WO2012083728A1 - 无卤树脂组合物及使用其的无卤覆铜板的制作方法 - Google Patents

无卤树脂组合物及使用其的无卤覆铜板的制作方法 Download PDF

Info

Publication number
WO2012083728A1
WO2012083728A1 PCT/CN2011/079308 CN2011079308W WO2012083728A1 WO 2012083728 A1 WO2012083728 A1 WO 2012083728A1 CN 2011079308 W CN2011079308 W CN 2011079308W WO 2012083728 A1 WO2012083728 A1 WO 2012083728A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
parts
halogen
resin
free
Prior art date
Application number
PCT/CN2011/079308
Other languages
English (en)
French (fr)
Inventor
何岳山
苏世国
Original Assignee
广东生益科技股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to EP11851266.4A priority Critical patent/EP2657296A4/en
Priority to US13/997,542 priority patent/US9076573B2/en
Priority to KR1020137019505A priority patent/KR101508083B1/ko
Publication of WO2012083728A1 publication Critical patent/WO2012083728A1/zh

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes 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
    • B32B15/04—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
    • B32B15/14—Layered products comprising a layer of metal next to a 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • 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
    • 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
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
    • H01B19/04—Treating the surfaces, e.g. applying coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • 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
    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1052—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing
    • Y10T156/1062—Prior to assembly

