use various types of surface treatment agents or wetting agents, dispersants alone or in appropriate combination as required.
The cyanate ester resin composition of the present invention may further comprise an organic filler (E). The organic filler (E) is not particularly limited, and may be selected from any one of silicone, liquid crystal polymer, thermosetting resin, thermoplastic resin, rubber, and core-shell rubber, or a mixture of at least two thereof, and silicone powder and/or core-shell rubber are more preferable. The organic filler (E) may be powder or granule. Among them, the silicone powder has good flame retardant properties, and the core-shell rubber has good toughening effect, so that it is preferable.
The amount of the organic filler (E) is not particularly limited. The amount of the organic filler (E) may be 1 to 30 parts by weight, for example, 2 parts by weight, 5 parts by weight, 7 parts by weight, 9 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 21 parts by weight, 24 parts by weight, 27 parts by weight, 29 parts by weight, preferably 3 to 25 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total amount of the cyanate ester resin (a) and the epoxy resin (B) or based on 100 parts by weight of the total amount of the cyanate ester resin (a), the epoxy resin (B), and the maleimide compound (C).
The term "comprising" as used herein means that it may include, in addition to the components, other components which impart different characteristics to the resin composition. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" as closed.
The cyanate ester resin composition of the present invention may be used in combination with a cyanate ester resin other than the cyanate ester resin (a) having the structure of formula (I) as long as it does not impair the inherent properties of the cyanate ester resin composition, and may be selected from the group consisting of bisphenol a type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol F type cyanate ester resin, tetramethylbisphenol F type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol P type cyanate ester resin, bisphenol S type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, naphthol novolac type cyanate ester resin, bisphenol a novolac type cyanate ester resin, trifunctional phenol type cyanate ester resin, tetrafunctional phenol type cyanate ester resin, anthracene type cyanate ester resin, dicyclopentadiene type cyanate ester resin, dicyclopentadiene phenol type cyanate ester resin, anthracene type cyanate ester resin, and the like, Biphenyl type cyanate ester resin, cyanate ester resin having an arylene ether structure in the molecule, phenolphthalein type cyanate ester resin, aralkyl type cyanate ester resin, bisphenol A type cyanate ester prepolymer, bisphenol E type cyanate ester prepolymer, bisphenol F type cyanate ester prepolymer, tetramethyl bisphenol F type cyanate ester prepolymer, bisphenol M type cyanate ester prepolymer, bisphenol P type cyanate ester prepolymer, bisphenol S type cyanate ester prepolymer, novolac type cyanate ester prepolymer, cresol novolac type cyanate ester prepolymer, naphthol novolac type cyanate ester prepolymer, bisphenol A novolac type cyanate ester prepolymer, trifunctional phenol type cyanate ester prepolymer, tetrafunctional phenol type cyanate ester prepolymer, anthracene type cyanate ester prepolymer, dicyclopentadiene type cyanate ester prepolymer, phenol type cyanate ester type prepolymer, phenol type cyanate ester type prepolymer, bisphenol, phenol type cyanate ester type prepolymer, etc. type cyanate ester type prepolymer, etc. having a type cyanate ester type prepolymer, etc. having a type cyanate ester type structure, A mixture of any one or at least two of biphenyl type cyanate ester prepolymer, cyanate ester prepolymer containing an arylene ether structure in the molecule, phenolphthalein type cyanate ester prepolymer, aralkyl type cyanate ester prepolymer or aralkyl phenol type cyanate ester prepolymer, such as a mixture of bisphenol A type cyanate ester resin and bisphenol F type cyanate ester resin, a mixture of tetramethyl bisphenol F type cyanate ester resin and bisphenol M type cyanate ester resin, a mixture of bisphenol S type cyanate ester resin and bisphenol E type cyanate ester resin, a mixture of bisphenol P type cyanate ester resin and novolac type cyanate ester resin, a mixture of cresol phenol type cyanate ester resin and naphthol phenol type cyanate ester resin, a mixture of bisphenol A phenol type cyanate ester resin and trifunctional phenol type cyanate ester resin, a mixture of tetrafunctional phenol type cyanate ester resin and anthracene type cyanate ester resin, fluorene type cyanate ester resin and dicyclopentadiene type