CN110204862B - Resin composition, prepreg, laminate, metal-clad laminate, and printed wiring board - Google Patents
Resin composition, prepreg, laminate, metal-clad laminate, and printed wiring board Download PDFInfo
- Publication number
- CN110204862B CN110204862B CN201910475295.0A CN201910475295A CN110204862B CN 110204862 B CN110204862 B CN 110204862B CN 201910475295 A CN201910475295 A CN 201910475295A CN 110204862 B CN110204862 B CN 110204862B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- maleic anhydride
- styrene
- type epoxy
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
-
- 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
-
- 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
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
A resin composition is provided which comprises a specific maleimide compound, a styrene-maleic anhydride copolymer, an epoxy resin and a specific phosphazene flame retardant in a certain ratio. Also provided are prepregs, laminates, metal-foil-clad laminates, and printed wiring boards made using the same. The resin composition has excellent dielectric properties, high flame retardancy, good heat resistance, low water absorption, low thermal expansion coefficient and high bonding property with a conductor after being cured.
Description
Technical Field
The invention relates to a thermosetting resin, in particular to a resin composition, and a prepreg, a laminated board, a metal foil-clad laminated board and a printed circuit board which are prepared by using the resin composition.
Background
With the progress of miniaturization, weight reduction, and multi-functionalization of electronic components, high integration of LSIs, chip components, and the like has progressed, and the form thereof has also rapidly changed to multi-angle and miniaturization. Therefore, in order to increase the mounting density of electronic components, the multilayer printed wiring board has been developed to have a fine wiring.
As a method for manufacturing a multilayer printed wiring board that meets these requirements, a build-up (Buildup) method has been proposed, and the method is becoming mainstream as a method for meeting weight reduction, size reduction, and miniaturization. In addition, in view of increasing environmental awareness, regulations on the restriction of materials that may generate harmful substances during combustion included in electronic components are also becoming more and more stringent. In conventional multilayer printed wiring boards, although a bromine compound for flame retardancy is used, it is predicted that the bromine compound cannot be used in the near future because harmful substances may be generated during combustion.
Among commonly used solders for connecting electronic components in multilayer printed wiring boards, lead-free solders not containing lead have been also put into practical use. Since the lead-free solder has a use temperature about 20 to 30 ℃ higher than that of a conventional eutectic solder, the material is required to have high heat resistance as compared with the conventional eutectic solder.
Meanwhile, with the high speed and multi-function of electronic product information processing, the application frequency is increasing, and the dielectric constant (Dk) and dielectric loss value (Df) are required to be lower and lower, so reducing Dk/Df has become a pursuing hot spot for substrate manufacturers.
Further, since the insulating resin layer containing no glass fiber tends to have a large thermal expansion coefficient due to the reduction in thickness of the multilayer printed wiring board, the difference in thermal expansion coefficient between the insulating resin layer and copper filling or stacking the through hole greatly affects the reliability of connection, and therefore, a material having a small thermal expansion coefficient is required for the insulating resin layer.
When the thermal expansion coefficient is decreased in the insulating resin layer, a method of filling a large amount of an inorganic filler having a small thermal expansion coefficient to decrease the thermal expansion coefficient of the entire insulating layer is used. However, such a method tends to cause many problems such as deterioration in fluidity and reduction in insulation reliability.
In addition, attempts have been made to achieve low thermal expansion by selection or improvement of resins. For example, as an example of a modified bismaleimide resin (see CN106103534_ a), there is a case where a maleimide resin having an imide skeleton, or a benzene skeleton is used to increase the crosslinking density and increase the glass transition temperature (Tg), thereby lowering the thermal expansion rate. However, the modified bismaleimide has difficult control in process, the resin varnish is difficult to store for a long time, and the introduction of a highly polar amine group into the modified bismaleimide has a great negative effect on the dielectric property (Dk/Df) of the resin composition.
On the other hand, for lowering Dk/Df, there are measures by introducing various low-polarity curing agents such as acid anhydrides. However, the commonly seen anhydrides such as methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, alicyclic acid anhydride and other small molecular anhydrides have too fast reaction speed, too strong volatility, high moisture absorption rate, poor solubility and low heat resistance, and are not adopted.
On the other hand, to achieve halogen-free flame retardancy, a phosphorus-containing compound is generally introduced to improve the flame retardancy of the resin composition. The phosphorus-containing compound is classified into a reactive type and an additive type from the viewpoint of reactivity. In order to achieve more excellent Dk/Df, an additive-type phosphorus-containing flame retardant is generally used. However, most of the commercially available additive-type phosphorus-containing flame retardants have a risk of melt-out in the PCB processing flow because the softening point is too low (<260 ℃), which in turn affects the reliability of the PCB.
There is still a need in the printed wiring board industry to find resin compositions having a high balance of properties.