Definitions

  • Halogen-free resin composition and method for producing halogen-free copper-clad laminate using the same
  • the present invention relates to the field of copper clad laminates, and more particularly to a resin-free composition and a method for producing a halogen-free copper clad laminate using the same. Background technique
  • a copper-clad laminate of a halide or a bismuth compound When a copper-clad laminate of a halide or a bismuth compound is burned, it not only emits a large amount of smoke, but also emits a toxic smell, and emits a highly toxic and corrosive hydrogen-hydrogen gas, which not only pollutes the environment but also endangers human health;
  • a phosphorus-containing resin to achieve a flame retardant effect, such as an epoxy resin containing a phosphorus-containing phenanthrene compound DOPO or ODOBP, or another epoxy resin containing a phosphorus-containing resin such as a phosphazene chloride, but the plate after soaking
  • a phosphorus-containing resin to achieve a flame retardant effect, such as an epoxy resin containing a phosphorus-containing phenanthrene compound DOPO or ODOBP, or another epoxy resin containing a phosphorus-containing resin such as a phosphazene chloride, but the plate
  • Cide ZL200410051855.3 uses a resin containing dihydrobenzoxazine to improve the phosphorus-containing epoxy resin to improve heat resistance, chemical resistance, and water absorption, but has dihydrobenzoxazine.
  • the resin is difficult to meet the flame retardancy standard of V-0 in UL94, and it is very brittle. It is difficult to meet the processing requirements of printed circuit boards.
  • the curing temperature of dihydrobenzoxazine itself is very high, and it is required to reach about 200 degrees Celsius. The board is difficult to cure completely.
  • Patent CN1333014C has the technology of directly filling the above system with macromolecular polyphenylene ether.
  • the technique is actually difficult to achieve the desired effect.
  • the reason is that the filling process of the organic macromolecular filler is difficult, the rubber is difficult to be glued, and it is difficult to disperse evenly.
  • Only when the polyphenylene ether molecules are crosslinked to the polymer can the polymer be effectively toughened and a slight decrease in dielectric constant and dielectric loss is brought about.
  • the polyphenylene ether structure itself is flame retardant, but its flame resistance is greatly reduced due to the introduction of reactive groups and a decrease in molecular weight. Summary of the invention
  • An object of the present invention is to provide a resin-free composition which has excellent heat resistance, moisture resistance and low dielectric loss.
  • Another object of the present invention is to provide a halogen-free copper-clad using the above halogen-free resin composition.
  • the manufacturing method of the board, the operation of the cylinder, the obtained halogen-free copper-clad board meets the requirements of halogen-free, and has the advantages of excellent heat resistance, moisture resistance and low dielectric loss.
  • the present invention provides a resin-free composition
  • a resin-free composition comprising a component and its parts by weight as follows: a reactive small molecule polyphenylene ether having a number average molecular weight of 500 to 3000, 5 to 30 parts by weight, polybenzazole 5 to 50 parts by weight of the azine resin, 15 to 65 parts by weight of the phosphorus-containing epoxy resin, 1 to 25 parts by weight of the composite curing agent, 0 to 5 parts by weight of the curing accelerator, 0 to 100 parts by weight of the filler, and benzene or ketone
  • the amount of solvent is appropriate.
  • the amount of each component is calculated based on 100 parts by weight of the total organic solids.
  • Y is selected from:
  • X is an alkyl group, a 0
  • Ri, R 2 , R 7 , R 8 , R 9 , R 10 , R u , R 15 and R 16 are the same or different alkyl or phenyl groups having 6 or less carbon atoms, R 3 , R 5 , R 6.
  • R 12 , R 13 and R 14 are the same or different hydrogen atoms or an alkyl group or a phenyl group having 6 or less carbon atoms.
  • the benzoxazine resin includes one or more of the following structures:
  • R 2 and R 3 are monosubstituted or polysubstituted, and R 2 and R 3 are hydrogen, methyl, allyl, alkynyl
  • R 4 and R 5 are each independently and are allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C8-alkyl, unsubstituted or substituted C1-C8-cycloalkyl.
  • the base epoxy resin in the phosphorus-containing epoxy resin is a difunctional epoxy resin, a polyfunctional epoxy resin or a mixture of the two, and the phosphorus content is 2 to 5%, and the epoxy equivalent is 200 to 600 g/mol.
  • the content of the elemental element in the composition of the glue solution is within the range of JPCA without standard, that is, controlled to be less than 0.09 parts by weight, thereby achieving better environmental protection.
  • the phosphorus-containing oxy-resin is preferably 25-55 parts by weight.
  • the composite curing agent is selected from one or more of dicyandiamide, an aromatic amine, an acid anhydride, a phenolic compound, and a phosphorus-containing aldehyde.
  • the curing accelerator is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, DMP-30 (2,4,6-tris(dimethylaminomethyl)phenol) And one or more of hexamethylenetetramine.
  • the filler is an organic or inorganic filler, and the inorganic filler is selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zeolite, wollastonite, silica, magnesia, calcium silicate, carbonate 4, clay, talc and mica.
  • the inorganic filler may be appropriately dose-adjusted according to the purpose of use, and the amount thereof is 100 parts by weight based on the total amount of the organic solids of the components in the composition of the above-mentioned glue, and is 0-100 parts by weight. Preferably, it is preferably 25-100 parts by weight.
  • the present invention also provides a method for producing a halogen-free copper-clad laminate using the above halogen-free resin composition, comprising the steps as follows:
  • Step 1 Take 5 ⁇ 30 parts by weight of reactive small molecule polyphenylene ether with a number average molecular weight of 500 ⁇ 3000, dissolve in a solvent such as benzene or ketone, and add polybenzophenone after completely dissolved at normal temperature or medium temperature. 5 to 50 parts by weight of the azine resin, stirred and mixed to prepare a standby solution;
  • Step 2 taking 15 to 65 parts by weight of the phosphorus-containing epoxy resin, 1 to 25 parts by weight of the composite curing agent, 0 to 5 parts by weight of the curing accelerator, and 0 to 100 parts by weight of the filler, and adding to the above-mentioned standby solution, stirring Get the glue;
  • Step 3 selecting a flat surface E-glass cloth, uniformly coating the prepared glue solution, and baking into a B-stage prepreg;
  • Step 4 According to the size of the press, the B-stage prepreg is cut into suitable sizes, stacked neatly, and a piece of copper foil is placed on the upper and lower sides, and placed in a vacuum hot press for pressing to obtain a copper-free board.
  • the medium temperature mentioned in step 1 refers to 30 ⁇ 80 °C.
  • the baking temperature is set according to the boiling point of the solvent used in the glue, and the baking temperature is generally 85 to 175 ° C, and the time is generally 5 to 20 minutes.
  • the pressing process adopts a stepwise pressing (step heating and boosting) method, and the specific steps are as follows: 15 min from room temperature to 150 ° C for 30 min, then 5 min to 180 ° C for 2 hr, last 30 min. Cool down room temperature; pressure lmin rises from zero to 0.6Mpa, hold pressure for 20min, then lmin rises to l.OMpa, hold pressure for 2.5hr; post-treatment conditions are 200 ⁇ 245 °C for 0 ⁇ 5hr.
  • the invention has the beneficial effects of: the method for manufacturing the halogen-free copper-clad board of the invention, operating the cylinder, and the obtained copper-free board has the advantages of excellent heat resistance, moisture resistance and low dielectric loss, and punching of the sheet Good processability, halogen content can meet the V-0 standard of the flame retardancy test UL-94 within the requirements of the JPCA halogen-free standard.
  • FIG. 1 is a flow chart of a method for fabricating a halogen-free copper clad laminate of the present invention. detailed description