cyanate ester resin mixture, biphenyl type cyanate ester resin and cyanate ester resin having an arylene ether structure in the molecule, dicyclopentadiene type cyanate ester resin and phenolphthalein type cyanate ester resin mixture, aralkyl type cyanate ester resin and aralkyl type cyanate ester resin mixture, novolac type cyanate ester resin and bisphenol a type cyanate ester prepolymer mixture, bisphenol a type cyanate ester prepolymer and bisphenol F type cyanate ester prepolymer mixture, tetramethyl bisphenol F type cyanate ester prepolymer and bisphenol M type cyanate ester prepolymer mixture, bisphenol S type cyanate ester prepolymer and bisphenol E type cyanate ester prepolymer mixture, bisphenol P type cyanate ester prepolymer and novolac type cyanate ester prepolymer mixture, cresol novolac type cyanate ester prepolymer and naphthol novolac type cyanate ester prepolymer mixture, a mixture of a bisphenol a novolac type cyanate ester prepolymer and a trifunctional phenol type cyanate ester prepolymer, a mixture of a tetrafunctional phenol type cyanate ester prepolymer and an anthracene type cyanate ester prepolymer, a mixture of fluorene type cyanate ester prepolymer and a dicyclopentadiene novolac type cyanate ester prepolymer, a mixture of a biphenyl type cyanate ester prepolymer and a cyanate ester prepolymer having an arylene ether structure in the molecule, a mixture of a dicyclopentadiene type cyanate ester prepolymer, a phenolphthalein type cyanate ester prepolymer, an aralkyl type cyanate ester prepolymer and an aralkyl type cyanate ester prepolymer, and in order to improve the heat resistance and flame retardancy of the cyanate ester resin composition, a novolak type cyanate ester resin, a cresol novolak type cyanate ester resin, a naphthol novolak type cyanate ester resin, a phenolphthalein type cyanate ester resin, an anthracene type cyanate ester resin, a biphenyl type cyanate ester resin, a naphthol type cyanate ester resin, a phenol novolak type cyanate ester resin, a phenol type cyanate ester resin, a dicyclopentadiene type cyanate ester prepolymer, a dicyclopentadiene phenol prepolymer, a dicyclopentadiene type cyanate ester prepolymer, a mixture, Cyanate ester resin having an arylene ether structure in the molecule, aralkyl type cyanate ester resin, novolac type cyanate ester prepolymer, cresol novolac type cyanate ester prepolymer, naphthol novolac type cyanate ester prepolymer, phenolphthalein type cyanate ester prepolymer, anthracene type cyanate ester prepolymer, biphenyl type cyanate ester prepolymer, cyanate ester prepolymer having an arylene ether structure in the molecule, aralkyl type cyanate ester prepolymer or aralkyl type cyanate ester prepolymer, or a mixture of at least two thereof, and particularly preferred are any one of the novolac type cyanate ester resin, naphthol novolac type cyanate ester resin, cyanate ester resin having an arylene ether structure in the molecule, aralkyl type cyanate ester resin, novolac type cyanate ester prepolymer, naphthol novolac type cyanate ester prepolymer, cyanate ester prepolymer having an arylene ether structure in the molecule, or any one of the aralkyl type cyanate ester prepolymers One or a mixture of at least two. These cyanate ester resins may be used alone or in combination of plural kinds as required.
The cyanate ester resin composition of the present invention can also be used in combination with various high polymers, rubbers, elastomers, as long as it does not impair the inherent properties of the cyanate ester resin composition. Specifically, for example, a liquid crystal polymer, a thermosetting resin, a thermoplastic resin, various flame retardant compounds or additives, and the like can be used. They may be used alone or in combination of plural kinds as required.
The cyanate ester resin composition of the present invention may also be used in combination with a curing accelerator as needed to control the curing reaction rate. The curing accelerator is not particularly limited and may be selected from curing accelerators commonly used for accelerating the curing of cyanate ester resins, epoxy resins, and specifically organic salts of metals such as copper, zinc, cobalt, nickel, manganese, imidazole and derivatives thereof, tertiary amines, and the like, such as zinc octoate.
The cyanate ester resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like.
The method for preparing the resin composition of the present invention is not particularly limited, and the resin composition of the present invention can be prepared by compounding, prepolymerization, prereaction, stirring, mixing the cyanate ester resin (a) having the structure of formula (I) with the epoxy resin (B) and the like by a known method.