Disclosure of Invention
The invention provides a resin composition, which comprises a maleimide compound shown as a formula (I), a styrene-maleic anhydride copolymer, an epoxy resin and a phosphazene flame retardant shown as a formula (II);
wherein R is1Is phenylene, biphenylene, naphthylene or dicyclopentadienyl, R2, R3Each of which is
Independently a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, n is an integer of 1 to 20;
wherein Rp is hydrogen atom, alkyl group having 1 to 5 carbon atoms, hydroxyl group or allyl group
One kind of the material is selected;
wherein the total weight of the maleimide compound, the styrene-maleic anhydride copolymer and the epoxy resin shown in the formula (I) is 100 parts by weight,
10 to 80 parts by weight of the maleimide compound;
the styrene-maleic anhydride copolymer is 5 to 50 parts by weight, wherein the molar ratio of styrene units to maleic anhydride units is 0.5 to 10, and the acid value of the styrene-maleic anhydride copolymer is 80 to 800 mgKOH/g;
10 to 60 parts by weight of the epoxy resin;
the phosphorus in the phosphazene flame retardant is 0.1 to 5 wt% relative to the total weight of the maleimide compound, the styrene-maleic anhydride copolymer, the epoxy resin, and the phosphazene flame retardant.
The equivalent ratio of the maleic anhydride group in the styrene-maleic anhydride copolymer to the epoxy group in the epoxy resin is preferably 0.5 to 1.5.
Preferably, the styrene-maleic anhydride copolymer is 10 to 40 parts by weight based on 100 parts by weight of the maleimide compound represented by formula (I), the styrene-maleic anhydride copolymer and the epoxy resin.
Preferably, the epoxy resin is a phosphorous epoxy resin, a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthalene type epoxy resin, a naphthol novolac type epoxy resin, a biphenyl type epoxy resin, a dicyclopentadiene type epoxy resin, an aralkyl type epoxy resin, an epoxy resin containing an arylene ether structure, or a mixture thereof.
Preferably, the epoxy resin is 20 to 50 parts by weight based on 100 parts by weight of the maleimide compound represented by formula (I), the styrene-maleic anhydride copolymer, and the epoxy resin.
Preferably, the phosphorus in the phosphazene flame retardant is 0.5 to 4 wt% relative to the total weight of the maleimide compound, the styrene-maleic anhydride copolymer, the epoxy resin, and the phosphazene flame retardant.
Preferably, the resin composition further comprises one or more of a co-curing agent, a filler, a curing accelerator, a silane coupling agent, a mold release agent, a pigment, and an emulsifier.
The present invention also provides a prepreg obtained by impregnating or coating a substrate with the resin composition according to the above and curing it.
The invention also provides a laminate comprising at least one prepreg according to the above.
The invention also provides a metal foil-clad laminate which comprises at least one prepreg and metal foils coated on one side or two sides of the prepreg.
The invention also provides a printed wiring board comprising at least one sheet of prepreg according to the above.
The thermosetting resin composition of the present invention has good compatibility, and has excellent dielectric properties, high flame retardancy, good heat resistance, low water absorption, low thermal expansion coefficient and high adhesion to conductors.
Detailed description of the preferred embodiments
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.
The invention provides a resin composition, which comprises a maleimide compound shown as a formula (I), a styrene-maleic anhydride copolymer and an epoxy resin; and a phosphazene flame retardant represented by the formula (II) and the like, wherein the maleimide compound is 10 to 80 parts by weight, the styrene-maleic anhydride copolymer is 5 to 50 parts by weight, the epoxy resin is 10 to 60 parts by weight, and the phosphorus in the phosphazene flame retardant is 0.1 to 5% by weight relative to the total weight of the maleimide compound, the styrene-maleic anhydride copolymer, the epoxy resin, and the phosphazene flame retardant, based on 100 parts by weight of the total weight of the maleimide compound, the styrene-maleic anhydride copolymer, and the epoxy resin represented by the formula (I). The inventors have unexpectedly found that a prepreg and a laminate using a resin composition containing a maleimide compound having a specific molecular structure, a styrene-maleic anhydride copolymer having a specific molecular structure, an epoxy resin and a phosphazene flame retardant having a specific molecular structure exhibit excellent dielectric properties, high flame retardancy, good heat resistance, low water absorption, a low coefficient of thermal expansion and high bondability to a conductor.
The individual components are described in detail below:
maleimide compound:
the maleimide compound having an unsaturated maleimide group used in the present invention is represented by the following general formula (I), and the method for synthesizing the maleimide compound is not particularly limited, and those skilled in the art can select it based on the prior art in combination with their own expertise. Specifically, for example, it can be obtained by reacting maleic anhydride with an amine compound having at least 2 primary amine groups in 1 molecule. The reaction is preferably carried out in an organic solvent. An example of the product is MIR-3000 manufactured by Nippon chemical Co. The compound is multifunctional biphenyl methane type maleimide, and has the advantages of good compatibility, high reaction rate, high heat resistance and good solubility to solvents in the system, thereby realizing high dielectric property, peeling strength, heat resistance and flame retardance.
Wherein R is1Is phenylene, biphenylene, naphthylene or dicyclopentadienyl, R2And R3 are each independently a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and n is an integer of 1 to 20.
Preferably, in the maleimide compound (A) with the structure of formula (I), n is an integer of 1-15, more preferably n is an integer of 1-10;
the content of the maleimide compound is in the range of 10 to 80 parts by weight relative to 100 parts by weight of the maleimide compound, the styrene-maleic anhydride copolymer and the epoxy resin in total, from the viewpoint of glass transition temperature and water absorption rate, and when the content is too high, insufficient curing or severe curing conditions may occur, and when the content is too low, excellent heat resistance may not be sufficiently exhibited; more preferably 20 to 60 parts by weight.
