CN110845706B - Thermosetting resin composition, prepreg using same, laminated board and printed circuit board - Google Patents
Thermosetting resin composition, prepreg using same, laminated board and printed circuit board Download PDFInfo
- Publication number
- CN110845706B CN110845706B CN201911205625.0A CN201911205625A CN110845706B CN 110845706 B CN110845706 B CN 110845706B CN 201911205625 A CN201911205625 A CN 201911205625A CN 110845706 B CN110845706 B CN 110845706B
- Authority
- CN
- China
- Prior art keywords
- resin
- resin composition
- thermosetting resin
- phenol
- 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
-
- 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
- C08G59/621—Phenols
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- C—CHEMISTRY; METALLURGY
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- B32B2307/30—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
- B32B2363/00—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides a thermosetting resin composition, and a prepreg, a laminated board and a printed circuit board using the thermosetting resin composition, wherein the thermosetting resin composition comprises epoxy resin, a curing agent, a curing accelerator and a composite flame-retardant filler; the composite flame-retardant filler comprises DOPO derivatives, melamine salt compounds and metal hydroxides; the DOPO derivative has a structure shown as a formula (1). By utilizing the matching of DOPO derivatives, melamine salt compounds and metal hydroxides in the composite flame-retardant filler, the flame retardance of a cured product can be effectively improved, and the cured product has good heat resistance and dip soldering resistance and low water absorption.
Description
Technical Field
The invention belongs to the technical field of laminated boards, and relates to a thermosetting resin composition, a prepreg using the thermosetting resin composition, a laminated board and a printed circuit board.
Background
The CEM-1 copper-clad laminate is prepared by respectively soaking electronic grade glass fiber cloth and bleached wood pulp paper as reinforcing materials in a resin composition for the copper-clad laminate to prepare a fabric and a core material, covering the fabric and the core material with copper foil and carrying out hot pressing. Flame retardance is one of the most concerned performances of the CEM-1 copper clad laminate, but the CEM-1 copper clad laminate takes a wood pulp paper bonding sheet as a core material, the wood pulp paper is combustible, and the difficulty in improving the flame retardance of the CEM-1 copper clad laminate is high on the premise of ensuring other performances of the CEM-1 copper clad laminate, particularly heat resistance, toughness, moisture resistance and the like. At present, the flame retardance of the halogen CEM-1 copper-clad laminate is mainly realized by adopting the traditional halogen-antimony synergistic flame retardant technology, however, with the continuous increase of environmental management substances, antimony oxide substances are considered by the European Union to be taken into the RoHS restricted substance list, once restriction is implemented in the future, the halogen-antimony synergistic flame retardant technology cannot be adopted, and therefore a new technology needs to be developed to replace the traditional technology.
CN103073744A provides a phosphorus-nitrogen-bromine composite system flame retardant, which mainly comprises melamine hydrobromide, ammonium polyphosphate and a flame-retardant synergistic synergist (2, 3-dimethyl-2, 3-diphenylbutane), and integrates the advantages of phosphorus-nitrogen and bromine flame retardants to complement the performances of the flame retardant, so that the flame retardant can achieve good flame retardance when applied to polypropylene plastics, but the application of the composite system flame retardant in the field of copper-clad laminates is not pointed out.
CN101768338A discloses a halogen-free antimony-free flame-retardant polyethylene terephthalate engineering plastic, a preparation method and application thereof. The plastic comprises the following components in percentage by weight: 39-65% of polyethylene terephthalate, 15-40% of a reinforcing agent, 0-8% of a toughening agent, 5-8% of a phosphorus flame retardant, 0-8% of a nitrogen flame retardant, 0-4% of a synergistic flame retardant, 0-0.5% of a nucleating agent and 0-0.5% of an antioxidant. The phosphorus-nitrogen flame-retardant system is compounded with the nano clay, so that halogen-free and antimony-free flame retardance of the composite material is realized, a high CTI value of the composite material is ensured, and the composite material is suitable for the field of electronic appliances, but the specific application in the technical field of copper-clad laminates is not pointed out.
CN101974206A discloses a halogen-free and antimony-free epoxy resin composition, which is composed of the following raw materials by weight: 5-30 parts of epoxy resin containing biphenyl structural units; 5-20 parts of modified phenolic resin; 50-300 parts of inorganic filler; 0.5-2.5% of a curing accelerator; 0.5-4.5 parts of a silane coupling agent; 0.1-5% of a coloring agent; 0.5-4.5% of a release agent. The epoxy resin composition can reach the flame retardant standard of UL-94V-0 level, but is suitable for semiconductor devices and is not applied to copper clad laminates.
Therefore, there is a need to develop an antimony-free CEM-1 copper clad laminate to meet the environmental requirements of the latest international environmental regulations on electronic products.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide a thermosetting resin composition, and a prepreg, a laminate and a printed circuit board using the same.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a thermosetting resin composition comprising an epoxy resin, a curing agent, a curing accelerator, and a composite flame retardant filler;
the composite flame-retardant filler comprises a DOPO derivative, a melamine salt compound and a metal hydroxide;
the DOPO derivative has a structure represented by the following formula (1):
wherein R is any one of substituted or unsubstituted alkylene of C2-C18 or substituted or unsubstituted aromatic alkylene of C6-C12.