Another object of the present invention is to provide a prepreg, a laminate, a metal-clad laminate and a printed wiring board prepared using the cyanate ester resin composition, wherein the laminate and the metal-clad laminate prepared using the prepreg have good heat resistance, wet heat resistance, mechanical properties, flame retardancy and reliability, and a low coefficient of thermal expansion in the plane direction, and are suitable for use as a substrate material for preparing a high-density printed wiring board.
The invention provides a prepreg prepared by using the cyanate ester resin composition, and the prepreg comprises a base material and the cyanate ester resin composition attached to the base material after impregnation and drying. The substrate according to the present invention is not particularly limited, and may be selected from known substrates for use in the production of various printed wiring board materials. Specifically, inorganic fibers (e.g., glass fibers such as E glass, D glass, L glass, M glass, S glass, T glass, NE glass, Q glass, and quartz), and organic fibers (e.g., polyimide, polyamide, polyester, polyphenylene ether, and liquid crystal polymer). The substrate is typically in the form of woven, nonwoven, roving, staple, fiber paper, or the like. Among the above substrates, the substrate of the present invention is preferably a glass fiber cloth.
There is no particular limitation on the method for producing the prepreg of the present invention as long as it is a method for producing a prepreg by combining the cyanate ester resin composition of the present invention with a substrate.
An organic solvent may be used as necessary in the cyanate ester resin composition for preparing the prepreg. The organic solvent is not particularly limited as long as it is compatible with a mixture of the cyanate ester resin (a) and the epoxy resin (B) having the structure of formula (I), and specific examples thereof include: 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 solvents may be used alone, or two or more of them may be used in combination as required.
The invention also provides a laminated board and a metal foil-clad laminated board prepared by using the prepreg. The laminated board comprises at least one prepreg, and the laminated board is obtained by laminating and curing the laminated prepregs. The metal foil-clad laminate comprises at least one prepreg, wherein one side or two sides of the laminated prepreg are covered with metal foils, and the metal foil-clad laminate is obtained by laminating and curing. The laminated board and the metal foil-clad laminated board prepared by using the prepreg have good heat resistance, humidity resistance, mechanical property, flame retardance and reliability and low in-plane thermal expansion coefficient, so that the prepreg is suitable for preparing a substrate material of a high-density printed circuit board.
The laminate of the present invention is not particularly limited in its preparation manner, and can be prepared by a known method such as: and placing one prepreg or stacking two or more prepregs, placing metal foils on one side or two sides of the prepreg or stacked prepregs as required, and laminating and curing to obtain the laminated board or metal foil-clad laminated board. The metal foil is not particularly limited and may be selected from metal foils used for printed wiring board materials. The lamination conditions can be selected from the general lamination conditions of a laminate for a printed wiring board and a multilayer board.
The invention also provides a printed wiring board comprising at least one prepreg as described above. The method for producing the printed wiring board of the present invention is not particularly limited, and can be produced by a known method.
The present invention will be described in more detail with reference to examples. It should be noted that the description and examples are intended to facilitate the understanding of the invention, and are not intended to limit the invention. The scope of the invention is to be determined by the claims appended hereto.
Examples
In the present invention, unless otherwise indicated, all reagents used were commercially available products and were used without further purification treatment. Further, "%" mentioned is "% by weight", and "parts" mentioned is "parts by weight".
Test method
The various copper clad laminates prepared in examples and comparative examples were tested with respect to glass transition temperature (Tg:. degree. C.), solder dip resistance (S), wet heat resistance, flexural modulus (GPa), in-plane coefficient of thermal expansion (CTE: ppm/. degree. C.), and flame retardancy according to the specific methods listed below.
Glass transition temperature (Tg:. degree.C.)
Copper foil was etched off from the copper clad laminate samples prepared in examples and comparative examples to prepare a size of 60mm × 12mm, the glass transition temperature (Tg:. degree. c) of the samples was measured by dynamic thermo-mechanical analysis (DMA), the peak temperature of tan δ when the temperature was raised from room temperature to 350 ℃ at a temperature raising rate of 10 ℃/min was taken as Tg, and the thickness of the test sample was 0.8 mm.
Resistance to dip soldering (S)
The copper clad laminate samples prepared in examples and comparative examples were prepared to have a size of 50mm x 50mm, the samples were immersed in a tin furnace at 288 ℃, delamination blistering was observed and the corresponding time was recorded, and the test sample thickness was 0.4 mm.
