CN107286325B - Resin composition and use thereof - Google Patents
Resin composition and use thereof Download PDFInfo
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- CN107286325B CN107286325B CN201610202968.1A CN201610202968A CN107286325B CN 107286325 B CN107286325 B CN 107286325B CN 201610202968 A CN201610202968 A CN 201610202968A CN 107286325 B CN107286325 B CN 107286325B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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Abstract
The present invention relates to a resin composition and its use. Specifically, the present invention relates to a resin composition comprising: 20-35 parts by weight of a multifunctional epoxy resin; 8-15 parts by weight of isocyanate modified epoxy resin; 5-10 parts by weight of bifunctional epoxy resin; 40-65 parts by weight of polyphenylene ether resin; and 8-16 parts by weight of cyanate ester resin. The invention also relates to products of the resin composition, which comprise resin films, bonding sheets, prepregs, composites, laminates and printed circuit boards. Through the combination of different resins, this application has realized the stack of product performance for the product still has heat-resisting, low dielectric loss and workable composite effect when having good outward appearance.
Description
Technical Field
The present invention relates to a resin composition and its use.
Background
The polyphenylene oxide resin has excellent dielectric properties due to the symmetrical molecular structure and low molecular dipole moment, and is popular among workers engaged in new material development. Resin matrices using modified polyphenylene ethers as curing agents have been widely used in composite substrates and high frequency circuit boards.
The resin composition of the prior art is: high molecular weight polybutadiene resin containing more than 70 wt% of vinyl, the weight average molecular weight MW is more than 100000, and accounts for 0-15 wt% of the weight of the composition; the low molecular weight polybutadiene resin contains more than 70 wt% of vinyl, has a weight average molecular weight MW of 1000-10000 and accounts for 10-40 wt% of the weight of the composition; the modified polyphenyl ether resin has the weight-average molecular weight of 1000-5000-. The main resin in the composition is unsaturated hydrocarbon, namely polybutadiene, and after curing and crosslinking, a network structure mainly comprises an aliphatic chain structure consisting of carbon-carbon and carbon-hydrogen single bonds, so that the polarity is small, the rotation of a molecular chain segment is easy, and the peeling strength and the mechanical strength of the metal-clad foil are low. When the metal-clad high-frequency substrate is applied to a high-frequency metal-clad substrate, the phenomena of wire throwing and poor wire dropping are easily caused. The prepreg impregnated by the composition has no viscosity or very small viscosity, and is not suitable for paving and molding of curved surface composite materials. In addition, the components of the composition have high molecular weight, so that the leveling property and the permeability of the reinforcing material are poor, and the appearance of prepreg and bonding sheet produced by impregnation is easy to generate air bubbles and adhesive lumps, thereby influencing the heat-resistant reliability of the base material.
In view of the above, the development of a prepreg, an adhesive sheet and a composite substrate having high metal-clad peel strength, good spreadability and good appearance has been required to satisfy the use demand of high-frequency circuits.
Disclosure of Invention
The invention aims to overcome the problems of low peeling strength of metal coating, low mechanical strength, poor laying formability of prepreg, poor bubble and gum nubby existing in appearance and the like of a composite material taking high molecular weight unsaturated hydrocarbon as a main body resin, and provides a resin composition which has high metal adhesion strength, high mechanical strength, good laying formability and good appearance and is applied to the production of the composite material.
Another object of the present invention is to provide use of the above resin composition in the preparation of resin films, adhesive sheets, prepregs, composites and laminates.
It is a further object of the present invention to provide use of the above resin composition for producing a high-frequency circuit substrate.
The resin composition of the present invention contains:
in one or more embodiments, the resin composition further comprises 0.01 to 0.05 parts by weight of an imidazole accelerator.
In one or more embodiments, the multifunctional epoxy resin is selected from the group consisting of: dicyclopentadiene type polyfunctional epoxy resin, o-phenyl novolac epoxy resin, or a combination thereof.
In one or more embodiments, the dicyclopentadiene-type multi-functional epoxy resin has the following structure:
wherein n is an integer of 1 to 10.
In one or more embodiments, the o-phenyl novolac epoxy resin has the following structure:
in the formula, a, b, c and d are respectively independent integers of 1-10, and each R is independently alkyl.