According to the invention, by utilizing the coordination of DOPO derivatives, melamine salt compounds and metal hydroxides in the composite flame-retardant filler, the flame retardance, dip soldering resistance and heat resistance of a cured product can be effectively improved, and relatively low water absorption can be obtained.
The R is a substituted or unsubstituted alkylene group of C2-C18, namely a substituted or unsubstituted alkylene group of C2, C3, C4, C5, C6, C8, C10, C12, C14, C16 or C18, preferably a substituted or unsubstituted alkylene group of C2-C5.
In the present invention, the R may be a substituted or unsubstituted C6-C12 (e.g., C6, C7, C8, C9, C10, C11, or C12) arylene group.
In the present invention, when the group has a substituent as described above, the substituent is selected from a phenyl group, a naphthyl group, or an alkyl group having from C1 to C4.
Preferably, the DOPO derivative represented by the formula (1) is any one of the following formulae (2), (3), (4) or (5), and further preferably the DOPO derivative represented by the formula (2):
in the present invention, the DOPO derivative represented by the formula (2) is more preferable from the viewpoints of stability of the structure of the DOPO derivative, phosphorus content, flame retardancy, and availability for industrial production.
Preferably, the melamine salt compound is any one of melamine polyphosphate, melamine cyanurate, or melamine borate, or a combination of at least two thereof, preferably melamine cyanurate. Melamine cyanurate is preferred in the present invention because it has a high nitrogen content in the melamine salt compound, good flame retardancy and good heat resistance.
Preferably, the metal hydroxide is magnesium hydroxide or aluminum hydroxide, and in view of the close flame retardancy between the two, magnesium hydroxide has a large surface polarity and is poor in compatibility with a resin, and aluminum hydroxide is more preferable.
Preferably, the weight ratio of the DOPO derivative, the melamine salt compound and the metal hydroxide in the composite flame-retardant filler is (0.9-1.1): (2.7-2.9): (2.9-3.1), and may be, for example, 0.9:2.7:2.9, 1.0:2.8:3.0, 1.1:2.9:3.1, 0.9:2.8:3.0, 1.0:2.7:2.9, 1.1:2.8:3.0, 0.9:2.9:3.1, 1.0:2.9:3.1, 1.1:2.7:2.9, 0.9:2.7:3.0, 1.0:2.7:3.1, 1.1:2.9:2.9, 0.9:2.8:2.9, 1.0:2.8: 2.9, 1.8: 2.9: 1.9: 2.9, 1.9: 2.9:2.9, 1.9: 2.9:2.9, 1.9: 2.9:2.9, 1.9: 2.9, 1.9: 2.9:2.9, 1.9, and 1.9: 2.9.
Under the condition that the weight ratio of the DOPO derivative, the melamine salt compound and the metal hydroxide meets the above range, the composite flame-retardant filler can enable the DOPO derivative, the melamine salt compound and the metal hydroxide to better exert the synergistic effect of the DOPO derivative, the melamine salt compound and the metal hydroxide, improve the flame retardance, the dip soldering resistance and the heat resistance of a cured product and reduce the water absorption rate of the cured product.
Preferably, the curing agent is a composite curing agent comprising a phenol novolac resin, a vegetable oil-modified phenol resin and a brominated phenolic compound.
The composite curing agent is used, three components can be matched with each other, and the composite curing agent contains the linear phenolic resin, so that the composite curing agent has high reactivity and low water absorption rate, and is favorable for improving the heat resistance and the damp-heat resistance of a cured product. The toughness of the cured product can be effectively improved due to the vegetable oil modified phenolic resin; because of containing the brominated phenolic compounds, the brominated phenolic compounds participate in the curing reaction and simultaneously provide a large amount of bromine, thereby being beneficial to improving the flame retardance of cured products. The three components act synergistically to further improve the flame retardance, heat resistance and flexibility of a cured product and reduce water absorption.
Preferably, the weight ratio of the linear phenolic resin, the vegetable oil modified phenolic resin and the brominated phenolic compound in the composite curing agent is (0.9-1.1): (2.9-3.1): (3.3-3.5), and for example, the weight ratio may be 0.9:2.9:3.3, 1.0:3.0:3.4, 1.1:3.1:3.5, 0.9:3.0:3.4, 1.0:2.9:3.3, 1.1:3.0:3.4, 0.9:3.1:3.5, 1.0:3.1:3.5, 1.1:2.9: 3.3.3, 0.9:2.9:3.4, 1.0:3.0:3.3, 1.1: 3.4, 0.9:3.0:3.5, 1.9: 2.9:3.4, 1.0:3.0: 3.3.3.3, 1.1: 3.4, 1.9: 3.3.3: 3.5, 1.3.4: 3.3.3.4: 1.3.3.3: 1.4, 3.3.5, 1.9: 3.3.4: 3.3.3.5, 1.3.3: 1.3.4: 3.3.4, 1.3.3.3.3.3.4: 3.3.3.3.3.3.3: 1.4: 1.3.4: 1.4, etc.
In addition, the brominated phenolic compounds in the composite flame-retardant filler and the composite curing agent can play a role in the synergistic flame-retardant effect between the phosphorus/nitrogen/bromine flame retardant and the metal hydroxide flame retardant, so that the flame retardance is further improved, the non-antimonization flame retardance is realized, and the V-0 level is reached.