Moisture and heat resistance
Copper foil was etched off from the copper foil-clad laminate samples prepared in examples and comparative examples to prepare 100mm × 100mm in size. The sample was dried at 105 ℃ for 2 hours. Then, the sample was treated with an autoclave tester at 121 ℃ and two atmospheres for 2 hours, and then immersed in tin in a tin furnace at 260 ℃ for 60 seconds, and observed whether the sample was delaminated, and judged as "OK" if delaminated and judged as "x" if delaminated and tested to have a thickness of 0.4 mm.
Flexural modulus (GPa)
The copper clad laminate samples prepared in examples and comparative examples were tested for flexural modulus at room temperature according to the test method requirements of ASTM D882 standard, with a test sample thickness of 0.8 mm.
Coefficient of thermal expansion in the in-plane direction (CTE: ppm/. degree. C.)
Copper foil was etched off from the copper clad laminate samples prepared in examples and comparative examples to prepare dimensions of 4mm × 60mm, and the in-plane thermal expansion coefficient of the samples was measured by thermomechanical analysis (TMA), wherein the test direction was a direction along a warp of a glass cloth, the temperature was raised from room temperature 25 ℃ to 300 ℃ at a temperature raising rate of 10 ℃/min, the in-plane thermal expansion coefficient was measured from 50 ℃ to 130 ℃, and the thickness of the test sample was 0.1 mm.
Flame retardancy
The copper clad laminate samples prepared in examples and comparative examples were etched to remove the copper foil, and tested for flame retardancy according to the test method requirements of the UL94 vertical burning test standard, with test sample thicknesses of 0.1, 0.4 mm.
Preparation example 1
Phenyl aralkyl naphthol phenolic type cyanate ester resin A1
Phenylaralkylnaphthol phenol-aldehyde type cyanate ester resin A1 was prepared by reacting phenylaralkylnaphthol phenol-aldehyde resin (SN-395, available from Nippon iron Co., Ltd.) with cyanogen chloride. The phenyl aralkyl naphthol phenol resin has a structure represented by the following formula (III) wherein R is a phenylene group; n is an integer of 1 to 10. The phenyl aralkyl naphthol phenolic cyanate ester resin A1 has a structure represented by the following formula (I'), wherein R is phenylene; n is an integer of 1 to 10.
Preparation example 2
Biphenylalkylnaphthol phenolic cyanate A2
533g of 1, 6-dihydroxynaphthalene, 167g of 4, 4' -bischloromethylbiphenyl, and 700g of chlorobenzene were charged into a flask equipped with a thermometer, a condenser, and a stirrer, and dissolved by slowly raising the temperature while stirring under nitrogen protection, followed by reaction at about 80 ℃ for 2 hours. Then, the temperature was raised to 180 ℃ while distilling off chlorobenzene, and the reaction was carried out at 180 ℃ for 1 hour. After the reaction, the solvent and unreacted monomers are removed by reduced pressure distillation, and then the mixture is washed by deionized water until the washing water is neutral, and then the biphenyl aralkyl naphthol phenol resin is obtained after drying. Then the prepared biphenyl aralkyl naphthol phenolic resin is reacted with cyanogen chloride to prepare the biphenyl aralkyl naphthol phenolic cyanate resin A2. The biphenyl aralkyl naphthol phenol resin has a structure represented by the following formula (III) wherein R is a biphenylene group; n is an integer of 1 to 10. The biphenyl aralkyl naphthol phenolic cyanate ester resin A2 has a structure represented by the following formula (I'), wherein R is biphenylene; n is an integer of 1 to 10.
Preparation example 3
Phenyl aralkyl phenolic cyanate resin A3
720g of resorcinol and 175g of 1, 4-bischloromethylbenzene were put into a flask equipped with a thermometer, a condenser and a stirrer, and the mixture was reacted at 130 ℃ for 3 hours while controlling the temperature under a nitrogen stream. Then, the temperature was raised to 160 ℃ to continue the reaction for 3 hours. After the reaction, unreacted monomers were removed by distillation under reduced pressure, and then washed with deionized water until the washing water was neutral, and dried to obtain a phenyl aralkyl phenol resin. Then the obtained phenyl aralkyl phenolic resin is reacted with cyanogen chloride to obtain phenyl aralkyl phenolic cyanate resin A3. The phenyl aralkyl phenolic resin has a structure represented by the following formula (IV), wherein R is phenylene; n is an integer of 1 to 10. The phenylaralkyl phenolic cyanate ester resin A3 has a structure represented by the following formula (V), wherein R is phenylene; n is an integer of 1 to 10.