In one or more embodiments, the isocyanate-modified epoxy resin is a TDI or MDI modified epoxy resin, or a combination thereof.
In one or more embodiments, the isocyanate-modified epoxy resin has the following structure:
wherein R is1Is a molecular chain of epoxy resin, R2Is isocyanate molecular chain.
In one or more embodiments, the difunctional epoxy resin is an alicyclic-containing epoxy resin, or a dehydroxylated (etherified hydroxyl groups in the molecular chain) epoxy resin, or a combination thereof.
In one or more embodiments, the difunctional epoxy resin has the following structure:
wherein R is3Is an aliphatic chain or an aromatic ring.
In one or more embodiments, the polyphenylene ether resin has a number average molecular weight of 1000 to 3000.
In one or more embodiments, the polyphenylene ether resin is terminated with hydroxyl groups.
In one or more embodiments, the polyphenylene ether resin has the following structure:
wherein e, f and g are each independently an integer of 1 to 20, and Y is a bond.
In one or more embodiments, the cyanate ester resin is selected from: one or the combination of more than two of bisphenol A cyanate ester, linear multifunctional cyanate ester resin, o-cresol multifunctional cyanate ester resin and dicyclopentadiene phenol type cyanate ester resin.
In one or more embodiments, the imidazole accelerators are selected from the group consisting of: 2-methylimidazole (2-MI), 2-ethyl-4-methylimidazole (2E4MI) or 2-phenylimidazole (2-PI), or a combination thereof.
In one or more embodiments, the resin composition comprises:
20-25 parts by weight of dicyclopentadiene type polyfunctional epoxy resin;
8-12 parts by weight of diphenylmethane diisocyanate-modified epoxy resin;
5-8 parts by weight of alicyclic epoxy resin;
40 to 50 parts by weight of a polyphenylene ether resin; and
8-12 parts by weight of bisphenol A cyanate ester.
In one or more embodiments, the resin composition comprises:
30-35 parts by weight of o-phenyl phenolic epoxy resin;
10-15 parts by weight of diphenylmethane diisocyanate-modified epoxy resin;
7-10 parts by weight of an alicyclic epoxy resin;
55-65 parts by weight of a polyphenylene ether resin; and
12-16 parts by weight of dicyclopentadiene phenol type cyanate ester resin.
The invention also includes a resin film, an adhesive sheet or a prepreg made of the resin composition of the invention, a composite material or a laminate made of the resin film or the adhesive sheet, and a printed circuit board made of the laminate.
The present invention also provides a method of improving the metal clad peel strength and/or mechanical strength of a resin film, bonding sheet, prepreg or composite, comprising preparing the resin film, bonding sheet, prepreg or composite using the resin composition described herein.
The present invention also provides a method of improving drape formability of a prepreg comprising preparing the prepreg using the resin composition described herein.
The invention also includes the use of the resin composition of the invention to improve the metal clad peel strength and/or mechanical strength of a resin film, bonding sheet, prepreg or composite, or to improve the drape formability of a prepreg.
The resin composition and the application thereof have the following beneficial effects:
Detailed Description
The resin composition adopts the polyfunctional epoxy resin with symmetrical structure and small molecular dipole moment, has high curing crosslinking density and ensures that the product has high heat resistance. The composition simultaneously uses isocyanate modified epoxy resin with excellent heat resistance and flexibility, and the molecular structure of the resin contains a large amount of N-C ═ O bonds, so that a cured substrate has good coating metal property. The curing agent adopts polyphenyl ether resin with symmetrical structure and low polarity and a small amount of cyanate resin, so that the excellent dielectric property of the product is ensured. The alicyclic or dehydroxylated bifunctional low molecular weight epoxy resin is used in a compounding manner, so that the viscosity of a resin system is reduced, and the infiltration and permeability of the reinforcing material are improved. Through the combination of different resins, this application has realized the stack of product performance for the product still has heat-resisting, low dielectric loss and workable composite effect when having good outward appearance.
Specifically, the present invention provides a resin composition containing a polyfunctional epoxy resin, an isocyanate-modified epoxy resin, a bifunctional epoxy resin, polyphenylene ether and a cyanate ester resin.
In the present application, the polyfunctional epoxy resin means a resin having an average of 3 or more epoxy groups per molecule.