  • the resin-free composition of the present invention is calculated based on 100 parts by weight of the total organic solids, and includes components and parts by weight thereof as follows: 5 to 30 parts by weight of reactive small molecule polyphenylene ether having a number average molecular weight of 500 to 3,000 5 to 50 parts by weight of the polybenzoxazine resin, 15 to 65 parts by weight of the phosphorus-containing epoxy resin, 1 to 25 parts by weight of the composite curing agent, 0 to 5 parts by weight of the curing accelerator, 0 to 100 parts by weight of the filler, and A suitable amount of benzene or ketone solvent.
  • the halogen-free resin composition is used for producing a halogen-free copper-clad laminate, and the obtained copper-free copper sheet satisfies the requirement of no heat resistance, moisture resistance, and low dielectric loss.
  • Y is selected from:
  • X is an alkyl group
  • Ri, R 2 , R 7 , R 8 , R 9 , R 10 , R u , R 15 and R 16 are the same or different alkyl or phenyl groups having 6 or less carbon atoms, R 3 , R 5 , R 6, R 12, R 13, R 14 are the same or different, a hydrogen atom or a carbon atom in the 6 alkyl or phenyl or less.
  • the polybenzoxazine resin includes one or more of the following structures:
  • R 2 and R 3 are monosubstituted or polysubstituted, and R 2 and R 3 are hydrogen, methyl, allyl, alkynyl
  • R 4 and R 5 are each independently and are allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C1-C8-alkyl, unsubstituted or substituted C1-C8-cycloalkyl.
  • the base epoxy resin in the phosphorus-containing epoxy resin is a difunctional epoxy resin, a polyfunctional epoxy resin or a mixture of the two, and the phosphorus content is 2 to 5%, and the epoxy equivalent is 200 to 600 g/mol.
  • the content of the elemental element in the composition of the glue solution is within the range of JPCA without standard, that is, controlled to be less than 0.09 parts by weight, thereby achieving better environmental protection.
  • the phosphorus-containing oxy-resin is preferably 25-55 parts by weight.
  • the composite curing agent is selected from one or more of dicyandiamide, an aromatic amine, an acid anhydride, a phenolic compound, and a phosphorus-containing phenolic aldehyde.
  • the curing accelerator is selected from the group consisting of 2-methylimidazole and 2-ethyl-4-methylimidine One or more of azole, 2-phenylimidazole, DMP-30 (2,4,6-tris(dimethylaminomethyl)phenol) and hexamethylenetetramine.
  • the filler is an organic or inorganic filler, and the inorganic filler is selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zeolite, wollastonite, silica, magnesia, calcium silicate, carbonate 4, clay, talc and mica.
  • the inorganic filler may be appropriately dose-adjusted according to the purpose of use, and the amount thereof is 100 parts by weight based on the total amount of the organic solids of the components in the composition of the above-mentioned glue, and is 0-100 parts by weight. Preferably, it is preferably 25-100 parts by weight.
  • the method for producing a halogen-free copper-clad laminate using the above halogen-free resin composition of the present invention comprises the following steps:
  • Step 1 Take 5 ⁇ 30 parts by weight of reactive small molecule polyphenylene ether with a number average molecular weight of 500 ⁇ 3000, dissolve in a solvent such as benzene or ketone, and add polybenzophenone after completely dissolved at normal temperature or medium temperature. 5 to 50 parts by weight of the azine resin is stirred and mixed to prepare a standby solution; wherein, the normal temperature is the normal temperature range described in the field of the copper clad laminate, and the medium temperature is specifically 30 to 80 ° C.
  • Step 2 taking 15 to 65 parts by weight of the phosphorus-containing epoxy resin, 1 to 25 parts by weight of the composite curing agent, 0 to 5 parts by weight of the curing accelerator, and 0 to 100 parts by weight of the filler are added to the above-mentioned standby solution, and uniformly stirred. A glue solution is obtained; wherein each component in steps 1, 2 is calculated as 100 parts by weight of the total organic solids.
  • Step 3 Select a flat surface E-glass cloth, uniformly coat the prepared glue, and bake it into a B-stage prepreg; during the baking of the B-stage prepreg, the baking temperature is based on the solvent used in the glue. The boiling point is set, the baking temperature range is generally 85 ⁇ 175 °C, and the time is generally 5 ⁇ 20min.
  • Step 4 According to the size of the press, the B-stage prepreg is cut into suitable sizes, stacked neatly, and a piece of copper foil is placed on the upper and lower sides, and placed in a vacuum hot press for pressing to obtain a copper-free board.
  • the pressing process adopts a stepwise pressing (step heating and boosting) method, and the specific steps are as follows: 15 min from room temperature to 150 ° C for 30 min, then 5 min to 180 ° C for 2 hr, and finally 30 min to cool the room temperature; Lmin rose from zero to 0.6Mpa, hold pressure for 20min, then lmin rose to l.OMpa, hold pressure for 2.5hr; post-treatment conditions were 200 ⁇ 245°C for 0 ⁇ 5hr.
  • the invention can improve the electrical properties of the system (reduce and stabilize Dk) and to toughen the system by introducing a reactive small molecule PPO (polyphenylene ether) into the phosphorus-containing epoxy/benzoxazine system.
  • PPO polyphenylene ether
  • the use of composite curing agents and their auxiliaries is very effective in catalyzing the polymerization between benzoxazine, PPO and epoxy.
  • a 300 x 300 cm, smooth, flat E-glass cloth was selected, and the above glue was applied to the adhesive, and baked in an oven at 155 ° C for 7 min to obtain a bonding sheet (B-stage prepreg).
  • Five sheets of embossed embossed sheets were superimposed, and copper foil with a thickness of 35 ⁇ m was attached to the upper and lower sides, and pressed in a vacuum hot press to obtain a halogen-free copper-clad laminate.
  • stepwise pressing step heating and boosting
  • step heating and boosting Pressed by stepwise pressing (step heating and boosting), which is held for 30 min from room temperature to 150 ° C after 15 min, then raised to 180 ° C for 5 min, then held for 2 hr, and finally cooled to room temperature for 30 min; Lmin keeps pressure from zero to 0.6Mpa 20min, then lmin rose to l.OMpa and held for 2.5hr.
  • composition of the 2 glue composition and the properties of the obtained copper clad laminate are shown in Tables 1 and 2 below.
  • a 300 x 300 cm, smooth, flat E-glass cloth was applied, and the above glue was uniformly applied, and baked at 155 ° C for 7 minutes in an oven to obtain a bonded sheet (B-stage semi-cured sheet).
  • Five sheets of embossed embossed sheets were superimposed, and copper foil with a thickness of 35 ⁇ m was attached to the upper and lower sides, and pressed in a vacuum hot press to obtain a halogen-free copper-clad laminate.
  • stepwise pressing which is raised from room temperature to 150 ° C for 30 min, then raised to 180 ° C for 5 min for 5 hr, and finally cooled to room temperature for 30 min; pressure lmin from zero liter Hold the pressure to 0.6Mpa for 20min, then lmin to l.OMpa for 2.5hr.
  • step heating and boosting which is raised from room temperature to 150 ° C for 30 min, then raised to 180 ° C for 5 min for 5 hr, and finally cooled to room temperature for 30 min; pressure lmin from zero liter Hold the pressure to 0.6Mpa for 20min, then lmin to l.OMpa for 2.5hr.
  • glass transition temperature (Tg) According to differential scanning calorimetry, according to IPC-TM- Measured by the DSC method specified in 650 2.4.25.
  • dielectric loss factor According to the resonance method using the strip line, the dielectric loss factor at 1 GHz is measured according to IPC-TM-650 2.5.5.5.
  • Bending strength The bending strength applied to the specimen of the specified size and shape at room temperature according to the IPC-TM-650 2.4.4 method.
  • the effect of not lowering the Tg (glass transition temperature), lowering the water absorption, lowering the dielectric constant, lowering the dielectric loss factor, and improving the toughness of the system can be achieved.
  • Punching processability is good, and the content of the element can reach the V-0 standard in the flame retardant test UL 94 within the range of JPCA without standard.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Textile Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Description

无卤树脂组合物及使用其的无卤覆铜板的制作方法 技术领域
本发明涉及覆铜板领域， 特别涉及一种无 树脂组合物及使用其的无 卤覆铜板的制作方法。 背景技术
当前， 电子、 电气工业正迅猛发展， 要求电子产品向轻量薄型化、 高 性能化、 高可靠性及环保方向发展， 因此也对印制线路板及覆铜箔板提出 了更高的要求。 其产品的具体要求表现为高耐热、 低热膨胀系数、 高耐湿 热、 环保阻燃、 低介电常熟和介电损耗及高弹性模量等。
卤化物、 锑化物等的覆铜板着火燃烧时， 不但发烟量大， 气味难闻， 而且会放出毒性大、 腐蚀性强的 化氢气体， 不仅污染环境， 也危害人体 健康； 目前工业上普遍使用含磷树脂来实现阻燃效果， 如含磷有菲型化合 物 DOPO或 ODOPB对应的环氧树脂， 或其它含磷树脂如三聚氯化磷腈化 物的环氧树脂， 但是浸泡后的板材会产生耐热性低、 吸水性高和耐化学性 差等等诸多问题。
为了解决上述的问题， 中国专利 ZL200410051855.3 利用含有二氢苯 并噁嗪的树脂来改善含磷环氧树脂以提高耐热性、 耐化学性、 降低吸水 性， 但是具有二氢苯并噁嗪的树脂较难达到 UL94 中 V-0的难燃性标准， 且本身很脆， 很难达到印刷电路板加工要求， 另外二氢苯并噁嗪本身的固 化温度很高， 要求达到 200摄氏度左右， 导致板材很难固化完全。
专利 CN1333014C有采用大分子聚苯醚直接填充进上述体系技术， 该 技术实际上很难达到预期效果， 原因是有机大分子填料填充工艺难度， 混 胶， 上胶难度大， 很难分散均匀。 只有将聚苯醚分子交联到聚合物上去才 能有效地增韧聚合物， 并且带来稍许介电常数和介电损耗的降低。 聚苯醚 结构本身是阻燃的， 但由于引入反应基团、 分子量的降低， 导致其耐燃性 大大降低。 发明内容
本发明的目的在于提供一种无 树脂组合物， 具有优异的耐热性、 耐 湿性及介电损耗低等优点。
本发明的另一目的在于提供一种使用上述无卤树脂组合物的无卤覆铜 板的制作方法， 操作筒单， 所制得的无卤覆铜板满足无卤要求， 具有优异 的耐热性、 耐湿性及介电损耗低等优点。
为实现上述目的， 本发明提供一种无 树脂组合物， 其包括组分及其 重量份如下： 数均分子量在 500~3000 的反应型小分子聚苯醚 5~30 重量 份、 聚苯并噁嗪树脂 5~50重量份、 含磷环氧树脂 15~65 重量份、 复合固 化剂 1~25重量份、 固化促进剂 0~5重量份、 填料 0-100重量份、 及苯类 或酮类溶剂适量。
其中各组分用量以总有机固形物总量 100重量份计算。
所述反应型小分子聚苯醚的化学结构式如下所示：
Figure imgf000004_0001
其中， m、 n为 0-25, 且 m、 n中至少一个不为 0; Y选自：
Figure imgf000004_0002
一 S _
X为烷基、 一 0
Ri, R2、 R7、 R8、 R9、 R10、 Ru、 R15、 R16为相同或不同的碳原子在 6 以下的烷基或苯基， R3、 、 R5、 R6、 R12、 R13、 R14为相同或不同的氢原 子或碳原子在 6以下的烷基或苯基。
所述苯并噁嗪树脂包括下述结构中的一种或多种：
Figure imgf000005_0001
其中， R2、 R3为单取代或多取代， R2、 R3为氢、 甲基、 烯丙基、 炔基
或醛基， 为一
Figure imgf000005_0002
， R4、 R5各自独立， 为 烯丙基、 未取代的或取代的苯基、 未取代的或取代的 C1-C8-烷基、 未取代 的或取代的 C1-C8-环烷基。
所述含磷环氧树脂中的基础环氧树脂为二官能团环氧树脂、 多官能团 环氧树脂或两者的混合物， 其含磷量为 2~5% , 环氧当量为 200~600g/mol; 所述胶液的组合物中的 素元素含量在 JPCA 无 标准要 求范围内， 即控制在 0.09重量份以下， 从而更好地达到环保效果。
所述含磷还氧树脂优选 25-55重量份。
所述复合固化剂选自双氰胺、 芳香胺、 酸酐以、 酚类化合物以及含磷 纷醛中的一种或多种。 所述固化促进剂选自 2-甲基咪唑、 2-乙基 -4 甲基咪唑、 2-苯基咪唑、 DMP-30 ( 2, 4, 6—三 （二甲胺基甲基）苯酚）及六次甲基四胺中的一种 或一种以上。
所述填料为有机或无机填料， 无机填料选自氢氧化铝、 氢氧化镁、 沸 石、 硅灰石、 二氧化硅、 氧化镁、 硅酸钙、 碳酸 4弓、 粘土、 滑石及云母等 通用无机填料中的一种或多种， 无机填料可以随使用目的作适当的剂量调 整， 其用量以上述胶液的组合物中组分的有机固形物总量 100 重量份计 算， 以 0-100重量份为宜， 最佳以 25-100重量份。
同时， 本发明还提供一种使用上述无卤树脂组合物的无卤覆铜板的制 作方法， 包括步骤如下：
步骤 1、 取数均分子量在 500~3000的反应型小分子聚苯醚 5~30重量 份， 溶于苯类或酮类等溶剂中， 在常温或中温条件下完全溶解后加入聚苯 并噁嗪树脂 5~50重量份， 搅拌混合， 制得备用溶液；
步骤 2、 取含磷环氧树脂 15~65重量份、 复合固化剂 1~25重量份、 固 化促进剂 0~5重量份及填料 0~100重量份加入到上述所得的备用溶液中， 搅拌均勾得到胶液；
步骤 3、 选取表面平整的 E-玻纤布， 均匀涂覆上述制得的胶液， 烘制 成 B-阶半固化片；
步骤 4、 根据压机大小， 将 B-阶半固化片切成合适的尺寸， 整齐叠 加， 并上下各放一张铜箔， 置于真空热压机中进行压制， 得到无 覆铜 板。
其中步骤 1中所述中温指 30~80°C。
所述步骤 3中烘制 B-阶半固化片的过程中， 烘制温度根据胶液所用溶 剂的沸点来设置， 烘制温度范围一般为 85~175°C , 时间一般为 5~20min。
所述步骤 4 中， 压制工艺采用阶梯式压制 （分步升温及升压） 法， 具 体步骤为： 15min从室温升至 150°C保持 30min, 然后 5min升至 180°C保 持 2hr, 最后 30min降温室温； 压力 lmin从零升至 0.6Mpa, 保压 20min, 然后 lmin 升至 l.OMpa , 保压 2.5hr; 后处理条件为 200~245 °C保持 0~5hr。
本发明的有益效果是： 本发明的无卤覆铜板的制作方法， 操作筒单， 所制得的无 覆铜板具有优异的耐热性、 耐湿性及介电损耗低等优点， 以 及板材沖孔加工性佳， 卤素含量在 JPCA 无卤标准要求范围内又能达到难 燃性试验 UL-94中的 V-0的标准。 附图说明
下面结合附图， 对本发明的具体实施方式详细描述， 以使本发明的技 术方案及其他有益效果显而易见。
附图中，
图 1为本发明的无卤覆铜板的制作方法流程图。 具体实施方式
本发明的无 树脂组合物， 以总有机固形物总量 100重量份计算， 其 包括组分及其重量份如下： 数均分子量在 500~3000 的反应型小分子聚苯 醚 5~30重量份、 聚苯并噁嗪树脂 5~50重量份、 含磷环氧树脂 15~65重量 份、 复合固化剂 1~25重量份、 固化促进剂 0~5重量份、 填料 0-100重量 份、 及苯类或酮类溶剂适量。 该无卤树脂组合物用于制作无卤覆铜板， 所 制得的无 覆铜板满足无 要求， 具有优异的耐热性、 耐湿性及介电损耗 低等优点。
其中， 所述反应型小分子聚苯醚的化学结构式如下所示：
Figure imgf000007_0001
其中， m、 n为 0-25, 且 m、 n中至少一个不为 0; Y选自：
Figure imgf000007_0002
一
X为烷基、
Ri, R2、 R7、 R8、 R9、 R10、 Ru、 R15、 R16为相同或不同的碳原子在 6 以下的烷基或苯基， R3、 、 R5、 R6、 R12、 R13、 R14为相同或不同的氢原 子或碳原子在 6以下的烷基或苯基。
所述聚苯并噁嗪树脂包括下述结构中的一种或多种：
Figure imgf000008_0001
其中， R2、 R3为单取代或多取代， R2、 R3为氢、 甲基、 烯丙基、 炔基
或醛基， 为一
Figure imgf000008_0002
， R4、 R5各自独立， 为 烯丙基、 未取代的或取代的苯基、 未取代的或取代的 C1-C8-烷基、 未取代 的或取代的 C1-C8-环烷基。
所述含磷环氧树脂中的基础环氧树脂为二官能团环氧树脂、 多官能团 环氧树脂或两者的混合物， 其含磷量为 2~5% , 环氧当量为 200~600g/mol; 所述胶液的组合物中的 素元素含量在 JPCA 无 标准要 求范围内， 即控制在 0.09重量份以下， 从而更好地达到环保效果。 所述含 磷还氧树脂优选 25-55重量份。
所述复合固化剂选自双氰胺、 芳香胺、 酸酐以、 酚类化合物以及含磷 酚醛中的一种或多种。 所述固化促进剂选自 2-甲基咪唑、 2-乙基 -4 甲基咪 唑、 2-苯基咪唑、 DMP-30 ( 2, 4, 6—三 （二甲胺基甲基）苯酚）及六次 甲基四胺中的一种或一种以上。
所述填料为有机或无机填料， 无机填料选自氢氧化铝、 氢氧化镁、 沸 石、 硅灰石、 二氧化硅、 氧化镁、 硅酸钙、 碳酸 4弓、 粘土、 滑石及云母等 通用无机填料中的一种或多种， 无机填料可以随使用目的作适当的剂量调 整， 其用量以上述胶液的组合物中组分的有机固形物总量 100 重量份计 算， 以 0-100重量份为宜， 最佳以 25-100重量份。
本发明的使用上述无卤树脂组合物的无卤覆铜板的制作方法， 如图 1 所示， 其包括步骤如下：
步骤 1、 取数均分子量在 500~3000的反应型小分子聚苯醚 5~30重量 份， 溶于苯类或酮类等溶剂中， 在常温或中温条件下完全溶解后加入聚苯 并噁嗪树脂 5~50 重量份， 搅拌混合， 制得备用溶液； 其中， 常温即为该 覆铜板领域中所述的常温的温度范围， 中温具体指 30~80°C。
步骤 2、 取含磷环氧树脂 15~65重量份、 复合固化剂 1~25重量份、 固 化促进剂 0~5重量份及填料 0~100重量份加入到上述所得的备用溶液中， 搅拌均匀得到胶液； 其中步骤 1、 2 中各组分以总有机固形物总量 100 重 量份计算。
步骤 3、 选取表面平整的 E-玻纤布， 均匀涂覆上述制得的胶液， 烘制 成 B-阶半固化片； 烘制 B-阶半固化片的过程中， 烘制温度根据胶液所用 溶剂的沸点来设置， 烘制温度范围一般为 85~175 °C , 时间一般为 5~20min。
步骤 4、 根据压机大小， 将 B-阶半固化片切成合适的尺寸， 整齐叠 加， 并上下各放一张铜箔， 置于真空热压机中进行压制， 得到无 覆铜 板。 所述压制工艺采用阶梯式压制 （分步升温及升压） 法， 具体步骤为： 15min从室温升至 150°C保持 30min, 然后 5min升至 180°C保持 2hr, 最后 30min降温室温； 压力 lmin从零升至 0.6Mpa, 保压 20min, 然后 lmin升 至 l.OMpa, 保压 2.5hr; 后处理条件为 200~245°C保持 0~5hr。
本发明通过在含磷环氧 /苯并噁嗪体系中引入反应型小分子 PPO (聚苯 醚） ， 既能改良体系电性能 （降低、 稳定 Dk ) , 又能增韧体系， 使之能 适用于更高层次的 PCB制作， 另外复合固化剂及其助剂的使用非常有效地 催化了苯并噁嗪、 PPO与环氧之间的聚合。
以下就二类无 阻燃路线的实施例对本发明作进一步描述， 但本发明 并非局限在实施例范围。
兹将本发明各实施例及比较例所用各组分说明如下。 下文中无特别说 明， 其％代表 "重量％" 。
反应型小分子聚苯醚：
( A ) MX90 ( SABIC Innovative Plastics商品名）
聚苯并噁嗪树脂：
( B-1 ) LZ 8280 (亨斯迈先进材料商品名）
( B-2 ) XU8282-1 (亨斯迈先进材料商品名）
( B-3 ) D125 (四川东材科技集团股份有限公司商品名）
含磷环氧树脂：
( C-l ) XZ 92530 ( DOW化学商品名）
( C-2 ) YEP250 (衢州广山化工有限公司商品名）
复合固化剂：
( D-1 )双氰胺
( D-2 )二氨基二苯砜
( D-3 ) PS 6313 (日本群荣化学工业株式会社商品名， 含氮量 20%, 羟当量 148 )
( D-3 ) XZ 92741 ( DOW化学商品名）
固化促进剂：
2-乙基 -4甲基咪唑
无机填料：
( F-1 ) 氢氧化铝（平均粒径为 3至 5 μ m, 纯度 99%以上）
( F-2 ) 525 (熔融二氧化硅， Sibelco商品名） 第一类实施例：
取数均分子量在 500~3000的反应型小分子聚苯醚 5~30重量份， 溶于 苯类、 酮类等溶剂中， 在常温或中温条件下完全溶解后加入聚苯并噁嗪树 脂 5~50重量份， 搅拌一定时间制得备用溶液； 取含磷环氧树脂 15~65 重 量份、 复合固化剂 1~25 重量份、 固化促进剂 0~5 重量份， 氢氧化铝为主 的无机填料 0~100 重量份加入到上述所得备用溶液中， 搅拌均勾得到胶 液。 选取 300 x 300cm、 表面光洁、 平整的 E-玻纤布， 均勾涂覆上述胶 液， 在烘箱中 155°C下烘烤 7min制得粘结片 （B-阶半固化片） 。 将 5张裁 去毛边的粘结片叠加， 上下各附上厚度为 35 μ ιη的铜箔， 置于真空热压机 中压制得到无卤覆铜板。 采用阶梯式压制法 （分步升温及升压）压制， 其 中， 以 15min从室温升至 150°C后保持 30min, 然后以 5min升至 180°C后 保持 2hr, 最后 30min 降至室温； 压力 lmin 从零升至 0.6Mpa后保压 20min, 然后 lmin升至 l.OMpa后保压 2.5hr。 具体实施例 1-3及比较例 1-
2胶液的组合物配方及制得覆铜板性能见下表 1、 2。
表 1 胶液的组合物配方 （一） （重量份 )
Figure imgf000011_0001
注： 表 1 中， 重量份的基准系以 （A) 、 （B) 、 （C) 、 （D)成份 的有机固形物按重量百分比 100份计。 表 2特性评估 （一）
Figure imgf000011_0002
( % )
介电常数
5.0 4.9 5.0 5.2 5.1
( IGHZ )
介电损耗
0.006 0.005 0.007 0.011 0.010 ( IGHZ )
弯曲强度
(横向） 655 650 640 565 450 ( N/mm2 )
沖孔性 〇 〇 〇 Δ Δ 第二类实施例：
取数均分子量在 500~3000 的反应型小分子聚苯醚 5~30重量份， 溶 于苯类、 酮类等溶剂中， 在常温或中温条件下完全溶解后加入聚苯并噁嗪 树脂 5~50 重量份， 搅拌一定时间制得备用溶液； 取含磷环氧树脂 15~65 重量份、 含磷酚醛为主的复合固化剂 1~25 重量份、 固化促进剂 0~5 重量 份， 不含氢氧化铝的无机填料 0-100重量份加入到上述所得备用溶液中， 搅拌均匀得到胶液。 选取 300 x 300cm、 表面光洁、 平整的 E-玻纤布， 均 匀涂覆上述胶液， 在烘箱中 155 °C下烘烤 7min 制得粘结片 （B-阶半固化 片） 。 将 5张裁去毛边的粘结片叠加， 上下各附上厚度为 35 μ ιη的铜箔， 置于真空热压机中压制得到无卤覆铜板。 采用阶梯式压制法 （分步升温及 升压）压制， 其中， 15min从室温升至 150°C保持 30min, 然后 5min升至 180°C保持 2hr, 最后 30min降至室温； 压力 lmin从零升至 0.6Mpa保压 20min, 然后 lmin升至 l.OMpa保压 2.5hr。 具体实施例 4-6及比较例 3-4 胶液的组合物配方及制得覆铜板性能见下表 3、 4。
表 3 胶液的组合物配方 （二） （重量份）
实施例 4 实施例 5 实施例 6 比较例 3 比较例 4
A 15 28 10 0 0
B1 0 0 31 0 0
B2 0 20 0 0 33
B3 34 0 0 33 0
C1 0 0 42 0 0
C2 42 29 0 48 44
D1 0 0 0 0 0 D2 4.0 0 2.0 4.0 0
D3 0 8.0 0 0 8.0
D4 15 15 15 15 15
E 0.1 0.1 0.1 0.1 0.1
Fl 0 0 0 0 0
F2 40 40 40 40 40 注： 表 3 中， 重量份的基准系以 （A) 、 （B) 、 （C) 、 （D)成份 的有机固形物按重量百分比 100份计。
表 4特性评估（二）
Figure imgf000013_0001
以上特性的测试方法如下：
(1) 、 玻璃化转变温度 (Tg): 根据差示扫描量热法， 按照 IPC-TM- 650 2.4.25 所规定的 DSC方法进行测定。
(2) 、 剥离强度 (PS) ： 按照 IPC-TM-650 2.4.8 方法中的 "热应 力后" 实验条件， 测试金属盖层的剥离强度。
(3) 、 耐燃烧性（难燃性） ： 依据 UL 94法测定。
(4) 、 耐浸焊性： 将在 121°C、 105Kpa 的加压蒸煮处理装置内保持 2 小时后的试样（ 100 X 100mm的基材）浸在加热至 260°C的焊锡槽中 20 秒钟， 以肉眼观察（hi)有无分层， （h2)有无发生白斑或起皱。 表中的 符号〇示无变化， Δ示发生白斑， X示发生分层。
(5) 、 吸水性： 按照 IPC-TM-650 2.6.2.1方法进行测定。
(6) 、 介电损耗因数： 根据使用条状线的共振法， 按照 IPC-TM-650 2.5.5.5测定 1GHz下的介电损耗因数。
(7) 、 弯曲强度： 按照 IPC-TM-650 2.4.4方法， 在室温下把负载施 加于规定尺寸和形状试样上的弯曲强度。
(8) 、 沖孔性： 将 1.60mm厚的基材放于一定图形的沖模上进行沖 孔， 以肉眼观察（hi ) 孔边无白圏， （h2) 孔边有白圏， （h3) 孔边裂 开， 表中分别以符号〇、 Δ、 X表示。
综上述结果可知， 依据本发明可达到不降低 Tg (玻璃化转变温度） 、 降低吸水性、 降低介电常数、 降低介电损耗因数的功效， 同时可改善体系 韧性， 所制得无 覆铜板板材沖孔加工性佳， 素含量在 JPCA无 标准 要求范围内能达到难燃性试验 UL 94中的 V-0的标准。
以上实施例， 并非对本发明的组合物的含量作任何限制， 凡是依据本 发明的技术实质或组合物成份或含量对以上实施例所作的任何细微修改、 等同变化与修饰， 均仍属于本发明技术方案的范围内。

Claims

权 利 要 求
1、 一种无 树脂组合物， 其包括组分及其重量份如下： 数均分子量 在 500~3000 的反应型小分子聚苯醚 5~30重量份、 聚苯并噁嗪树脂 5~50 重量份、 含磷环氧树脂 15~65 重量份、 复合固化剂 1~25 重量份、 固化促 进剂 0~5重量份、 填料 0~100重量份、 及苯类或酮类溶剂适量。
2、 如权利要求 1 所述的无卤树脂组合物， 其中， 所述反应型小分子 聚苯醚的化学结构式如下所示：
Figure imgf000015_0001
其中， m、 n为 0-25, 且 m、 n中至少一个不为 0; Y选自：
X
Figure imgf000015_0002
为烷基、 一 s _ 一 o一
Ri, R2、 R7、 R8、 R9、 R10、 Ru、 R15、 R16为相同或不同的碳原子在 6 以下的烷基或苯基， R3、 、 R5、 R6、 R12、 R13、 R14为相同或不同的氢原 子或碳原子在 6以下的烷基或苯基。
3、 如权利要求 1 所述的无 树脂组合物， 其中， 所述聚苯并噁嗪树 脂包括下述结构中的一种或多种：
Figure imgf000016_0001
其中， R2、 R3为单取代或多取代， R2、 R3为氢、 甲基、 烯丙基、 炔基
或醛基， 为一
Figure imgf000016_0002
， R4、 R5各自独立， 为 烯丙基、 未取代的或取代的苯基、 未取代的或取代的 C1-C8-烷基、 未取代 的或取代的 C1-C8-环烷基。
4、 如权利要求 1 所述的无 树脂组合物， 其中， 所述含磷环氧树脂 中的基础环氧树脂为二官能团环氧树脂、 多官能团环氧树脂或两者的混合 物， 其含磷量为 2~5% , 环氧当量为 200~600g/mol。
5、 如权利要求 1 所述的无 树脂组合物， 其中， 所述复合固化剂选 自双氰胺、 芳香胺、 酸酐以、 酚类化合物以及含磷酚醛中的一种或多种。
6、 如权利要求 1 所述的无 树脂组合物， 其中， 所述固化促进剂选 自 2-甲基咪唑、 2-乙基 -4 甲基咪唑、 2-苯基咪唑、 DMP-30 及六次甲基四 胺中的一种或一种以上； 所述填料为有机或无机填料， 无机填料选自氢氧 化铝、 氢氧化镁、 沸石、 硅灰石、 二氧化硅、 氧化镁、 硅酸 4弓、 碳酸 4丐、 粘土、 滑石及云母中的一种或多种。
7、 一种使用如权利要求 1 所述的无卤树脂组合物的无卤覆铜板的制 作方法， 包括步骤如下：
步骤 1、 取数均分子量在 500~3000的反应型小分子聚苯醚 5~30重量 份， 溶于苯类或酮类溶剂中， 在常温或中温条件下完全溶解后加入聚苯并 噁嗪树脂 5~50重量份， 搅拌混合， 制得备用溶液；
步骤 2、 取含磷环氧树脂 15~65重量份、 复合固化剂 1~25重量份、 固 化促进剂 0~5重量份及填料 0~100重量份加入到上述所得的备用溶液中， 搅拌均勾得到胶液；
步骤 3、 选取表面平整的 E-玻纤布， 均匀涂覆上述制得的胶液， 烘制 成 B-阶半固化片；
步骤 4、 根据压机大小， 将 B-阶半固化片切成合适的尺寸， 整齐叠 加， 并上下各放一张铜箔， 置于真空热压机中进行压制， 得到无 覆铜 板。
8、 如权利要求 7所述的无卤覆铜板的制作方法， 其特征在于， 步骤 1 中所述中温指 30~80°C。
9、 如权利要求 7 所述的无卤覆铜板的制作方法， 其中， 所述步骤 3 中烘制 B-阶半固化片的过程中， 烘制温度根据胶液所用溶剂的沸点来设 置， 烘制温度为 85~175 °C , 时间为 5~20min。
10、 如权利要求 7所述的无卤覆铜板的制作方法， 其中， 所述步骤 4 中， 压制工艺采用阶梯式压制法， 具体步骤为： 15min从室温升至 150°C 保持 30min, 然后 5min升至 180°C保持 2hr, 最后 30min降温室温； 压力 lmin 从零升至 0.6Mpa , 保压 20min , 然后 lmin 升至 l.OMpa , 保压 2.5hr; 后处理条件为 200~245 °C保持 0~5hr。
PCT/CN2011/079308 2010-12-23 2011-09-03 无卤树脂组合物及使用其的无卤覆铜板的制作方法 WO2012083728A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP11851266.4A EP2657296A4 (en) 2010-12-23 2011-09-03 HALOGEN-FREE RESIN COMPOSITION AND METHOD FOR PRODUCING A HALOGEN-FREE COPPER-COATED LAMINATE THEREWITH
US13/997,542 US9076573B2 (en) 2010-12-23 2011-09-03 Halogen-free resin composition and method for fabricating halogen-free copper clad laminate using the same
KR1020137019505A KR101508083B1 (ko) 2010-12-23 2011-09-03 비할로겐계 수지 조성물 및 이를 이용한 비할로겐계 구리 피복 라미네이트의 제작방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201010602780A CN102093666B (zh) 2010-12-23 2010-12-23 无卤树脂组合物及使用其的无卤覆铜板的制作方法
CN201010602780.9 2010-12-23

Publications (1)

Publication Number Publication Date
WO2012083728A1 true WO2012083728A1 (zh) 2012-06-28

Family

ID=44126945

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2011/079308 WO2012083728A1 (zh) 2010-12-23 2011-09-03 无卤树脂组合物及使用其的无卤覆铜板的制作方法

Country Status (5)

Country Link
US (1) US9076573B2 (zh)
EP (1) EP2657296A4 (zh)
KR (1) KR101508083B1 (zh)
CN (1) CN102093666B (zh)
WO (1) WO2012083728A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116373415A (zh) * 2023-06-05 2023-07-04 山东森荣新材料股份有限公司 Ptfe陶瓷填料复合高频覆铜板的制备方法

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102093666B (zh) * 2010-12-23 2012-09-26 广东生益科技股份有限公司 无卤树脂组合物及使用其的无卤覆铜板的制作方法
WO2013029271A1 (zh) * 2011-09-02 2013-03-07 广东生益科技股份有限公司 无卤树脂组合物以及使用其制作覆铜板的方法
CN102977551B (zh) * 2011-09-02 2014-12-10 广东生益科技股份有限公司 无卤树脂组合物以及使用其制作覆铜板的方法
CN102977583B (zh) * 2011-09-05 2015-08-05 深圳光启高等理工研究院 改性聚苯醚和基于改性聚苯醚制备基材的方法
US9243164B1 (en) 2012-02-21 2016-01-26 Park Electrochemical Corporation Thermosetting resin composition containing a polyphenylene ether and a brominated fire retardant compound
US9051465B1 (en) 2012-02-21 2015-06-09 Park Electrochemical Corporation Thermosetting resin composition containing a polyphenylene ether and a brominated fire retardant compound
CN104845363B (zh) * 2014-02-14 2017-04-05 广东生益科技股份有限公司 一种无卤树脂组合物及其用途
CN104845366B (zh) * 2014-02-14 2017-04-05 广东生益科技股份有限公司 一种无卤树脂组合物及其用途
CN104845365B (zh) * 2014-02-14 2017-04-05 广东生益科技股份有限公司 一种无卤树脂组合物及其用途
CN104845364B (zh) * 2014-02-14 2017-04-05 广东生益科技股份有限公司 一种无卤树脂组合物及其用途
CN105419348B (zh) * 2016-01-18 2018-11-27 广东生益科技股份有限公司 一种树脂组合物以及使用它的预浸料和层压板
CN106009663B (zh) * 2016-08-02 2017-04-19 广东同宇新材料有限公司 一种具有UV‑blocking功能的树脂组合物
CN106700548B (zh) * 2016-12-30 2019-04-30 广东生益科技股份有限公司 一种含有苯并噁嗪树脂组合物的制备方法及由其制成的预浸料和层压板
CN106854361B (zh) * 2016-12-30 2019-11-12 广东生益科技股份有限公司 一种含有苯并噁嗪的树脂组合物的制备方法及由其制成的预浸料和层压板
CN109439245B (zh) * 2018-09-11 2021-03-26 法施达(大连)实业集团有限公司 一种双组份环氧界面胶黏剂及其制备方法
CN109867914B (zh) * 2019-01-30 2020-08-14 常州中英科技股份有限公司 一种聚多巴胺改性的碳氢组合物基半固化片及其制备的覆铜板
CN109796728B (zh) * 2019-01-30 2020-04-17 常州中英科技股份有限公司 一种聚多酚改性的碳氢组合物基半固化片及其制备的覆铜板
CN110561855B (zh) * 2019-09-04 2022-04-01 重庆德凯实业股份有限公司 一种无卤中Tg高CTI阻燃环氧玻纤布基层压板及其制备方法
CN112135427B (zh) * 2020-10-10 2022-08-12 珠海市浩东电子科技有限公司 一种用于动力电池的线路板
CN114161804A (zh) * 2021-11-08 2022-03-11 安徽鸿海新材料股份有限公司 一种环氧纸玻纤布复合基覆铜板及其制备方法
CN115230287B (zh) * 2022-07-20 2024-04-02 广德华昌新材料有限公司 一种覆铜板的制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004027000A (ja) * 2002-06-25 2004-01-29 Matsushita Electric Works Ltd エポキシ樹脂組成物、プリプレグ及び積層板
CN1548473A (zh) * 2003-05-09 2004-11-24 广州宏仁电子工业有限公司 一种胶液、使用该胶液的无卤阻燃覆铜箔基板及其制作方法
CN100999145A (zh) * 2005-12-31 2007-07-18 四川东材企业集团有限公司 一种高玻璃化转变温度无卤阻燃玻璃布层压板的制备方法
CN1333014C (zh) 2003-08-08 2007-08-22 长春人造树脂厂股份有限公司 不含卤素的树脂组合物
US20080132629A1 (en) * 2006-12-05 2008-06-05 Nan Ya Plastics Corporation Synthesis of new dihydrobenzoxazine
US20090176104A1 (en) * 2008-01-04 2009-07-09 Li-Chun Chen Resin composition and application thereof
CN101735562A (zh) * 2009-12-11 2010-06-16 广东生益科技股份有限公司 环氧树脂组合物及其制备方法及采用其制作的层压材料及覆铜箔层压板
CN102093666A (zh) * 2010-12-23 2011-06-15 广东生益科技股份有限公司 无卤树脂组合物及使用其的无卤覆铜板的制作方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100384932C (zh) 2004-10-11 2008-04-30 广东生益科技股份有限公司 一种热固性树脂组合物以及使用它的预浸料、印刷电路用层压板
GB0806434D0 (en) * 2008-04-09 2008-05-14 Zephyros Inc Improvements in or relating to structural adhesives
CN101280093B (zh) * 2008-05-13 2010-12-15 广东生益科技股份有限公司 一种无卤阻燃环氧树脂组合物、使用其制作的挠性覆铜板及其制作方法
CN101457012B (zh) * 2008-12-31 2011-06-15 广东生益科技股份有限公司 一种树脂组合物及使用该树脂组合物涂覆金属箔、使用其制作的覆铜板

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004027000A (ja) * 2002-06-25 2004-01-29 Matsushita Electric Works Ltd エポキシ樹脂組成物、プリプレグ及び積層板
CN1548473A (zh) * 2003-05-09 2004-11-24 广州宏仁电子工业有限公司 一种胶液、使用该胶液的无卤阻燃覆铜箔基板及其制作方法
CN1333014C (zh) 2003-08-08 2007-08-22 长春人造树脂厂股份有限公司 不含卤素的树脂组合物
CN100999145A (zh) * 2005-12-31 2007-07-18 四川东材企业集团有限公司 一种高玻璃化转变温度无卤阻燃玻璃布层压板的制备方法
US20080132629A1 (en) * 2006-12-05 2008-06-05 Nan Ya Plastics Corporation Synthesis of new dihydrobenzoxazine
US20090176104A1 (en) * 2008-01-04 2009-07-09 Li-Chun Chen Resin composition and application thereof
CN101735562A (zh) * 2009-12-11 2010-06-16 广东生益科技股份有限公司 环氧树脂组合物及其制备方法及采用其制作的层压材料及覆铜箔层压板
CN102093666A (zh) * 2010-12-23 2011-06-15 广东生益科技股份有限公司 无卤树脂组合物及使用其的无卤覆铜板的制作方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2657296A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116373415A (zh) * 2023-06-05 2023-07-04 山东森荣新材料股份有限公司 Ptfe陶瓷填料复合高频覆铜板的制备方法
CN116373415B (zh) * 2023-06-05 2023-07-28 山东森荣新材料股份有限公司 Ptfe陶瓷填料复合高频覆铜板的制备方法

Also Published As

Publication number Publication date
US9076573B2 (en) 2015-07-07
KR20130125383A (ko) 2013-11-18
CN102093666B (zh) 2012-09-26
CN102093666A (zh) 2011-06-15
KR101508083B1 (ko) 2015-04-07
EP2657296A4 (en) 2014-08-27
US20130284358A1 (en) 2013-10-31
EP2657296A1 (en) 2013-10-30

Similar Documents

Publication Publication Date Title
WO2012083728A1 (zh) 无卤树脂组合物及使用其的无卤覆铜板的制作方法
JP6381802B2 (ja) ノンハロゲン樹脂組成物、及びそれを用いて製造されたプリプレグと積層板
KR101799717B1 (ko) 열경화성 수지 조성물 및 그 용도
KR100705269B1 (ko) 비할로겐 난연성 에폭시 수지 조성물, 이를 이용한프리프레그 및 동박 적층판
US8581107B2 (en) Halogen-free flame-retardant epoxy resin composition, and prepreg and printed circuit board using the same
EP2752449B1 (en) Halogen-free resin composition and method for preparation of copper clad laminate with same
EP3219758B1 (en) Thermosetting resin composition and prepreg and laminated board prepared therefrom
WO2015188377A1 (zh) 一种苯氧基环三磷腈活性酯、无卤树脂组合物及其用途
WO2012083727A1 (zh) 无卤高tg树脂组合物及用其制成的预浸料与层压板
WO2012083725A1 (zh) 无卤阻燃性树脂组合物及其应用
WO2016011705A1 (zh) 一种无卤树脂组合物以及使用它的预浸料和印制电路用层压板
CN109851997B (zh) 一种热固性树脂组合物及使用其的预浸料、层压板和覆金属箔层压板
WO2016119356A1 (zh) 一种无卤树脂组合物及用其制作的预浸料和层压板
CN109651763B (zh) 一种热固性树脂组合物及使用其的预浸料、层压板和覆金属箔层压板
WO2014089934A1 (zh) 一种无卤阻燃树脂组合物及其用途
WO2015154315A1 (zh) 一种无卤无磷阻燃树脂组合物
CN109608828B (zh) 一种热固性树脂组合物及使用其的预浸料、层压板和覆金属箔层压板
CN109535628B (zh) 一种阻燃型树脂预聚物及使用其制备的热固性树脂组合物、半固化片和层压板
WO2015184652A1 (zh) 一种无卤树脂组合物以及使用它的预浸料和印制电路用层压板
TWI496824B (zh) 環氧樹脂組成物及由其製成的預浸材和印刷電路板
US9963590B2 (en) Halogen-free resin composition, and a prepreg and a laminate used for printed circuit using the same
CN114605779B (zh) 一种热固性树脂组合物及包含其的预浸料、电路基板和印刷电路板
US8383738B2 (en) Epoxy resin composition, and prepreg and printed circuit board using the same
KR20200055795A (ko) 에폭시 수지 조성물, 프리프레그, 적층판 및 인쇄회로기판
JP6369892B2 (ja) リン含有難燃性エポキシ樹脂

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11851266

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 13997542

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2011851266

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20137019505

Country of ref document: KR

Kind code of ref document: A