Example 1
30 parts by weight of phenyl aralkyl naphthol phenol type cyanate ester resin A1, 70 parts by weight of biphenyl aralkyl type phenol epoxy resin (NC-3000FH, supplied by Nippon chemical Co., Ltd.), 0.02 part by weight of zinc octanoate was dissolved in methyl ethyl ketone and mixed uniformly, adjusted to an appropriate viscosity with methyl ethyl ketone, and stirred and mixed uniformly to obtain a liquid cement. And E glass fiber cloth with the thickness of 0.1mm is used for soaking the glue solution, and then the prepreg is prepared after drying and removing the solvent. Laminating 1,4 and 8 sheets of the above prepregs, respectively, pressing electrolytic copper foil with a thickness of 18 μm on both sides, and curing in a press at a curing pressure of 45Kg/cm for 2 hours2The curing temperature was 220 ℃ to obtain a copper clad laminate having a thickness of 0.1, 0.4, 0.8 mm.
Example 2
50 parts by weight of phenylalkylnaphthol phenol type cyanate ester resin A1, 50 parts by weight of biphenylaralkylphenol epoxy resin (NC-3000H, supplied by Nippon chemical Co., Ltd.), 0.02 part by weight of zinc octanoate was dissolved in methyl ethyl ketone and mixed uniformly, adjusted to an appropriate viscosity with methyl ethyl ketone, and stirred and mixed uniformly to obtain a liquid cement. According to the same production process as in example 1, copper clad laminates having thicknesses of 0.1, 0.4, and 0.8mm were obtained.
Example 3
70 parts by weight of phenyl aralkyl naphthol phenol type cyanate ester resin A1, 30 parts by weight of biphenyl aralkyl type phenol epoxy resin (NC-3000H, supplied by Nippon chemical Co., Ltd.), 0.02 part by weight of zinc octanoate was dissolved in methyl ethyl ketone and mixed uniformly, adjusted to an appropriate viscosity with methyl ethyl ketone, and stirred and mixed uniformly to obtain a glue solution. According to the same production process as in example 1, copper clad laminates having thicknesses of 0.1, 0.4, and 0.8mm were obtained.
Comparative example 1
A copper clad laminate having a thickness of 0.1, 0.4 or 0.8mm was obtained in the same manner as in example 2 except that 50 parts by weight of phenylalkylnaphtholic cyanate ester resin (obtained by the method of Synthesis example 1 of China patent application CN 101240111A) was used in place of 50 parts by weight of phenylalkylnaphthol novolac cyanate ester resin A1 used in example 2.
Comparative example 2
A copper clad laminate having a thickness of 0.1, 0.4 or 0.8mm was obtained in the same manner as in example 2 except that 50 parts by weight of the phenyl aralkyl phenolic cyanate ester resin A3 was used in place of 50 parts by weight of the phenyl aralkyl phenolic cyanate ester resin A1 used in example 2.
The copper clad laminates obtained in examples 1-3 and comparative examples 1-2 above were tested with respect to glass transition temperature (Tg:. degree. C.), solder dip resistance (S) and wet heat resistance according to the measurement methods described specifically above, and the specific results are shown in Table 1 below.
TABLE 1 physical Property test data of copper clad laminates prepared in examples 1 to 3 and comparative examples 1 to 2
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Tg，℃ | 240 | 270 | 300 | 240 | 255 |
| Resistance to dip soldering, S | ＞120 | ＞120 | ＞120 | ＞120 | ＞120 |
| Moisture and heat resistance | OK | OK | OK | OK | × |
Example 4
30 parts by weight of phenyl aralkyl naphthol phenolType cyanate ester resin A1, 65 parts by weight of biphenylaralkyl type novolac epoxy resin (NC-3000-FH, available from Nippon chemical Co., Ltd.), 5 parts by weight of bisphenol A type epoxy resin (bisphenol A type epoxy resin: (B))
1055, supplied by DIC corporation), 0.02 part by weight of zinc octylate was dissolved in butanone and mixed uniformly, and then 200 parts by weight of spherical fused silica (SC2050, supplied by Admatechs), 2 parts by weight of epoxy silane coupling agent (Z-6040, supplied by dow corning) were added and adjusted to an appropriate viscosity with butanone, and stirred, mixed and dispersed uniformly to obtain a glue solution. And E glass fiber cloth with the thickness of 0.1mm is used for soaking the glue solution, and then the prepreg is prepared after drying and removing the solvent. Laminating 1,4 and 8 sheets of the above prepregs, respectively, and laminating electrolytic copper foils with a thickness of 18 μm on both sides thereof, and curing in a press at a curing pressure of 45Kg/cm for 2 hours2The curing temperature was 220 ℃ to obtain a copper clad laminate having a thickness of 0.1, 0.4, 0.8 mm.