The polyfunctional epoxy resin suitable for use in the present application preferably has a symmetrical structure and a high crosslinking density after curing, so that the resin composition of the present application has high heat resistance. Thus, in certain embodiments, the multifunctional epoxy resin may be selected from: dicyclopentadiene type polyfunctional epoxy resin, o-phenyl novolac epoxy resin, or a combination thereof. Polyfunctional epoxy resins with structural symmetry are preferred.
As an example, the dicyclopentadiene type multifunctional epoxy resin may have the following structure:
wherein n is an integer of 1 to 10, such as an integer of 1 to 8, 3 to 10, 3 to 8, etc.
As an example, the o-phenyl novolac epoxy resin may have the following structure:
in each formula, a, b, c and d are independently integers of 1-10, such as integers of 1-8, 3-10, 3-8, etc.; each R is independently an alkyl group.
As used herein, "alkyl" generally refers to a saturated hydrocarbon group, typically having an atomic number in the range of 1 to 30, such as 1 to 20, 1 to 15, 1 to 10, 3 to 15, 3 to 20, 5 to 10, and the like.
The resin composition of the present application can be prepared using dicyclopentadiene type multifunctional epoxy resin and o-phenyl novolac epoxy resin known in the art.
The resin composition described herein generally contains 20 to 35 parts by weight of a multifunctional epoxy resin. In certain embodiments, the multifunctional epoxy resin may be included in an amount ranging from, for example, 20 to 30 parts by weight, 20 to 25 parts by weight, 23 to 35 parts by weight, 23 to 30 parts by weight, 25 to 35 parts by weight, 30 to 35 parts by weight, and the like.
The isocyanate-modified epoxy resin suitable for use herein is generally an isocyanate-modified epoxy resin having excellent heat resistance and flexibility. It is to be understood that the "isocyanate-modified epoxy resin" in the compositions herein refers to a different epoxy resin than the "multifunctional epoxy resin" and the "difunctional epoxy resin" in the compositions herein. The "multifunctional epoxy resins" and "difunctional epoxy resins" do not include "isocyanate-modified" epoxy resins.
In the present application, the isocyanate-modified epoxy resin generally includes TDI (toluene diisocyanate) or MDI (diphenylmethane diisocyanate) modified epoxy resin, or a combination thereof. More preferably, the molecular structure of the resin contains N-C ═ O bonds, so that the cured substrate has good metal coverage.
Thus, in certain embodiments, the isocyanate-modified epoxy resin has the following structure:
wherein R is1Is a molecular chain of epoxy resin, R2Is isocyanate molecular chain.
For example, when the isocyanate-modified epoxy resin is TDI (toluene diisocyanate) or MDI (diphenylmethane diisocyanate) modified epoxy resin, the R is2Is the molecular chain of toluene diisocyanate or diphenylmethane diisocyanate.
Isocyanate-modified epoxy resins known in the art may be used in the practice of the present invention. The resin composition described herein generally contains 8 to 15 parts by weight of an isocyanate-modified epoxy resin. In certain embodiments, the isocyanate modified epoxy resin may be included in an amount ranging from, for example, 8 to 12 parts by weight, 8 to 10 parts by weight, 10 to 15 parts by weight, or 12 to 15 parts by weight, etc.
The bifunctional epoxy resin suitable for use in the present application may be an alicyclic-containing epoxy resin or a dehydroxylated (etherified hydroxyl group in molecular chain) epoxy resin, or a combination thereof. Preferably, the use of such difunctional epoxy resins reduces the viscosity of the resin system and increases wet out permeability to the reinforcement.
In one or more embodiments, the difunctional epoxy resin may have the following structure:
wherein R is3Is an aliphatic chain or an aromatic ring.
In the present application, a fatty chain generally refers to a carbon chain derived from a fatty acid, and may be saturated or unsaturated, and the number of carbon atoms is generally in the range of 2 to 30, for example, 2 to 4, 6 to 12, 14 to 24, 4 to 24, and the like. Aromatic rings refer to planar ring systems having conjugation, and typical aromatic rings include benzene, naphthalene, pyridine, indole, and the like.