Styrene-maleic anhydride copolymer:
the styrene-maleic anhydride copolymer used in the present invention greatly affects the curing of the resin composition. The styrene-maleic anhydride copolymer comprises styrene units and maleic anhydride units, wherein the molar ratio of the styrene units to the maleic anhydride units is between 0.5: 1 and 10: 1, and the acid value is 80-800 mgKOH/g. Such a styrene-maleic anhydride copolymer is well compatible in the system of the present invention, thereby realizing high dielectric properties, peel strength, heat resistance and moist heat resistance. When the molar ratio of the two units or the acid value is out of the above range, the obtained styrene-maleic anhydride copolymer is not well compatible with the system, and it is difficult to obtain excellent dielectric strength, peel strength, heat resistance and moist heat resistance. The content of the styrene-maleic anhydride copolymer is 5 to 50 parts by weight relative to 100 parts by weight of the maleimide compound, the styrene-maleic anhydride copolymer and the epoxy resin in total. When the content is too high, the flame retardancy and moist heat resistance of the resin composition are not satisfactory, and when the content is too low, the dielectric properties of the resin composition cannot be ensured. Preferably, the content of the styrene-maleic anhydride copolymer is 10 to 40 parts by weight.
Epoxy resin:
the epoxy resin according to the present invention is not particularly limited, and is selected from epoxy resins having at least two epoxy groups, and for example, may be selected from 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, bisphenol Z type epoxy resins, bisphenol AP type epoxy resins, bisphenol TMC 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 resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, dicyclopentadiene type novolac epoxy resin, aralkyl type novolac 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. From the viewpoint of compatibility with the system of the composition of the present invention, high heat resistance, low relative dielectric constant, high adhesiveness, low thermal expansibility, and high glass transition temperature, a phosphorus-containing epoxy resin, a phenol novolac epoxy resin, a cresol novolac epoxy resin, a naphthalene epoxy resin, a naphthol novolac epoxy resin, a biphenyl epoxy resin, a dicyclopentadiene phenol epoxy resin, an aralkyl phenol epoxy resin, an epoxy resin containing an arylene ether structure, or a mixture thereof is preferable, and a phenol novolac epoxy resin, an o-cresol novolac epoxy resin, a naphthol novolac epoxy resin, a phenol novolac epoxy resin, a biphenyl epoxy resin, a dicyclopentadiene novolac epoxy resin, a phenol epoxy resin, a naphthol novolac epoxy resin, a phenol novolac epoxy resin, a dicyclopentadiene epoxy resin, a phenol novolac resin, a phenol resin, a naphthol novolac epoxy resin, a phenol resin, or a mixture thereof is more preferable, Aralkyl type epoxy resins, aralkyl novolac type epoxy resins. From the viewpoint of low dielectric constant and low cost, dicyclopentadiene type epoxy resins and dicyclopentadiene novolac type epoxy resins are more preferable. One kind of the epoxy resin may be used alone, or two or more kinds may be used in combination.
The content of the epoxy resin is 10 to 60 parts by weight relative to 100 parts by weight of the maleimide compound, the styrene-maleic anhydride copolymer and the epoxy resin in total. When the content is too high, the dielectric properties of the resin composition are insufficient, and when the content is too low, the adhesive strength of the resin composition is lowered. Preferably, the content of the epoxy resin is 20 to 50 parts by weight.
In the composition of the present invention, when the styrene-maleic anhydride copolymer and the epoxy resin satisfy a certain ratio relationship, the resin composition can achieve a balance among moist heat resistance, dielectric properties and adhesive strength. Preferably, the equivalent ratio of the maleic anhydride group in the styrene-maleic anhydride copolymer and the epoxy group in the epoxy resin is 0.5 to 1.5, and further preferably 0.80 to 1.20.
Phosphazene flame retardant:
the phosphazene flame retardant shown in the formula (II) has a high melting point and good compatibility with a system of the composition, so that the composition has flame retardant property and also has high peel strength, heat resistance, damp-heat resistance and heat migration resistance. The present inventors have found that a specific maleimide compound of the formula (I), a styrene-maleic anhydride copolymer, and an epoxy composition provide excellent dielectric properties, good heat resistance, low water absorption, a low coefficient of thermal expansion, and high adhesion to a conductor, but are still insufficient in flame retardancy. In order to improve the flame retardancy of the composition, flame retardants, in particular halogen-free phosphorus-containing flame retardants, may be added. However, the halogen-free phosphorus-containing flame retardant with low melting point has poor compatibility with a resin system after being added, reduces the heat resistance of the resin system, solves the problem of melting precipitation of a PCB in a high-temperature process, and influences the heat resistance, dielectric property and reliability of the laminated board. The inventors have surprisingly found that the phosphazene flame retardant represented by the formula (II) has good system compatibility with the resin composition of the invention, so that the resin composition has high peeling strength, heat resistance, wet heat resistance and good dielectric property while having high-efficiency flame retardant property, and the migration problem of the phosphorus-containing flame retardant does not occur.