Preferably, the phenolic hydroxyl equivalent weight of the phenolic novolac resin is 100g/eq to 300g/eq, such as 100g/eq, 120g/eq, 150g/eq, 180g/eq, 200g/eq, 230g/eq, 250g/eq, 280g/eq, or 300 g/eq.
Preferably, the phenol novolac resin is any one of phenol novolac resin, bisphenol a novolac resin, o-cresol novolac resin, triphenol novolac resin, naphthalene novolac resin, biphenyl novolac resin, or dicyclopentadiene novolac resin, or a combination of at least two of them, preferably phenol novolac resin or o-cresol novolac resin, and more preferably phenol novolac resin.
Preferably, the phenolic resin has a phenolic hydroxyl group equivalent of 100g/eq to 130g/eq, such as 100g/eq, 105g/eq, 110g/eq, 115g/eq, 120g/eq, 125g/eq, or 130 g/eq.
Preferably, the phenolic hydroxyl equivalent of the vegetable oil modified phenolic resin is 100g/eq to 600g/eq, such as 100g/eq, 120g/eq, 150g/eq, 180g/eq, 200g/eq, 230g/eq, 250g/eq, 280g/eq, 300g/eq, 350g/eq, 380g/eq, 400g/eq, 420g/eq, 450g/eq, 480g/eq, 500g/eq, 550g/eq, 580g/eq, 600g/eq, and the like.
Preferably, the vegetable oil-modified phenolic resin is any one of or a combination of at least two of tung oil-modified phenolic resin, epoxy soybean oil-modified phenolic resin, cardanol-modified phenolic resin, linseed oil-modified phenolic resin and castor oil-modified phenolic resin, preferably tung oil-modified phenolic resin or cardanol-modified phenolic resin, and more preferably cardanol-modified phenolic resin.
Preferably, the phenolic hydroxyl equivalent of the cardanol modified phenolic resin is 120 g/eq-160 g/eq, such as 120g/eq, 125g/eq, 130g/eq, 135g/eq, 140g/eq, 145g/eq, 150g/eq, 155g/eq or 160 g/eq.
Preferably, the brominated phenolic compound is tetrabromobisphenol a or tribromophenol, and tetrabromobisphenol a is preferred because the former has better thermal stability and reactivity than the latter.
Preferably, the epoxy equivalent of the epoxy resin is 100g/eq to 350g/eq, such as 100g/eq, 130g/eq, 150g/eq, 180g/eq, 200g/eq, 230g/eq, 260g/eq, 280g/eq, 300g/eq, 330g/eq, or 350 g/eq.
Preferably, the epoxy resin has a relative molecular mass of 300 to 1000, such as 300, 350, 400, 500, 600, 700, 800, 900, 1000, and the like.
Preferably, the epoxy resin is any one of or a combination of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, o-cresol type novolac epoxy resin, phenol type novolac epoxy resin, biphenyl type novolac epoxy resin, or dicyclopentadiene type epoxy resin, preferably bisphenol a type epoxy resin or bisphenol F type epoxy resin, and more preferably bisphenol a type epoxy resin.
Preferably, the equivalent weight of the bisphenol A type epoxy resin is 160g/eq to 220g/eq, such as 160g/eq, 170g/eq, 180g/eq, 190g/eq, 200g/eq, 210g/eq, or 220 g/eq.
Preferably, the bisphenol A epoxy resin is a low molecular weight epoxy resin with the relative molecular mass of 350-650, such as 350, 400, 450, 500, 550, 600 or 650.
In the invention, bisphenol A epoxy resin is used as main resin to participate in crosslinking and curing reaction, and the epoxy resin with proper epoxy equivalent and molecular weight is selected, thus being beneficial to improving the permeability of the wood pulp paper.
Preferably, the composite flame retardant filler is contained in the thermosetting resin composition in an amount of 30 to 45 parts by weight, for example, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight or 45 parts by weight, based on 100 parts by weight of the epoxy resin.
Preferably, the curing agent is contained in the thermosetting resin composition in an amount of 65 to 85 parts by weight, for example, 65 parts by weight, 68 parts by weight, 70 parts by weight, 73 parts by weight, 75 parts by weight, 78 parts by weight, 80 parts by weight, 83 parts by weight or 85 parts by weight, based on 100 parts by weight of the epoxy resin.
Preferably, the curing accelerator is contained in the thermosetting resin composition in an amount of 0.1 to 0.8 parts by weight, for example, 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, or 0.8 part by weight based on 100 parts by weight of the epoxy resin.
Preferably, the curing accelerator is any one of tertiary amine, tertiary phosphine, organic metal complex, quaternary ammonium salt or imidazole compound or the combination of at least two of the tertiary amine, the tertiary phosphine, the organic metal complex, the quaternary ammonium salt and the imidazole compound.
Preferably, the imidazole compound is any one or a mixture of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole or 1-cyanoethyl-2-methylimidazole.
In the invention, the addition amount of the curing accelerator is not too large, which can cause the resin composition to react too fast, the byproducts to be too large, the performance of the cured product to be reduced and the manufacturability to be poor; if the amount of the curing accelerator is too small, the reaction is too slow, which is not favorable for the production of prepregs and affects the production efficiency, so the gelation time of the glue is preferably controlled to be 100-200 s.
In another aspect, the present invention provides a resin solution obtained by dissolving or dispersing the thermosetting resin composition described above in a solvent.
Preferably, the solvent is a solvent having a boiling point of 50 ℃ to 180 ℃. The boiling point of the solvent is matched with the semi-curing processing temperature of the paper-based bonding sheet, so that the solvent removal requirement in the semi-curing stage is met, and meanwhile, the solvent meets the permeability of the paper base and the compatibility with resin.
Preferably, the solvent is any one of methanol, ethanol, acetone, butanone, ethylene glycol monobutyl ether, methyl acetate, ethyl acetate or cyclohexanone or a mixture of at least two of the methanol, the ethanol, the acetone, the butanone, the ethylene glycol monobutyl ether, the methyl acetate, the ethyl acetate and the cyclohexanone.
Preferably, the solid content of the resin cement is 60% to 80%, for example, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78% or 80%, particularly preferably 68% to 78%, and the resin cement having the solid content in this range can improve the permeability of the reinforcing material, and can obtain a prepreg having a highly uniform resin layer thickness.
In another aspect, the present invention provides a prepreg comprising a reinforcing material and the thermosetting resin composition as described above attached thereto by impregnation drying.
Preferably, the reinforcing material is wood pulp paper or cotton pulp paper.
In another aspect, the present invention provides a laminate comprising at least one prepreg as described above.
In another aspect, the present invention provides a metal-clad laminate comprising at least one prepreg as described above and a metal foil clad on one or both sides of the stacked prepreg.
In another aspect, the present invention provides a printed circuit board comprising a laminate or metal-foil-clad laminate as described above.
Compared with the prior art, the invention has the following beneficial effects:
(1) by utilizing the cooperation and synergistic effect of the DOPO derivative, the melamine salt compound and the metal hydroxide in the composite flame-retardant filler, the flame retardance of a cured product can be effectively improved, and the cured product has good heat resistance and dip soldering resistance and low water absorption.
(2) According to the invention, the brominated phenolic compound in the composite flame-retardant filler and the composite curing agent is used as a flame retardant, so that the synergistic flame-retardant effect between a phosphorus/nitrogen/bromine flame retardant and a metal hydroxide flame retardant can be exerted, the antimonization-free flame retardance is realized, the flame retardance reaches UL94V-0 level, and the limit requirement of international environmental regulations on antimony compounds is met, and the resin composition can enable a cured product of the resin composition to have the advantages of good heat resistance, dip-soldering resistance, low water absorption rate and the like, wherein T260 can reach 28-40 min, the dip-soldering resistance at 288 ℃ can reach 108-132 s, the water absorption rate is as low as below 0.11%, and the bending strength is as high as above 340 MPa.
(3) The CEM-1 copper clad laminate prepared by the thermosetting resin composition has the flame retardance reaching UL94V-0 grade requirement, meanwhile, the dip-soldering resistance at 288 ℃ is improved to 108-132 s, compared with a bromine-antimony synergistic system, the dip-soldering resistance is improved by 25-38%, the water absorption is reduced to 0.08-0.11%, and compared with the bromine-antimony synergistic system, the dip-soldering resistance is reduced by 21-42%; the T260 is increased to 28-40 min, and is increased by 17-42% compared with a bromine-antimony synergistic system. Therefore, the antimony-free CEM-1 copper-clad laminate has outstanding comprehensive performance advantages of excellent heat resistance, dip soldering resistance, low water absorption rate and the like while ensuring flame retardance.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The specific components and component contents (in parts by weight) of the resin compositions of examples 1 to 14 and comparative examples 1 to 14 are shown in tables 1 and 2.
TABLE 1 examples 1-14 resin compositions specific components and component amounts
TABLE 2 concrete components and component contents of resin compositions of comparative examples 1 to 14
The code numbers of the components and the corresponding component names in tables 1 and 2 are as follows:
a: epoxy resin:
a-1 bisphenol A type epoxy resin with the epoxy equivalent of 180g/eq and the molecular weight of 350;
a-2 bisphenol A epoxy resin with the epoxy equivalent of 190g/eq and the molecular weight of 450;
a-3 phenol novolac epoxy resin having an epoxy equivalent of 215g/eq and a molecular weight of 600;
a-4 o-cresol novolac epoxy resin with epoxy equivalent of 180g/eq and molecular weight of 600;
b: curing agent:
b-1 a phenol-type linear phenol resin having a phenolic hydroxyl group equivalent of 105 g/eq;
b-2 phenol-type linear phenolic resin with 120g/eq of phenolic hydroxyl equivalent;
b-3, cardanol modified phenolic resin with 130g/eq of phenolic hydroxyl equivalent;
b-4 cardanol modified phenolic resin with 145g/eq of phenolic hydroxyl equivalent;
b-5 tetrabromobisphenol A;
b-6: tribromophenol;
c: curing accelerator: 2-methylimidazole;
d: flame-retardant filler:
d-1: DOPO derivatives of formula (2) (SPDO-3000, supplier: Huaian Innovative materials science and technology Co., Ltd.);
d-1': DOPO having a structure represented by formula (3) disclosed in paragraph 0084 of specification CN104086593B
Derivative (A):
d-1': DOPO having the structure of formula (4) disclosed in CN104086593B in paragraph 0081
Derivative (A):
d-1': DOPO having the structure of formula (5) disclosed in CN104086593B, paragraph 0095
Derivative (A):
d-2: melamine cyanurate (trade name: XS-MC-151, supplier: Asahon non-halogen Smoke Elimination flame retardant Co., Ltd.);
d-2': melamine polyphosphate (brand: SX-MPP, supplier: Asahon non-halogen Smoke Elimination flame retardant Co., Ltd.);
d-3: aluminum hydroxide;
e: DOPO-based phenolic resins (JFH-23101P60, supplier: Suzhou Kyoho New materials science and technology Co., Ltd.);
f: trishydroxyethyl isocyanurate;
g: antimony trioxide;
the method for producing the copper clad laminate using the resin compositions of examples 1 to 14 and comparative examples 1 to 14 was as follows:
adding epoxy resin, composite curing agent (phenol type linear phenolic resin, cardanol modified phenolic resin and tetrabromobisphenol A) and curing accelerator into a container according to a proportion, stirring to mix uniformly, adding composite flame-retardant filler according to the proportion, stirring uniformly by using a high-speed dispersion machine, and finally adjusting the solid content of the solution to 76% by using a solvent to prepare a glue solution.
The prepared resin composition glue solution is soaked by using wood pulp paper or cotton pulp paper special for CEM-1, a core material prepreg is prepared by drying in an oven, the core material prepreg is overlapped in a plurality of sheets, a fabric prepreg is matched at the outer side of the lamination, copper foil is arranged at one side or two sides of the outer side of the fabric prepreg, the process condition of the hot press forming process is not particularly limited, and the copper clad laminate with the thickness of 1.6mm is generally prepared by hot pressing at the temperature of 165 ℃ and the pressure of 8MPa for 60 min.
The copper clad laminate prepared as described above was tested for flame retardancy, solder dip resistance at 288 ℃, water absorption, T260, and flexural strength, and the test results are shown in tables 3 and 4.
The performance test methods are as follows:
a: flame retardancy: the test was carried out according to the UL-94 standard.
B: solder dip resistance at 288 ℃: the substrate was immersed in a tin furnace at 288 ℃ and the corresponding time was recorded when blistering or delamination of the substrate occurred.
C: water absorption: the measurement was carried out by IPC-TM-6502.6.2.1 method.
D: t260: it is the time before the delamination of the sheet at the set temperature of 260 c due to the action of heat.
E: bending strength: the measurement was carried out according to the IPC-TM-6502.4.4B method.
TABLE 3 test results of copper clad laminates
TABLE 4 test results of copper clad laminates
The following points can be obtained from tables 3 and 4:
from the test results, it can be seen that in examples 1 to 14, the composite flame retardant filler and the brominated phenolic compound are used as the flame retardant, so that the synergistic flame retardant effect between the phosphorus/nitrogen/bromine flame retardant and the metal hydroxide flame retardant can be exerted, the antimoneless flame retardant is realized, when the resin composition consisting of the flame retardant, the epoxy resin and the composite curing agent is cured, the flame retardant has good heat resistance, dip soldering resistance and low water absorption rate, wherein the T260 can reach 28 to 40min, the dip soldering resistance at 288 ℃ can reach 108 to 132s, the water absorption rate is as low as below 0.11%, the bending strength is as high as above 340Mpa, and the flame retardant requirement of UL94V-0 level is also met.
In comparative example 1, when the DOPO derivative (SPDO-3000) alone was used as a flame retardant, the flame retardant effect was not significant even if the amount of addition was increased, and the water absorption of the cured product was increased and the heat resistance was greatly reduced due to the high phosphorus content, as compared with example 1; in comparative example 2, when melamine cyanurate (XS-MC-151) was used alone as a flame retardant, V-0 flame retardancy could not be satisfied even with a large amount of addition; in comparative example 3, when aluminum hydroxide alone was used as a flame retardant, the V-0 flame retardancy could not be satisfied even with a large amount of addition, and the increase in the rigidity of the cured product due to the high content of the inorganic filler affects the machinability; in comparative example 4, the V-0 flame retardance was not satisfied even when only the composite flame retardant filler was used as the flame retardant without using tetrabromobisphenol A.
In comparative example 5, the DPOP-based phenol resin (JFH-23101P60) was used in place of the DOPO derivative (SPDO-3000) of the formula (2) in an equal amount, and the cured product was inferior in all properties to example 4; in comparative example 6, when trishydroxyethyl isocyanurate was used in place of melamine cyanurate (XS-MC-151) in an equal amount, the cured product was degraded in various properties.
In comparative example 7, when the phenol type phenol novolac resin alone was used as the curing agent, the cured product cross-linking density was improved, the heat resistance was improved, and the rigidity was increased, as compared with example 3, but the V-0 flame retardant requirement could not be satisfied; in comparative example 8, when the cardanol modified phenolic resin is used alone as the curing agent, the toughness of the cured product is improved due to the high content of the toughening component, so that the mechanical processability is facilitated, but the V-0 grade flame retardant requirement cannot be met; in comparative example 9, when tetrabromobisphenol A alone was used as a curing agent, the cured product was excellent in flame retardancy, but the bromine content was too high, which decreased the crosslinking density of the cured product and deteriorated the heat resistance.