The resin composition of the present application can be prepared using various alicyclic-containing epoxy resins or dehydroxylated epoxy resins (in which the hydroxyl groups in the molecular chain are etherified) known in the art. The resin composition described herein generally contains 5 to 10 parts by weight of an isocyanate-modified epoxy resin. In certain embodiments, the isocyanate modified epoxy resin may be included in an amount ranging from, for example, 5 to 8 parts by weight, 6 to 9 parts by weight, 5 to 7 parts by weight, or 7 to 10 parts by weight, etc.
The number average molecular weight of the polyphenylene ether suitable for use in the present invention is usually in the range of 1000 to 3000. Preferably, the polyphenylene ether is terminated with hydroxyl groups. In certain embodiments, the polyphenylene ether structure is symmetrical. In other embodiments, the polyphenylene ether has a lower polarity. The polyphenylene ether resin used in the present application should allow the prepared resin composition product to have excellent dielectric properties.
In one or more embodiments, the present application uses a polyphenylene ether resin having the structure:
wherein e, f and g are each independently an integer of 1 to 20, for example, an integer of 1 to 15, 1 to 10, 3 to 15, 3 to 10, 5 to 15; y is a bond.
In certain embodiments, f ═ g.
The resin composition of the present invention can be prepared using known polyphenylene ether resins. The resin composition described herein generally contains 40 to 65 parts by weight of a polyphenylene ether resin. In certain embodiments, the polyphenylene ether resin may be included in an amount ranging from, for example, 40 to 60 parts by weight, 45 to 65 parts by weight, 40 to 50 parts by weight, 40 to 55 parts by weight, or 50 to 65 parts by weight, etc.
The cyanate ester resin suitable for use in the present invention may be one or a combination of two or more of various cyanate ester resins known in the art, such as bisphenol a type cyanate ester, linear polyfunctional cyanate ester resin, o-cresol type polyfunctional cyanate ester resin, and dicyclopentadiene phenol type cyanate ester resin. Preferably, the cyanate ester resin is used in combination with a polyphenylene ether resin, so that the resin composition prepared has the desired dielectric properties.
The resin composition described herein generally contains 8 to 16 parts by weight of a cyanate ester resin. In certain embodiments, the cyanate ester resin may be included in an amount ranging from, for example, 8 to 12 parts by weight, 8 to 10 parts by weight, 10 to 16 parts by weight, 10 to 13 parts by weight, or 12 to 16 parts by weight, etc.
The resin composition of the present application may further contain other additives conventionally added to resin compositions in the art for various purposes, including but not limited to, at least one of hardening accelerator, flame retardant, inorganic filler, solvent and surfactant.
The hardening accelerator may be any of various hardening accelerators known in the art for use in resin preparation, and may include, inter alia, imidazole accelerators such as 2-methylimidazole (2-MI), 2-ethyl-4-methylimidazole (2E4MI), 2-phenylimidazole (2-PI), or any combination thereof.
Generally, the resin composition of the present invention may contain 0.01 to 0.05 parts by weight of a hardening accelerator.
The flame retardant may be a compound having a flame retardant element or a flame retardant functional group, which is well known in the art, and may be a phosphorus-containing compound, a nitrogen-containing compound, or a bromine-containing compound, such as bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone-bis- (diphenyl phosphate), bisphenol a-bis- (diphenyl phosphate), and the like.
The amount of the flame retardant in the resin composition may be in its conventional amount, and can be easily determined by those skilled in the art according to conventional technical means. Generally, the flame retardant may be used in an amount of 0.5 to 30 parts by weight in the resin composition of the present invention.
The inorganic filler may be any of a variety of inorganic fillers conventionally used in resin compositions in the art, including, but not limited to, silica (molten, non-molten, porous, or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, silicon nitride, calcined kaolin, or combinations thereof.
The amount of the inorganic filler to be used can be easily determined depending on the actual use of the resin composition. Generally, the amount of the inorganic filler in the resin composition of the present invention may be 10 to 100 parts by weight, for example, 30 to 80 parts by weight.
The solvent may be various solvents known in the art for use in the resin composition, including but not limited to solvents such as methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, propylene glycol methyl ether, and the like, or a mixed solvent thereof.