Wherein Rp is one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group or an allyl group.
From the viewpoint of the phosphorus content, the phosphorus in the phosphazene flame retardant is 0.1 to 5% by weight relative to the total weight of the maleimide compound, the styrene-maleic anhydride copolymer, the epoxy resin, and the phosphazene flame retardant, preferably the weight of phosphorus contained in the phosphazene flame retardant accounts for 0.5 to 4% by weight of the composition, and more preferably 1 to 3% by weight.
The invention may further comprise one or more of optional co-curing agents, fillers, curing accelerators, silane coupling agents, release agents, pigments, emulsifiers.
Co-curing agent:
the composition of the present invention may also contain a co-curing agent. As the co-curing agent, one or more of an amine-based curing agent, a thiol-based curing agent, a cyanate-based curing agent, an isocyanate-based curing agent, an active ester-based curing agent, a phenol-based curing agent, and benzoxazine may be included. Among them, from the viewpoint of high adhesiveness and low thermal expansion, an amine-based curing agent, a cyanate-based curing agent, an active ester-based curing agent, and a phenol-based curing agent are preferable, and an amine-based curing agent and a phenol-based curing agent are more preferable. The amount of the co-curing agent added may be adjusted as necessary.
Examples of the amine-based curing agent may include: dicyandiamide; chain aliphatic amines other than dicyandiamide, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, tetramethylguanidine, and triethanolamine; cyclic aliphatic amines such as isophoronediamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4-amino-3-methyldicyclohexyl) methane, N-aminoethylpiperazine, 3, 9-bis (3-aminopropyl) -2, 4, 8, 10-tetraoxaspiro [5.5] undecane, and the like; and aromatic amines such as xylylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and diaminodiphenyl ether (ODA). Among them, diaminodiphenyl ether and dicyandiamide are preferable from the viewpoint of low relative dielectric constant and low water absorption.
Examples of the phenolic curing agent may include: biphenyl type phenol curing agent, naphthalene type phenol curing agent, novolak resin type curing agent, naphthylene ether type phenol curing agent, and triazine skeleton-containing phenol curing agent.
Filling:
the resin composition of the present invention may further contain an inorganic filler. The inorganic filler described in the present invention is not particularly limited, and the inorganic filler may be an inorganic filler known in the field of prepregs and laminates as long as it does not significantly deteriorate the performance of the resin composition of the present invention. By adding an inorganic filler to the resin composition, a resin composition having excellent mechanical properties, moist heat resistance, flame retardancy, dielectric properties and thermal expansion coefficient can be obtained. The inorganic filler may be 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 silicon 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 sulfate, boron nitride, aluminum nitride, silicon carbide, silicon oxide, strontium titanate, barium sulfate, boron nitride, aluminum nitride, magnesium oxide, alumina, boron nitride, silicon carbide, magnesium oxide, boron titanate, and glass, Any one or a mixture of at least two of alumina, zinc borate, zinc stannate, clay, kaolin, talc, mica, composite 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 fibers, or hollow glass, for example, 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, composite silica powder, E glass powder, A mixture of D glass frit, L glass frit and M glass frit, a mixture of S glass frit, T glass frit, NE glass frit and quartz glass frit, a mixture of clay, kaolin, talc and mica, a mixture of short glass fibers and hollow glass. The fused silica is preferable in that an inorganic filler can be further added. The fused silica may be any of pulverized and spherical fused silica, and spherical fused silica is preferably mainly used in order to increase the amount of fused silica and to suppress an increase in melt viscosity of the curable composition.
The average particle diameter (d50) of the inorganic filler is not particularly limited, but from the viewpoint of dispersibility, the average particle diameter (d50) is preferably 0.1 to 10 micrometers, for example, 0.2 micrometers, 0.8 micrometers, 1.5 micrometers, 2.1 micrometers, 2.6 micrometers, 3.5 micrometers, 4.5 micrometers, 5.2 micrometers, 5.5 micrometers, 6 micrometers, 6.5 micrometers, 7 micrometers, 7.5 micrometers, 8 micrometers, 8.5 micrometers, 9 micrometers, 9.5 micrometers, and more preferably 0.2 to 5 micrometers. The inorganic fillers of different types, different particle size distributions, or different average particle diameters may be used alone or in combination of plural kinds as required.
The amount of the inorganic filler used in the present invention is not particularly limited. The amount of the inorganic filler may be 10 to 200 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, preferably 20 to 150 parts by weight, and more preferably 30 to 100 parts by weight, based on 100 parts by weight of the maleimide compound, the styrene-maleic anhydride copolymer, and the epoxy resin in total.
The inorganic filler of the present invention may be used in combination with a surface treatment 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, 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, preferably aminosilane coupling agents, epoxy silane coupling agents, phenyl silane coupling agents, and further preferably aminosilane coupling agents. 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 resin composition of the present invention may further include an organic filler. The organic filler is not particularly limited, and may be selected from any one of silicone, liquid crystal polymer, thermosetting resin, thermoplastic resin, rubber, or core-shell rubber, or a mixture of at least two thereof. The organic filler may be powder or granules. The amount of the organic filler added may be adjusted as necessary.