Compared with the embodiment 1, in the comparative example 10, the weight of the DOPO derivative (SPDO-3000) in the composite flame-retardant filler is less, so that the phosphorus content of the system is reduced, and the V-0 grade flame-retardant requirement cannot be met; in comparative example 11, the composite flame-retardant filler contained less melamine cyanurate (XS-MC-151) and more aluminum hydroxide, which still failed to satisfy the V-0 flame-retardant requirement, and the cured product had a lower heat resistance and an increased rigidity; in comparative example 12, since the weight ratio of the phenol type linear phenol resin in the composite curing agent was small, the crosslinking density of the cured product was decreased and the heat resistance was deteriorated; in comparative example 13, the weight ratio of the cardanol-modified phenol resin in the composite curing agent was small, and as a result, the cured product rigidity increased, and the machinability deteriorated; in comparative example 14, tetrabromobisphenol A and antimony trioxide were used as flame retardants, and the flame retardant satisfied V-0 flame retardancy, but did not satisfy the requirement of no antimonization, and were inferior in heat resistance and solder dip resistance.
Therefore, the flame retardance of the CEM-1 copper clad laminate prepared by the thermosetting resin composition reaches UL94V-0 level requirement, meanwhile, the dip-soldering resistance at 288 ℃ is improved to 108-132 s, compared with a bromine-antimony synergistic system, the dip-soldering resistance is improved by 25-38%, the water absorption is reduced to 0.08-0.11%, and compared with the bromine-antimony synergistic system, the dip-soldering resistance is reduced by 21-42%; the T260 is increased to 28-40 min, and is increased by 17-42% compared with a bromine-antimony synergistic system. Therefore, the antimony-free CEM-1 copper-clad laminate has outstanding comprehensive performance advantages of high heat resistance, dip soldering resistance, low water absorption rate and the like while ensuring flame retardance.
The applicant states that the thermosetting resin composition, the prepreg, the laminate and the printed circuit board using the same of the present invention are described by the above examples, but the present invention is not limited to the above examples, that is, the present invention is not limited to the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (43)
1. A thermosetting resin composition, characterized in that the thermosetting resin composition comprises an epoxy resin, a curing agent, a curing accelerator and a composite flame-retardant filler;
the composite flame-retardant filler comprises a DOPO derivative, a melamine salt compound and a metal hydroxide;
the DOPO derivative has a structure represented by the following formula (1):
wherein R is any one of substituted or unsubstituted alkylene of C2-C18 or substituted or unsubstituted arylene of C6-C12;
the weight ratio of the DOPO derivative to the melamine salt compound to the metal hydroxide in the composite flame-retardant filler is (0.9-1.1) to (2.7-2.9) to (2.9-3.1);
the curing agent is a composite curing agent and comprises linear phenolic resin, vegetable oil modified phenolic resin and brominated phenolic compounds;
the weight ratio of the linear phenolic resin, the vegetable oil modified phenolic resin and the brominated phenolic compound in the composite curing agent is (0.9-1.1): (2.9-3.1): (3.3-3.5).
2. The thermosetting resin composition of claim 1, wherein R is a substituted or unsubstituted alkylene group having from C2 to C5.
3. The thermosetting resin composition of claim 1, wherein when R has a substituent, the substituent is selected from phenyl, naphthyl or C1-C4 alkyl.
4. The thermosetting resin composition according to claim 1, wherein the DOPO derivative represented by the formula (1) is any one of the following formulae (2), (3), (4) or (5):
5. the thermosetting resin composition according to claim 4, wherein the DOPO derivative represented by the formula (1) is a DOPO derivative represented by the formula (2).
6. The thermosetting resin composition of claim 1, wherein the melamine salt compound is any one of melamine polyphosphate, melamine cyanurate, or melamine borate, or a combination of at least two thereof.
7. The thermosetting resin composition of claim 6, wherein the melamine salt compound is melamine cyanurate.
8. The thermosetting resin composition claimed in claim 1, wherein the metal hydroxide is magnesium hydroxide or aluminum hydroxide.
9. The thermosetting resin composition claimed in claim 8, wherein the metal hydroxide is aluminum hydroxide.
10. The thermosetting resin composition according to claim 1, wherein the phenolic novolac resin has a phenolic hydroxyl group equivalent of 100 to 300 g/eq.
11. The thermosetting resin composition claimed in claim 1, wherein the phenol novolac resin is any one of phenol-type phenol-formaldehyde resin, bisphenol a-type phenol-formaldehyde resin, o-cresol-type phenol-formaldehyde resin, triphenol phenol-formaldehyde resin, naphthalene phenol-formaldehyde resin, biphenyl phenol-formaldehyde resin or dicyclopentadiene phenol-formaldehyde resin or a combination of at least two thereof.
12. The thermosetting resin composition claimed in claim 11, wherein the phenol novolac resin is a phenol-type phenol-formaldehyde resin or an o-cresol-type phenol-formaldehyde resin.