The amount of the organic solvent is not limited, and generally, 100 to 300 parts by weight of the organic solvent, for example, 100 to 220 parts by weight, may be used per 100 parts by weight of the resin composition. Preferably, the amount of the organic solvent used is such that the solid content of the resulting resin solution is in the range of 50 to 65 mass%.
The surfactant may be various surfactants known in the art for use in resins, including but not limited to silane compounds or siloxane compounds. The surfactant may be used in an amount of 0.1 to 10 parts by weight in the resin composition of the present invention.
The resin composition of the present application can be used for producing a resin film, an adhesive sheet, a prepreg, a laminate, a printed wiring board, or the like.
For example, the resin composition of the present application may be baked and heated to be cured to form a resin film.
Or, the components of the resin composition can be mixed according to the dosage proportion, and the mixture is added into an organic solvent to prepare a resin solution with the solid content of 50-65% (mass percentage). The resin composition is then attached to a reinforcing material by impregnation or the like, and is formed into a semi-cured state by heating at a high temperature (for example, 80 to 180 ℃) to obtain the adhesive sheet or prepreg of the present application. In other words, the adhesive sheet or prepreg of the present application generally includes a reinforcing material and the resin composition of the present invention.
In certain embodiments, the high temperature heating process comprises: 80-85 ℃/2-3 minutes, 130-135 ℃/3-4 minutes, and then 175-180 ℃/5-6 minutes.
The reinforcing material can be fiber material, woven fabric and non-woven fabric, such as glass fiber cloth, etc., to increase the mechanical strength of the bonding sheet.
Further, the semi-cured adhesive sheet or resin film (as an insulating layer in a laminate) may be laminated in a predetermined number of sheets, and a metal foil may be applied to both or one side of the sheet, and the sheet may be pressed at high temperature and high pressure into a laminate or a composite without applying a metal foil to the composite. The metal foil may be made of copper, aluminum, nickel, platinum, silver, gold or their alloys. The high temperature is generally 180 to 240 ℃ and the high pressure is generally 200 to 450 psi. Thus, when copper is used, the laminate is a copper clad laminate. The laminated board can be further processed by a circuit process to manufacture a printed circuit board, in particular a high-frequency circuit board.
Accordingly, the present application includes finished resin products including resin films, adhesive sheets, prepregs, laminates or printed circuit boards, especially high frequency circuit boards, prepared using the resin compositions of the present application.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention uses the multifunctional epoxy resin with symmetrical structure, the molecular chain contains a large amount of aromatic rings, the curing crosslinking density is high, and the cured product has good heat resistance and mechanical strength.
2. The isocyanate modified epoxy adopted by the invention has a large amount of five-membered heterocyclic rigid structures in the molecular main chain, so that the product has excellent heat resistance and toughness. Meanwhile, the molecular structure contains a large number of N-C ═ O bonds, so that the cured substrate has good metal coating property
3. Because the curing agent adopts polyphenyl ether with symmetrical structure, low polarity and low molecular weight, the components of the composition have good intermiscibility, the phase separation problem does not exist, and the excellent and uniform dielectric property of the product is ensured.
4. The invention simultaneously uses the alicyclic or dehydroxylated low molecular weight difunctional epoxy resin with low molecular weight, low viscosity and symmetrical structure, so that the product has the comprehensive advantages of low dielectric loss and good appearance.
5. The invention has simple production process and wide application prospect in bonding sheets, prepreg, composite materials and circuit substrates. The obtained composite material or circuit board has high heat resistance and low dielectric loss, and is suitable for use as a substrate for high-frequency circuits.
The present invention will be described below by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. The methods, reagents and conditions employed in the examples are, unless otherwise indicated, those conventional in the art.
Further, it is to be understood that, unless otherwise specified, the parts by weight of the respective components referred to in the present application are relative, that is, the resin composition contains 20 to 35 parts by weight of the polyfunctional epoxy resin, 8 to 15 parts by weight of the isocyanate modified epoxy resin, 5 to 10 parts by weight of the bifunctional epoxy resin, 40 to 65 parts by weight of the polyphenylene ether resin and 8 to 16 parts by weight of the cyanate ester resin, meaning that 8 to 15 parts by weight of the isocyanate modified epoxy resin, 5 to 10 parts by weight of the bifunctional epoxy resin, 40 to 65 parts by weight of the polyphenylene ether resin and 8 to 16 parts by weight of the cyanate ester resin are used per 20 to 35 parts by weight of the polyfunctional epoxy resin.