Curing accelerator:
the resin composition of the present invention may further comprise a curing accelerator which lowers the curing temperature of the resin and accelerates the curing speed of the resin. Examples of the curing accelerator may include: phosphorus-based accelerators, tertiary amines, imidazoles, organic acid metal salts, lewis acids, amine complex salts, and the like.
Preferably, the curing accelerator is an imidazole-based curing accelerator or a pyridine-based curing accelerator, and examples of the imidazole-based curing accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, salts thereof with a group selected from the group consisting of, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, imidazole compounds such as 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1, 2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. The pyridine curing accelerator is selected from triethylamine, benzyldimethylamine and dimethylaminopyridine. When a curing accelerator (other than the metal-based curing accelerator) is added to the resin composition of the present invention, the curing accelerator is preferably in the range of 0.005 to 5 parts by mass, more preferably in the range of 0.01 to 3 parts by mass, based on 100 parts by mass of the maleimide compound, the styrene-maleic anhydride copolymer and the epoxy resin in total. When the amount is within this range, the heat-curable resin composition can be more efficiently cured and the storage stability of the resin varnish can be improved.
In addition, various blending agents such as a silane coupling agent, a release agent, a pigment, an emulsifier, and the like may be added to the resin composition of the present invention as necessary.
The resin composition of the present invention exhibits excellent solvent solubility. Therefore, the resin composition may be compounded with an organic solvent in addition to the above-mentioned respective components. Examples thereof include aromatic hydrocarbons, aprotic polar solvents, alcohols, ketones, glycol ethers, and the like. Aprotic polar solvents, alcohols, ketones, and amide solvents are preferred. Examples of the aromatic hydrocarbon include benzene, toluene, and xylene. Examples of the alcohols include methanol, ethanol, propanol, and butanol. Examples of ketones include acetone, Methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MIBK), diisopropyl ketone, di-tert-butyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, cyclohexyl methyl ketone, acetophenone, acetylacetone, and dioxane. Specific examples of the aprotic polar solvent include dimethyl sulfoxide (DMSO), formamide, N-methylformamide, N-dimethylformamide, acetamide, N-methylacetamide, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, and the like. Specific examples of the glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, and propylene glycol monomethyl ether acetate.
The resin composition of the present invention may also be used in combination with a maleimide resin other than the specific maleimide resin, as long as it does not impair the inherent properties of the resin composition. The maleimide resin which may be selected may be bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, 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 (4- (4-maleimidophenoxy) -phenyl) sulfone, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) ketone, bis (3, 5-methyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) ketone, bis (4-methyl-maleimidophenyl) ketone, bis (4-methyl-phenyl) ketone, bis (4-methyl-phenyl) ether, bis (4-methyl-phenyl) ketone, bis (4-phenyl) ketone, or (4-phenyl) ether, or a-methyl-phenyl) ether, Any one or a mixture of at least two of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane and polyphenylmethanemaleimide (Polyphenylmethane maleimido). These maleimide resins may be used singly or in combination of plural kinds as required, or these maleimide resins may be modified with an allyl compound or an amine compound and then used.
The 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 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. The thermosetting resin may be selected from the group consisting of phenolic resins, cyanate ester resins, benzoxazine resins, polyphenylene ether resins, silicone resins, allyl resins, amine compounds and dicyclopentadiene resins. They may be used alone or in combination of plural kinds as required.
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 resin composition of the present invention can be used for various electronic material applications, and can be prepared, for example, by a method of thoroughly mixing the respective single components to homogeneity using an extruder, a kneader, a roll, or the like.
When a printed circuit board is produced using the thermosetting resin composition of the present invention, the following methods may be mentioned: a reinforcing base material is impregnated with a varnish-like thermosetting resin composition containing the resin of the present invention, a curing agent, an organic solvent, other additives, and the like, and a copper foil is stacked and thermally pressed. Examples of the reinforcing base material that can be used here include: paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass felt, glass roving cloth and the like. When the above method is described in detail, the varnish-like thermosetting resin composition is first heated at a heating temperature suitable for the type of solvent used, preferably 50 to 170 ℃ for 3 to 15 minutes to obtain a prepreg as a cured product. The mass ratio of the thermosetting resin composition and the reinforcing base material used in this case is not particularly limited, and it is generally preferably prepared so that the resin component in the prepreg is 30 to 90 mass%. Next, the prepregs obtained as described above are laminated by a conventional method, appropriately laminated with copper foil, and thermally pressed at 170 to 250 ℃ under a pressure of 1 to 10MPa for 10 minutes to 3 hours to obtain the target printed circuit board.
Examples
The present invention will be described in more detail with reference to the following examples, which, however, are not intended to limit the present invention in any way. In each example, a resin varnish, a prepreg, and a copper-clad laminate were prepared, and the resulting copper-clad laminate was evaluated. The evaluation method is as follows.
Evaluation method
(A) Glass transition temperature (Tg)
The temperature at which the elastic modulus change reaches the maximum (tan. delta. change rate is maximum) was measured for the above-described evaluation sample using a viscoelasticity measuring apparatus (DMA: solid viscoelasticity measuring apparatus manufactured by Rheometric corporation RSAII, Rectangular stretching (Rectangular stretching) method; frequency 1Hz, temperature increase rate 5 ℃/min) and evaluated as the glass transition temperature.