13. The thermosetting resin composition claimed in claim 1, wherein the phenol novolac resin is a phenol-type phenol resin.
14. The thermosetting resin composition claimed in claim 13, wherein the phenolic phenol resin has a phenolic hydroxyl group equivalent of 100 to 130 g/eq.
15. The thermosetting resin composition according to claim 1, wherein the vegetable oil-modified phenol resin has a phenolic hydroxyl group equivalent of 100 to 600 g/eq.
16. The thermosetting resin composition of claim 1, wherein the vegetable oil-modified phenolic resin is any one of or a combination of at least two of tung oil-modified phenolic resin, epoxy soybean oil-modified phenolic resin, cardanol-modified phenolic resin, linseed oil-modified phenolic resin, and castor oil-modified phenolic resin.
17. The thermosetting resin composition claimed in claim 1, wherein the vegetable oil-modified phenol resin is a tung oil-modified phenol resin or a cardanol-modified phenol resin.
18. The thermosetting resin composition claimed in claim 1, wherein the vegetable oil-modified phenol resin is a cardanol-modified phenol resin.
19. The thermosetting resin composition of claim 18, wherein the cardanol-modified phenolic resin has a phenolic hydroxyl group equivalent of 120-160 g/eq.
20. The thermosetting resin composition of claim 1, wherein the brominated phenolic compound is tetrabromobisphenol a or tribromophenol.
21. The thermosetting resin composition of claim 20, wherein the brominated phenolic compound is tetrabromobisphenol a.
22. The thermosetting resin composition according to claim 1, wherein the epoxy equivalent of the epoxy resin is 100 to 350 g/eq.
23. The thermosetting resin composition according to claim 1, wherein the epoxy resin has a relative molecular mass of 300 to 1000.
24. The thermosetting resin composition claimed in claim 1, wherein the epoxy resin is any one of or a combination of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, o-cresol type novolac epoxy resin, phenol type novolac epoxy resin, biphenyl type novolac epoxy resin, or dicyclopentadiene type epoxy resin.
25. The thermosetting resin composition of claim 24, wherein the epoxy resin is a bisphenol a type epoxy resin or a bisphenol F type epoxy resin.
26. The thermosetting resin composition of claim 25, wherein the epoxy resin is a bisphenol a type epoxy resin.
27. The thermosetting resin composition of claim 25, wherein the epoxy resin is the bisphenol a epoxy resin and has an epoxy equivalent of 160g/eq to 220 g/eq.
28. The thermosetting resin composition claimed in claim 25, wherein the epoxy resin is a low molecular weight epoxy resin having a relative molecular mass of 350 to 650 of the bisphenol a type epoxy resin.
29. The thermosetting resin composition according to claim 1, wherein the composite flame retardant filler is contained in an amount of 30 to 45 parts by weight based on 100 parts by weight of the epoxy resin in the thermosetting resin composition.
30. The thermosetting resin composition according to claim 1, wherein the curing agent is contained in an amount of 65 to 85 parts by weight based on 100 parts by weight of the epoxy resin.
31. The thermosetting resin composition according to claim 1, wherein the curing accelerator is contained in an amount of 0.1 to 0.8 part by weight based on 100 parts by weight of the epoxy resin in the thermosetting resin composition.
32. The thermosetting resin composition claimed in claim 1, wherein the curing accelerator is any one of or a combination of at least two of tertiary amine, tertiary phosphine, organometallic complex, quaternary ammonium salt or imidazole compound.
33. The thermosetting resin composition of claim 32, wherein the imidazole-based compound is any one or a mixture of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 1-cyanoethyl-2-methylimidazole.
34. A resin cement obtained by dissolving or dispersing the thermosetting resin composition according to any one of claims 1 to 33 in a solvent.
35. The resin glue solution of claim 34, wherein the solvent is a solvent with a boiling point of 50 ℃ to 180 ℃.
36. The resin glue solution of claim 34, wherein the solvent is any one of methanol, ethanol, acetone, butanone, ethylene glycol monobutyl ether, methyl acetate, ethyl acetate or cyclohexanone, or a mixture of at least two of the above.
37. The resin cement according to claim 34, wherein the solid content of the resin cement is 60-80%.
38. The resin cement according to claim 37, wherein the solid content of the resin cement is 68-78%.
39. A prepreg comprising a reinforcing material and the thermosetting resin composition according to any one of claims 1 to 33 attached thereto by impregnation drying.
40. The prepreg of claim 39, in which the reinforcing material is wood pulp paper or cotton pulp paper.
41. A laminate comprising at least one prepreg according to claim 39 or 40.
42. A metal-clad laminate comprising at least one prepreg according to claim 39 or 40 and a metal foil clad on one or both sides of the laminated prepreg.