Example 1
20 parts by weight of dicyclopentadiene type polyfunctional epoxy resin, 8 parts by weight of MDI modified epoxy resin, 5 parts by weight of alicyclic epoxy resin, 40 parts by weight of polyphenylene ether, 8 parts by weight of bisphenol A type cyanate ester and 0.01 part by weight of 2-methylimidazole (2-MI) were weighed and added to 122 parts by weight of methyl ethyl ketone to prepare a resin solution having a solid content of 60%.
The resin solution was impregnated with 8 sheets (200mm by 200mm) of 7628 quartz cloth. Baking the obtained product in an oven at the speed of 80 ℃/2 min +130 ℃/3 min +175 ℃/5 min to prepare the semi-solidified bonding sheet.
The 8 bonding sheets are overlapped and aligned, and 1 piece of 35um copper foil is arranged on each of the upper and lower sides. In a vacuum press, the temperature is 210 ℃ and the pressure is 25kgf/cm2Pressing for 160 minutes to prepare the double-sided copper-clad plate with the thickness of 1.6 mm.
Example 2
Weighing 35 parts by weight of o-phenylphenol aldehyde type multifunctional epoxy resin, 15 parts by weight of MDI modified epoxy resin, 10 parts by weight of alicyclic epoxy resin, 65 parts by weight of polyphenylene oxide, 16 parts by weight of dicyclopentadiene phenol type cyanate ester resin and 0.05 part by weight of 2-methylimidazole (2-MI), and adding the obtained mixture into 212 parts by weight of butanone to prepare a resin solution with the solid content of 60%.
The resin solution was impregnated with 8 sheets (200mm by 200mm) of 7628 quartz cloth. Baking the obtained product in an oven at the speed of 80 ℃/2 min +130 ℃/3 min +175 ℃/5 min to prepare the semi-solidified bonding sheet.
The 8 bonding sheets are overlapped and aligned, and 1 piece of 35um copper foil is arranged on each of the upper and lower sides. In a vacuum press, the temperature is 210 ℃ and the pressure is 25kgf/cm2Condition (2) of pressing 160And (5) preparing the double-sided copper-clad plate with the thickness of 1.6mm in minutes.
Comparative example
Weighing 20 parts by weight of high molecular weight polybutadiene resin, 35 parts by weight of low molecular weight polybutadiene resin and 45 parts by weight of polyphenyl ether resin, adding a proper amount of toluene, mixing, adding 11 parts by weight of TAIC cross-linking agent and 6 parts by weight of DCP initiator, and stirring at normal temperature until the mixture is uniform.
8 pieces (200mm by 200mm) of 7628 quartz cloth were immersed in the resin solution and baked at 110 ℃ for 6 minutes. A bonding sheet in a semi-cured state is produced.
The other conditions are the same as the embodiment 1, and the double-sided copper-clad plate with the thickness of 1.6mm is manufactured.
Test example
Comparative examples were compared to examples 1 and 2 using existing process conditions and the results are given in table 1:
TABLE 1
Therefore, the prepreg and the composite material prepared by the resin composition have good heat resistance, mechanical strength, metal adhesion strength and dielectric property, and the prepreg prepared by impregnation has good appearance and proper paving molding viscosity.
Claims (12)
1. A resin composition, characterized in that the resin composition contains:
20-35 parts by weight of a multifunctional epoxy resin;
8-15 parts by weight of isocyanate modified epoxy resin;
5-10 parts by weight of bifunctional epoxy resin;
40-65 parts by weight of polyphenylene ether resin; and
8-16 parts by weight of cyanate ester resin;
wherein the multifunctional epoxy resin is selected from: a dicyclopentadiene type polyfunctional epoxy resin, an o-phenylphenol aldehyde epoxy resin, or a combination thereof, the o-phenylphenol aldehyde epoxy resin having the following structure:
in the formula, a is an integer of 1-10;
the dicyclopentadiene type polyfunctional epoxy resin has the following structure:
in the formula, n is an integer of 1-10;
the isocyanate modified epoxy resin is toluene diisocyanate modified epoxy resin or diphenylmethane diisocyanate modified epoxy resin, and has the following structure:
wherein R is1Is a molecular chain of epoxy resin, R2Is isocyanate molecular chain;
the bifunctional epoxy resin is alicyclic epoxy resin or dehydroxylation epoxy resin with etherified hydroxyl in a molecular chain, and the alicyclic epoxy resin has the following structure:
the dehydroxylation epoxy resin with etherified hydroxyl groups in the molecular chain has the following structure:
wherein R is3Is an aliphatic chain or an aromatic ring;
the polyphenylene ether resin has the following structure:
Wherein e, f and g are each independently an integer of 1 to 20, and Y is a bond; and
the cyanate ester resin is selected from: bisphenol a cyanate ester, dicyclopentadiene phenol cyanate ester resin, or a combination thereof.
2. The resin composition according to claim 1, wherein the polyphenylene ether resin has a number average molecular weight of 1000 to 3000.
3. The resin composition according to claim 1, wherein the resin composition comprises:
20-25 parts by weight of dicyclopentadiene type polyfunctional epoxy resin;
8-12 parts by weight of diphenylmethane diisocyanate-modified epoxy resin;
5-8 parts by weight of alicyclic epoxy resin;
40 to 50 parts by weight of a polyphenylene ether resin; and
8-12 parts by weight of bisphenol A cyanate ester.
4. The resin composition according to claim 1, wherein the resin composition comprises:
30-35 parts by weight of o-phenyl phenolic epoxy resin;
10-15 parts by weight of diphenylmethane diisocyanate-modified epoxy resin;
7-10 parts by weight of an alicyclic epoxy resin;
55-65 parts by weight of a polyphenylene ether resin; and
12-16 parts by weight of dicyclopentadiene phenol type cyanate ester resin.
5. The resin composition according to any one of claims 1 to 4, further comprising at least one of a hardening accelerator, a flame retardant, an inorganic filler, a solvent and a surfactant.
6. The resin composition according to claim 5, wherein the resin composition contains 0.01 to 0.05 parts by weight of a hardening accelerator.
7. The resin composition according to claim 6, wherein the hardening accelerator is an imidazole accelerator selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, or a combination thereof.
8. The resin composition according to claim 5, wherein the resin composition contains a solvent, and the solid content of the resin composition is in a range of 50 to 65% by mass.
9. A resin film, an adhesive sheet or a prepreg, characterized in that the resin film, the adhesive sheet or the prepreg is produced using the resin composition according to any one of claims 1 to 8.
10. A composite or laminate made using the resin film or adhesive sheet of claim 9.
11. A printed circuit board produced using the laminate as claimed in claim 10.
12. Use of the resin composition according to any one of claims 1 to 8 for improving the metal-clad peel strength and/or mechanical strength of a resin film, bonding sheet, prepreg or composite, or for improving the drape formability of a prepreg.
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| CN110452545B (en) * | 2018-05-07 | 2021-12-17 | 广东生益科技股份有限公司 | Resin composition, prepreg for printed circuit, and metal-clad laminate |
| CN109181234A (en) * | 2018-08-09 | 2019-01-11 | 陕西生益科技有限公司 | A kind of high thermal conductivity high tenacity resin combination and its application |
| CN109135652A (en) * | 2018-08-09 | 2019-01-04 | 陕西生益科技有限公司 | A kind of high thermal conductivity toughened resin composition and its application |
| CN111100423A (en) * | 2019-12-27 | 2020-05-05 | 惠柏新材料科技（上海）股份有限公司 | Single-liquid epoxy resin composition and fiber-reinforced composite material |
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| KR101177251B1 (en) * | 2003-06-06 | 2012-08-24 | 히다치 가세고교 가부시끼가이샤 | Adhesive sheet, dicing tape integrated type, adhesive sheet, and semiconductor device producing method |
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| CN103788576B (en) * | 2013-12-02 | 2017-01-11 | 上海南亚覆铜箔板有限公司 | Epoxy resin composition and preparation method thereof |
| CN104945853B (en) * | 2015-07-22 | 2018-07-27 | 江苏华海诚科新材料股份有限公司 | A kind of composition epoxy resin suitable for high voltage surfaces mount device package |
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