(B) Coefficient of Thermal Expansion (CTE)
The measurement was carried out according to the IPC-TM-6502.4.24 method.
(C) Dielectric constant (Dk) and dielectric loss factor (Df)
The dielectric constant and dielectric loss factor at 1GHz were measured according to the plate capacitance method.
(D) Peel strength
The measurement was carried out according to IPC-TM-6502.4.8.
(E) Evaluation of Wet Heat resistance
After etching the copper foil on the surface of the copper clad laminate, evaluating the substrate; placing the substrate in a pressure cooker, processing for 3 hours under the conditions of 120 ℃ and 105KPa, then soaking in a tin furnace at 288 ℃, and recording corresponding time when the substrate is layered and exploded; the evaluation was concluded when the substrate had not blistered or delaminated in the tin oven for more than 5 minutes. No foaming and no delamination were noted as O, and foaming or delamination were noted as X.
(F) Flame retardancy
Measured according to the UL 94 vertical burning method.
(G) Resistance to thermal migration
After the copper-clad plate is subjected to 5 times of lead-free reflow soldering process (the material temperature is more than 260 ℃), a sliced sample is prepared, and the resin form of the sliced sample is observed under an electron microscope. The occurrence of no migration or delamination in the resin layer was designated as O, and the occurrence of migration or delamination in the resin layer was designated as X.
The raw materials used in the examples included:
maleimide compound:
(A1) biphenylalkyl maleimide resin "MIR-3000-70 MT" (manufactured by Nippon Kabushiki Kaisha) having a structure represented by the formula (I)
(A2) Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane "KI-70" (Nippon KI Co., Ltd.) having no structure represented by the formula (I)
Styrene-maleic anhydride copolymer (B):
(B1) "SMA EF 30" (styrene/maleic anhydride 3, manufactured by SARTOMER Co., Ltd.), and acid value of 280mgKOH/g
(B2) "SMA EF 40" (styrene/maleic anhydride 4, manufactured by SARTOMER Co., Ltd.), and an acid value of 215mgKOH/g
Epoxy resin (C):
(C1) dicyclopentadiene type epoxy resin "HP-7200H" (manufactured by DIC corporation)
(C2) Biphenylalkyl epoxy resin "NC-3000-H" (manufactured by Nippon Kabushiki Kaisha)
Flame retardant (D):
(D1) a high melting point phosphazene compound (Otsuka chemical Co., Ltd.) having the following formula
(D2) Phosphazene Compound "SPB-100" (Otsuka chemical Co., Ltd.)
(D3) Phosphate ester Compound "PX-200" (Daba chemical Co., Ltd.)
Co-curing agent (E):
(E1)4, 4-diaminodiphenyl ether "DDE" (manufactured by Shandong Wanda chemical)
(E2) Dicyandiamide "Dicy" (Ningxia Darong)
(E3) Biphenylalkyl phenol resin "MEH-7851" (manufactured by Minghe Kangji Co., Ltd.)
Inorganic filler (F): spherical silica "DQ 1028L" (manufactured by Jiangsu Uniry)
Curing accelerator (G): 2-phenylimidazole "2 PZ" (manufactured by four chemical industries, Ltd.)
Comparative curing agent:
(B3) methylhexahydrophthalic anhydride "MHHPA" (manufactured by Guangdong Shengshida)
(B4) Nadic methyl anhydride "MNA" (manufactured by Taiwan Changchun, China)
Resin varnishes of examples and comparative examples were prepared with the compositions listed in tables 1 to 5 below, and the above-mentioned various essential components and the like.
Each of the resin varnishes thus obtained was impregnated with 2116 glass cloth (0.1mm) and dried at 155 ℃ for 5 minutes to obtain a prepreg. Then, 8 sheets of the prepreg were stacked, and an 18 μm-thick reverse copper foil (manufactured by Mitsui metals Co., Ltd.) was laminated on both sides, and the resultant was heated and pressed at 200 ℃ and 25kgf/cm2(2.45MPa) for 90 minutes to prepare a copper clad laminate having a thickness of 1.0mm, and the relative dielectric constant, the adhesiveness to the metal foil, the glass transition temperature, the thermal expansibility, the flame retardancy and the processability were measured and evaluated in accordance with the above-mentioned methods.
The results are shown in tables 1 to 5.
Table 1 examples 1-6
Table 2 examples 7-12
TABLE 3 COMPARATIVE EXAMPLES 1 to 6
TABLE 4 COMPARATIVE EXAMPLES 7 to 12
TABLE 5 COMPARATIVE EXAMPLES 13 to 14
As can be seen from tables 1-2, in examples 1-12, the performance of the compositions was excellent by varying the amounts and types of the individual components in the resin compositions.
In comparative example 1, the dielectric properties, peel strength, heat resistance and flame retardancy of the resin composition were greatly reduced by replacing the polyfunctional biphenyl aralkyl type maleimide resin represented by the formula (I) with the non-bifunctional maleimide resin represented by the formula (I) as compared with example 7.