Example 5
50 parts by weight of phenylalkylnaphthol phenol type cyanate ester resin A1, 50 parts by weight of biphenylaralkylnovolak type novolak epoxy resin (NC-3000H, supplied by Nippon chemical Co., Ltd.), 0.02 part by weight of zinc octanoate was dissolved in butanone and mixed uniformly, and then 110 parts by weight of boehmite (APYRAL AOH 30, supplied by Nabaltec), 1 part by weight of an epoxysilane coupling agent (Z-6040, supplied by Dow Corning), 1 part by weight of a dispersant (BYK-W903, supplied by BYK) were added and adjusted to an appropriate viscosity with butanone, and stirred, mixed and dispersed uniformly to prepare a glue solution. According to the same production process as in example 4, copper clad laminates having thicknesses of 0.1, 0.4, and 0.8mm were obtained.
Example 6
70 parts by weight of a phenyl aralkyl naphthol phenol type cyanate ester resin A1, 30 parts by weight of a naphthylene ether type naphthol epoxy resin (EXA-7311, supplied by DIC corporation), 0.02 part by weight of zinc octylate were dissolved in methyl ethyl ketone and mixed uniformly, and then 170 parts by weight of spherical fused silica (SC2050, supplied by Admatechs), 5 parts by weight of a core-shell structured silicone powder (KMP-605, supplied by shin-Etsu chemical), 1.5 parts by weight of an epoxy silane coupling agent (Z-6040, supplied by Dow Corning) were added and adjusted to an appropriate viscosity with methyl ethyl ketone, and stirred, mixed and dispersed uniformly to prepare a glue solution. According to the same production process as in example 4, copper clad laminates having thicknesses of 0.1, 0.4, and 0.8mm were obtained.
Example 7
30 parts by weight of phenyl aralkyl naphthol phenol type cyanate ester resin A1, 20 parts by weight of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70, supplied by KIchemical Industry Co., Ltd.), 50 parts by weight of biphenyl aralkyl type novolac epoxy resin (NC-3000H, supplied by Nippon chemical Co., Ltd.), 0.02 part by weight of zinc octylate dissolved in DMF and butanone and mixed uniformly, after which 170 parts by weight of spherical fused silica (SC2050, supplied by Admatech), 5 parts by weight of core-shell structured organosilicon powder (KMP-605, supplied by shin-Etsu chemical), 1 part by weight of epoxy silane coupling agent (Z-6040, supplied by Dow Corning) were added, and adjusted to an appropriate viscosity with butanone, stirred, mixed and dispersed uniformly to prepare a glue solution. According to the same production process as in example 4, copper clad laminates having thicknesses of 0.1, 0.4, and 0.8mm were obtained.
Example 8
40 parts by weight of phenyl aralkyl naphthol phenol type cyanate ester resin A1, 5 parts by weight of phenol novolac type cyanate ester resin (PT-30, supplied by LONZA), 5 parts by weight of 2, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane (BMI-80, supplied by KIchemical Industry Co., Ltd.), 25 parts by weight of phenylalkyl naphthol phenol epoxy resin (ESN-385, supplied by Nippon iron), 25 parts by weight of biphenylaralkyl phenol epoxy resin (NC-3000-FH, supplied by Nippon chemical Co., Ltd.), 0.02 part by weight of zinc octoate was dissolved in DMF, and butanone was mixed well, after which 150 parts by weight of spherical fused silica (SC2050, supplied by Admatech), 1 part by weight of epoxy silane coupling agent (Z-6040, supplied by Dow Corning), 1 part by weight of dispersant (BYK-W903), supplied by BYK) and adjusted to a suitable viscosity with butanone, stirred, mixed and dispersed uniformly to obtain a glue solution. According to the same production process as in example 4, copper clad laminates having thicknesses of 0.1, 0.4, and 0.8mm were obtained.
Example 9
A copper clad laminate having a thickness of 0.1, 0.4 or 0.8mm was obtained in the same manner as in example 4 except that 30 parts by weight of the phenyl aralkyl naphthol phenol type cyanate ester resin A1 used in example 4 was replaced with 30 parts by weight of the biphenyl aralkyl naphthol phenol type cyanate ester resin A2.
Comparative example 3
A copper clad laminate having a thickness of 0.1, 0.4 or 0.8mm was obtained in the same manner as in example 5 except that 50 parts by weight of phenylalkylnaphtholic cyanate ester resin (obtained by the method of Synthesis example 1 of China patent application CN 101240111A) was used in place of 50 parts by weight of phenylalkylnaphthol novolac cyanate ester resin A1 used in example 5.
Comparative example 4
A copper clad laminate having a thickness of 0.1, 0.4 or 0.8mm was obtained in the same manner as in example 8 except that 40 parts by weight of phenylalkylnaphtholic cyanate ester resin (obtained by the method of Synthesis example 1 of China patent application CN 101240111A) was used in place of 40 parts by weight of phenylalkylnaphthol novolac cyanate ester resin A1 used in example 8.
Comparative example 5
A copper clad laminate having a thickness of 0.1, 0.4 or 0.8mm was obtained in the same manner as in example 5 except that 50 parts by weight of the phenyl aralkyl phenolic cyanate ester resin A3 was used in place of 50 parts by weight of the phenyl aralkyl phenolic cyanate ester resin A1 used in example 5.
Comparative example 6
A copper clad laminate having a thickness of 0.1, 0.4 or 0.8mm was obtained in the same manner as in example 8 except that 40 parts by weight of the phenyl aralkyl phenol aldehyde type cyanate ester resin A1 used in example 8 was replaced with 40 parts by weight of the phenyl aralkyl phenol aldehyde type cyanate ester resin A3.
The copper clad laminates obtained in examples 4 to 9 and comparative examples 3 to 6 described above were tested with respect to the solder dip resistance (S), the moist heat resistance, the flexural modulus (GPa), the in-plane coefficient of thermal expansion (CTE: ppm/. degree. C.) and the flame retardancy according to the measurement methods described specifically above, and the specific results are shown in Table 2 below.
Table 2 physical property test data of copper clad laminates prepared in examples 4 to 9
| Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | |
| Resistance to dip soldering, S | ＞120 | ＞120 | ＞120 | ＞120 | ＞120 | ＞120 |
| Moisture and heat resistance | OK | OK | OK | OK | OK | OK |
| Flexural modulus, GPa | 32 | 29 | 32 | 32 | 31 | 32 |
| CTE，ppm/℃ | 6 | 12 | 6 | 6 | 8 | 6 |
| Flame retardancy | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
Table 2 physical property test data of copper clad laminates prepared in the subsequent comparative examples 3 to 6
| Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Resistance to dip soldering, S | ＞120 | ＞120 | ＞120 | ＞120 |
| Moisture and heat resistance | OK | OK | OK | × |
| Flexural modulus, GPa | 27 | 28 | 28 | 29 |
| CTE，ppm/℃ | 15 | 10.5 | 15 | 10.5 |
| Flame retardancy | V-0 | V-0 | V-0 | V-1 |
As is clear from comparison of the results shown in tables 1 and 2, when the epoxy resin (B) and the cyanate ester resin (a) having the structure of formula (I) are selected within the scope of the present invention, a cyanate ester resin composition having excellent properties can be obtained, and the metal-clad laminate obtained using the cyanate ester resin composition has good heat resistance, wet heat resistance, mechanical properties, flame retardancy and reliability, and a low coefficient of thermal expansion in the plane direction, and is suitable for use as a substrate material for manufacturing a high-density printed wiring board.
As described above, the cyanate ester resin composition, and the prepreg, the laminate and the metal foil-clad laminate prepared using the same according to the present invention have good heat resistance, moist heat resistance, mechanical properties (e.g., flexural modulus), flame retardancy and reliability, and a low coefficient of thermal expansion in the plane direction, and are suitable for use as a substrate material for manufacturing a high-density printed wiring board.
The embodiments of the present invention are described only for the preferred embodiments of the present invention, and not for the purpose of limiting the spirit and scope of the present invention, and various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention, and the technical contents of the present invention as claimed are all described in the claims.