43. A printed circuit board comprising the laminate of claim 41 or the metal foil-clad laminate of claim 42.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911205625.0A CN110845706B (en) | 2019-11-29 | 2019-11-29 | Thermosetting resin composition, prepreg using same, laminated board and printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911205625.0A CN110845706B (en) | 2019-11-29 | 2019-11-29 | Thermosetting resin composition, prepreg using same, laminated board and printed circuit board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110845706A CN110845706A (en) | 2020-02-28 |
| CN110845706B true CN110845706B (en) | 2022-06-24 |
Family
ID=69606634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911205625.0A Active CN110845706B (en) | 2019-11-29 | 2019-11-29 | Thermosetting resin composition, prepreg using same, laminated board and printed circuit board |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110845706B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667266A (en) * | 2021-09-10 | 2021-11-19 | 四川玄武岩纤维新材料研究院(创新中心) | Thermosetting resin flame-retardant composition and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120055705A1 (en) * | 2009-05-19 | 2012-03-08 | Albemarle Corporation | Dopo-derived flame retardant and epoxy resin composition |
| CN104086593A (en) * | 2014-07-14 | 2014-10-08 | 中国科学院宁波材料技术与工程研究所 | DOPO derivatives as well as preparation method and application thereof |
| CN104371273A (en) * | 2014-11-11 | 2015-02-25 | 广东生益科技股份有限公司 | Halogen-free resin composition and prepreg and laminate prepared therefrom |
| CN107383776A (en) * | 2016-05-16 | 2017-11-24 | 广东广山新材料股份有限公司 | A kind of bromine phosphorus synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate |
| CN109354827A (en) * | 2018-09-30 | 2019-02-19 | 陕西生益科技有限公司 | It is a kind of have halogen without antimony resin combination, using its prepreg, laminate and printed circuit board |
-
2019
- 2019-11-29 CN CN201911205625.0A patent/CN110845706B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120055705A1 (en) * | 2009-05-19 | 2012-03-08 | Albemarle Corporation | Dopo-derived flame retardant and epoxy resin composition |
| CN104086593A (en) * | 2014-07-14 | 2014-10-08 | 中国科学院宁波材料技术与工程研究所 | DOPO derivatives as well as preparation method and application thereof |
| CN104371273A (en) * | 2014-11-11 | 2015-02-25 | 广东生益科技股份有限公司 | Halogen-free resin composition and prepreg and laminate prepared therefrom |
| CN107383776A (en) * | 2016-05-16 | 2017-11-24 | 广东广山新材料股份有限公司 | A kind of bromine phosphorus synergistic fire-proof resin composition, compositions of thermosetting resin, pre-impregnated sheet and composite metal substrate |
| CN109354827A (en) * | 2018-09-30 | 2019-02-19 | 陕西生益科技有限公司 | It is a kind of have halogen without antimony resin combination, using its prepreg, laminate and printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110845706A (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102181143B (en) | High-frequency thermosetting resin composition, prepreg and laminated sheet | |
| EP1948735B1 (en) | Flame retardant prepregs and laminates for printed circuit boards | |
| CN110951216B (en) | Thermosetting resin composition, and prepreg and laminated board using same | |
| CN102051026B (en) | Halogen-free flame-retardant epoxy resin composition and application thereof | |
| CN102174242B (en) | Halogen-free resin composition and prepreg and laminated board made of same | |
| KR101849833B1 (en) | Epoxy resin composition, and, prepreg and copper clad laminate manufactured using the composition | |
| US20180022899A1 (en) | Flame retardant resin composition, thermosetting resin composition, composite metal substrate and flame retardant electronic material | |
| KR101830539B1 (en) | Flame retardant resin composition, the thermosetting resin compositions, prepreg and composite metal substrate | |
| CN101906239A (en) | Halogen-free flame-retardant resin composition and application thereof in manufacturing copper-clad plate | |
| CN105482452A (en) | Halogen-free resin composition as well as prepreg, laminated board and printed circuit board containing halogen-free resin composition | |
| CN104109347A (en) | Halogen-free thermosetting resin composition, prepreg and laminated plate | |
| CN109354827B (en) | Halogen-containing antimony-free resin composition, prepreg using same, laminated board and printed circuit board | |
| CN109233209B (en) | Halogen-containing antimony-free resin composition, prepreg using same, laminated board and printed circuit board | |
| CN109438677B (en) | Composite curing agent, resin composition containing composite curing agent, prepreg and laminated board | |
| CN109608828B (en) | Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same | |
| CN105801814B (en) | A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits | |
| CN110845706B (en) | Thermosetting resin composition, prepreg using same, laminated board and printed circuit board | |
| CN103965588A (en) | Halogen-free thermosetting resin composition, prepreg and laminated board | |
| KR101898365B1 (en) | A halogen-free thermosetting resin composition, and a prepreg and a laminate used for printed circuit using the same | |
| CN111806001A (en) | Preparation method of dip-soldering-resistant high-flexibility CEM-1 copper-clad plate | |
| US9963590B2 (en) | Halogen-free resin composition, and a prepreg and a laminate used for printed circuit using the same | |
| CN108192281B (en) | Halogen-free thermosetting resin composition, and prepreg, laminated board, metal foil-clad laminated board and printed circuit board using same | |
| CN108047647B (en) | Halogen-free thermosetting resin composition, and prepreg, laminated board, metal foil-clad laminated board and printed circuit board using same | |
| WO2003042291A1 (en) | Halogen-free phosphorous- and nitrogen-containing flame-resistant epoxy resin compositions, and prepregs derived from thereof | |
| CN109306149B (en) | Halogen-containing antimony-free resin composition, prepreg using same, laminated board and printed circuit board |
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 |