In comparative examples 2 and 3, the dielectric properties, peel strength, heat resistance and wet heat resistance of the resin composition were significantly reduced by replacing the styrene-maleic anhydride copolymer with a conventional small molecular acid anhydride, as compared with example 7.
In comparative examples 4, 5 and 6, the peel strength, heat resistance, wet heat resistance and migration resistance of the resin composition were significantly reduced by replacing the phosphazene flame retardant with another phosphorus-containing flame retardant as compared with example 7.
In comparative examples 7 to 14, the properties of the resin compositions were deteriorated to various degrees when the respective components were out of the scope of the claims.
The thermosetting resin composition of the present invention has good compatibility, and has excellent dielectric properties, high flame retardancy, good heat resistance, low water absorption, low thermal expansion coefficient and high adhesion to conductors.
It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments of the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (13)
1. A resin composition comprising:
maleimide compound shown as a formula (I), styrene-maleic anhydride copolymer, epoxy resin and phosphazene flame retardant shown as a formula (II);
wherein R is1Is phenylene, biphenylene, naphthylene or dicyclopentadienyl, R2、R3Each independently is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and n is an integer of 1 to 20;
wherein Rp is one of a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, a hydroxyl group or an allyl group;
wherein the total weight of the maleimide compound, the styrene-maleic anhydride copolymer and the epoxy resin shown in the formula (I) is 100 parts by weight,
10 to 80 parts by weight of the maleimide compound;
the styrene-maleic anhydride copolymer is 5 to 50 parts by weight, wherein the molar ratio of styrene units to maleic anhydride units is 0.5 to 10, and the acid value of the styrene-maleic anhydride copolymer is 80 to 800 mgKOH/g;
10 to 60 parts by weight of the epoxy resin;
the phosphorus in the phosphazene flame retardant is 0.1 to 5 wt% relative to the total weight of the maleimide compound, the styrene-maleic anhydride copolymer, the epoxy resin, and the phosphazene flame retardant.
2. The resin composition according to claim 1, wherein an equivalent ratio of the maleic anhydride group in the styrene-maleic anhydride copolymer and the epoxy group in the epoxy resin is 0.5 to 1.5.
3. The resin composition according to claim 1 or 2, wherein the styrene-maleic anhydride copolymer is 10 to 40 parts by weight based on 100 parts by weight of the maleimide compound represented by formula (I), the styrene-maleic anhydride copolymer and the epoxy resin.
4. The resin composition according to claim 1 or 2, wherein the epoxy resin is a phosphorus-containing epoxy resin, a naphthalene-type epoxy resin, a biphenyl-type epoxy resin, a dicyclopentadiene-type epoxy resin, an aralkyl-type epoxy resin, an arylene ether structure-containing epoxy resin, or a mixture thereof.
5. The resin composition according to claim 1 or 2, wherein the epoxy resin is a phosphorus-containing epoxy resin, a phenol novolac type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a dicyclopentadiene type epoxy resin, an aralkyl type epoxy resin, or a mixture thereof.
6. The resin composition according to claim 1 or 2, wherein the epoxy resin is a phosphorus-containing epoxy resin, a cresol novolac type epoxy resin, a naphthalene type epoxy resin, a naphthol novolac type epoxy resin, a biphenyl type epoxy resin, a dicyclopentadiene novolac type epoxy resin, an aralkyl novolac type epoxy resin, or a mixture thereof.
7. The resin composition according to claim 1 or 2, wherein the epoxy resin is 20 to 50 parts by weight based on 100 parts by weight of the maleimide compound represented by formula (I), the styrene-maleic anhydride copolymer, and the epoxy resin.
8. The resin composition of claim 1 or 2, wherein the phosphorus in the phosphazene flame retardant is 0.5 to 4 weight percent relative to the total weight of the maleimide compound, the styrene-maleic anhydride copolymer, the epoxy resin, and the phosphazene flame retardant.
9. The resin composition according to claim 1 or 2, wherein the resin composition further comprises one or more of a co-curing agent, a filler, a curing accelerator, a silane coupling agent, a mold release agent, a pigment, and an emulsifier.
10. A prepreg obtained by impregnating or coating a substrate with the resin composition according to any one of claims 1 to 9 and curing it.
11. A laminate comprising at least one prepreg according to claim 10.
12. A metal-clad laminate comprising at least one prepreg according to claim 10 and a metal foil clad on one or both sides of the prepreg.