Claims (18)
1. A cyanate ester resin composition, said cyanate ester resin composition comprising:
a cyanate ester resin (a) represented by the following formula (I'):
wherein R is biphenylene; and n is an integer from 1 to 20; and
an epoxy resin (B).
2. The cyanate ester resin composition according to claim 1, wherein n is an integer of 1 to 15.
3. The cyanate ester resin composition according to claim 1, wherein n is an integer of 1 to 10.
4. The cyanate ester resin composition according to claim 1, wherein the cyanate ester resin (a) accounts for 10 to 90% by weight of the total weight of the cyanate ester resin (a) and the epoxy resin (B).
5. The cyanate ester resin composition according to claim 1, wherein the cyanate ester resin (a) accounts for 20 to 80% by weight of the total weight of the cyanate ester resin (a) and the epoxy resin (B).
6. The cyanate ester resin composition according to claim 1, wherein said cyanate ester resin (a) accounts for 30 to 70% by weight of the total weight of cyanate ester resin (a) and epoxy resin (B).
7. The cyanate ester resin composition according to claim 1, wherein said epoxy resin (B) is selected from epoxy resins containing at least two epoxy groups.
8. The cyanate ester resin composition according to claim 1, wherein said cyanate ester resin composition further comprises a maleimide compound (C).
9. The cyanate ester resin composition according to claim 8, wherein the amount of the maleimide compound (C) is 5 to 80 parts by weight based on 100 parts by weight of the total weight of the cyanate ester resin (A) and the maleimide compound (C).
10. The cyanate ester resin composition according to claim 8, wherein the amount of the maleimide compound (C) is 10 to 70 parts by weight based on 100 parts by weight of the total weight of the cyanate ester resin (A) and the maleimide compound (C).
11. The cyanate ester resin composition according to claim 1 or 8, wherein said cyanate ester resin composition further comprises an inorganic filler (D).
12. The cyanate ester resin composition according to claim 11, wherein the amount of said inorganic filler (D) is 10 to 300 parts by weight based on 100 parts by weight of the total weight of said cyanate ester resin (a) and epoxy resin (B) or 100 parts by weight based on the total weight of said cyanate ester resin (a), epoxy resin (B) and maleimide compound (C).
13. The cyanate ester resin composition according to claim 11, wherein the amount of said inorganic filler (D) is 30 to 270 parts by weight based on 100 parts by weight of the total weight of said cyanate ester resin (a) and epoxy resin (B) or 100 parts by weight based on the total weight of said cyanate ester resin (a), epoxy resin (B) and maleimide compound (C).
14. The cyanate ester resin composition according to claim 11, wherein the amount of said inorganic filler (D) is 50 to 250 parts by weight based on 100 parts by weight of the total weight of said cyanate ester resin (a) and epoxy resin (B) or 100 parts by weight based on the total weight of said cyanate ester resin (a), epoxy resin (B) and maleimide compound (C).
15. A prepreg comprising a substrate and the cyanate ester resin composition according to any one of claims 1 to 14 attached to the substrate after drying by impregnation.
16. A laminate comprising at least one prepreg according to claim 15.
17. A metal-foil-clad laminate comprising at least one prepreg according to claim 15 and a metal foil clad on one or both sides of the prepreg.
18. A printed wiring board comprising at least one prepreg according to claim 15.
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| JP2014012763A (en) * | 2012-07-04 | 2014-01-23 | Ajinomoto Co Inc | Resin composition |
| CN107207855A (en) * | 2015-03-31 | 2017-09-26 | 三菱瓦斯化学株式会社 | Resin composition for printed circuit board, prepreg, resin compounded piece and clad with metal foil plywood |
| CN107406582A (en) * | 2015-03-31 | 2017-11-28 | 三菱瓦斯化学株式会社 | Cyanate esters, include the hardening resin composition of the compound and its solidfied material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014012763A (en) * | 2012-07-04 | 2014-01-23 | Ajinomoto Co Inc | Resin composition |
| CN107207855A (en) * | 2015-03-31 | 2017-09-26 | 三菱瓦斯化学株式会社 | Resin composition for printed circuit board, prepreg, resin compounded piece and clad with metal foil plywood |
| CN107406582A (en) * | 2015-03-31 | 2017-11-28 | 三菱瓦斯化学株式会社 | Cyanate esters, include the hardening resin composition of the compound and its solidfied material |
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