13. A printed wiring board comprising at least one prepreg according to claim 10.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910475295.0A CN110204862B (en) | 2019-05-31 | 2019-05-31 | Resin composition, prepreg, laminate, metal-clad laminate, and printed wiring board |
| TW108129019A TWI716967B (en) | 2019-05-31 | 2019-08-14 | Resin composition, prepreg, laminate, metal-clad laminate and printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910475295.0A CN110204862B (en) | 2019-05-31 | 2019-05-31 | Resin composition, prepreg, laminate, metal-clad laminate, and printed wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110204862A CN110204862A (en) | 2019-09-06 |
| CN110204862B true CN110204862B (en) | 2021-11-30 |
Family
ID=67790296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910475295.0A Active CN110204862B (en) | 2019-05-31 | 2019-05-31 | Resin composition, prepreg, laminate, metal-clad laminate, and printed wiring board |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110204862B (en) |
| TW (1) | TWI716967B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021212314A1 (en) * | 2020-04-21 | 2021-10-28 | 穗晔实业股份有限公司 | Thermosetting resin composition |
| JP6830586B1 (en) | 2020-07-22 | 2021-02-17 | 株式会社伏見製薬所 | Cyclic phosphazene compound having an oxaphosphorin ring-containing structure |
| TWI803069B (en) * | 2021-11-26 | 2023-05-21 | 南亞塑膠工業股份有限公司 | Resin composition |
| CN115637013A (en) * | 2022-10-31 | 2023-01-24 | 深圳伊帕思新材料科技有限公司 | Bismaleimide composition, semi-cured film and copper foil substrate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047718A (en) * | 2017-12-29 | 2018-05-18 | 广东生益科技股份有限公司 | Maleimide resin composition, prepreg, laminate and printed circuit board (PCB) |
| CN108219371A (en) * | 2017-12-29 | 2018-06-29 | 广东生益科技股份有限公司 | Composition epoxy resin, prepreg, laminate and printed circuit board |
| CN108401433A (en) * | 2016-12-07 | 2018-08-14 | 日立化成株式会社 | Resin varnish, prepreg, plywood and printed wiring board |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3865783A (en) * | 1972-05-18 | 1975-02-11 | Akzona Inc | Flame-retardant polyester |
| TWI491671B (en) * | 2013-05-21 | 2015-07-11 | Elite Material Co Ltd | Low dielectric halogen-free resin compositions and circuit boards for which they are used |
| TWI678393B (en) * | 2017-09-07 | 2019-12-01 | 台燿科技股份有限公司 | Resin composition, and pre-preg, metal-clad laminate and printed circuit board prepared using the same |
-
2019
- 2019-05-31 CN CN201910475295.0A patent/CN110204862B/en active Active
- 2019-08-14 TW TW108129019A patent/TWI716967B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108401433A (en) * | 2016-12-07 | 2018-08-14 | 日立化成株式会社 | Resin varnish, prepreg, plywood and printed wiring board |
| CN108047718A (en) * | 2017-12-29 | 2018-05-18 | 广东生益科技股份有限公司 | Maleimide resin composition, prepreg, laminate and printed circuit board (PCB) |
| CN108219371A (en) * | 2017-12-29 | 2018-06-29 | 广东生益科技股份有限公司 | Composition epoxy resin, prepreg, laminate and printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI716967B (en) | 2021-01-21 |
| TW201940589A (en) | 2019-10-16 |
| CN110204862A (en) | 2019-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110204862B (en) | Resin composition, prepreg, laminate, metal-clad laminate, and printed wiring board | |
| CN107254144B (en) | Resin composition, and prepreg and laminate using same | |
| TWI657108B (en) | Epoxy resin composition, prepreg, laminate and printed circuit board | |
| KR101897426B1 (en) | Halogen-free resin composition and prepreg and laminated prepared therefrom | |
| US10513605B2 (en) | Halogen-free epoxy resin composition, prepreg, laminate and printed circuit board containing the same | |
| TWI532784B (en) | A halogen-free resin composition and use thereof | |
| CN110218415B (en) | Resin composition, prepreg, laminate, metal-clad laminate, and printed wiring board | |
| KR101798809B1 (en) | Halogen-free resin composition and prepreg and laminated board prepared therefrom | |
| CN108485182B (en) | High-frequency resin composition and prepreg and laminated board manufactured by using same | |
| CN109988298B (en) | Modified polyphenyl ether resin, thermosetting resin composition and application thereof | |
| WO2017092472A1 (en) | Halogen-free epoxy resin composition and prepreg, laminated board and printed circuit board containing same | |
| EP2690120A1 (en) | Resin composition, prepreg and resin sheet, and metal foil-clad laminate | |
| JP5682110B2 (en) | Thermosetting resin composition, prepreg and laminate using the same | |
| WO2016074288A1 (en) | Thermosetting resin composition and prepreg and laminated board prepared therefrom | |
| CN108047718B (en) | Maleimide resin composition, prepreg, laminate, and printed wiring board | |
| TWI706997B (en) | Halogen-free flame-retardant thermosetting resin composition, prepreg for printed circuit and metal-clad laminate | |
| WO2019127391A1 (en) | Maleimide resin composition, prepreg, laminate and printed circuit board | |
| CN108117723B (en) | Thermosetting resin composition, prepreg using same and laminated board for printed circuit | |
| KR20200055795A (en) | Epoxy resin composition, prepreg, laminated board and printed circuit board | |
| JP2005209489A (en) | Insulation sheet | |
| CN109970952B (en) | Cyanate ester resin composition and use thereof | |
| JP7330648B2 (en) | Thermosetting maleimide resin composition, and uncured resin film and cured resin film made of the resin composition | |
| CN109694462B (en) | Thermosetting resin composition, and prepreg, metal foil-clad laminate and printed circuit board using same | |
| CN109971130B (en) | Cyanate ester resin composition and use thereof | |
| TWI753194B (en) | Resin composition, prepreg for printed circuit, and metal-clad laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |