CN105585821A - Halogen-free resin composition, no-flow prepreg prepared from halogen-free resin composition and manufacturing method of prepreg - Google Patents
Halogen-free resin composition, no-flow prepreg prepared from halogen-free resin composition and manufacturing method of prepreg Download PDFInfo
- Publication number
- CN105585821A CN105585821A CN201610055607.9A CN201610055607A CN105585821A CN 105585821 A CN105585821 A CN 105585821A CN 201610055607 A CN201610055607 A CN 201610055607A CN 105585821 A CN105585821 A CN 105585821A
- Authority
- CN
- China
- Prior art keywords
- halogen
- resin
- epoxy resin
- parts
- free
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a halogen-free epoxy resin composition, a no-flow prepreg prepared from the halogen-free resin composition and a manufacturing method of the prepreg. The halogen-free epoxy resin composition comprises the following components in parts by weight: 15-60 parts of epoxy resin, 5-30 parts of phenoxy resin, 20-50 parts of phosphorus-containing phenolic resin, 20-60 parts of inorganic filler, 1-5 parts of curing agent, 0.3-1.5 parts of accelerator and 20-40 parts of solvent. The solid content is 60-75%. The method for manufacturing the no-flow prepreg from the halogen-free resin composition comprises the following steps: weighing the components according to the weight parts; uniformly mixing the solvent with all the other components to prepare a resin adhesive solution of which the GT is 250-300; and coating the resin adhesive solution on glass fiber cloth, and drying in a 150-200-DEG C drying oven for 5-10 minutes. The composition is free of halogens; under the synergistic actions of the epoxy group, phosphorus element and inorganic filler, the no-flow prepreg prepared from the composition can implement halogen-free flame retardancy, and the flame retardancy can reach Grade UL94V; and the prepreg has the advantages of environment friendliness, high heat resistance, low thermal expansion coefficient, high flexibility, high binding strength, no flow and the like.
Description
Technical field
The invention belongs to technical field of electronic materials, be specifically related to a kind of halogen-free epoxy resin composition and use not flow prepreg and preparation method thereof of its making.
Background technology
In recent years, along with electronic product is towards multifunction future development, the integrated level of electronic devices and components is also more and more higher, is promoting electronic product towards thin light short and small future development. Rigid-flex combined board (Rigid-Flexible) is as a kind of special interconnection technique, owing to can meeting the three-dimensional requirement of installing of electronic devices and components, for the design of printed circuit board provides larger freedom, be nowadays widely used in the electronic products such as computer, display, Aero-Space, communication apparatus, digital camera and Medical Devices.
At present, in the processing procedure of rigid-flex combined board, acrylic acid film or the mylars of adopting as binding material more, but because the dimensional stability of pure film condensation material itself is poor, pressing-in temp is higher, and its heat resistance is also more and more difficult to meet rigid-flex combined board production requirement, therefore need the substitution material of exploitation for boning between rigid plate and flexible board badly. Flow prepreg (No-FlowPrepreg) is because it does not flow and have the features such as certain caking property at second curing resin layer of HTHP, in rigid/flexible combined printed circuit board processing procedure, as a kind of special binder materials'use.
On the other hand, the common requirement of resin combination for the manufacture of printed circuit base board will have good anti-flammability, at present in industry mainly with brominated resin combination or realize fire-retardant to adding brominated flame-retardant in composition epoxy resin, and brominated epoxy resin is in the process of burning, can produce toxic gas. Along with European Union environmental protection instruction " about scrapping electric/electronic device instruction " (WEEE) and " ROHS " formal enforcement (RoHS), the non-halogen emphasis that has become industry exploitation of electronic material. Realize at present the halogen-free flameproof of board substrate, general way be in resin system, add phosphorous, resinamines or phosphorous, containing nitrogen combustion inhibitor.
Adopt the resin system taking the epoxy resin of modified rubber as key component but current existing not gummosis semi-solid preparation product, composition system fluidity can be reduced containing rubber components, thereby reach the not effect of gummosis, but also can cause the glass transition temperature of resin combination on the low side, reduce its heat resistance and cohesive force. Thereby cause with the adhesion of Kapton poorly, produce when rigid-flex combined board and need to carry out plasma treatment to improve its cohesive force to polyimides face; When pressing, easily there is hickie, thereby cause heat resistance slightly poor.
The preparation method of a kind of resin combination and the low flow prepreg of use is disclosed in Japan Patent 2006-316104, in its formula system taking containing benzoxazine ring resin as matrix resin, use melamine modified phenolic resin, polyphosphate and organic phosphorus compound to carry out phosphorus nitrogen cooperative flame retardant simultaneously, reach not halogen-containing effect. But the prepreg fluidity of its made is bigger than normal, be 4% left and right, and peel strength is lower only has 0.7-1.1kN/m.
Summary of the invention
The object of this reality invention is to provide a kind of halogen-free resin composition and uses low flow prepreg of its making and preparation method thereof to solve the problem that prior art exists.
In order to realize above-mentioned object, adopt following technical scheme:
A kind of halogen-free resin composition, comprises following component and weight portion: epoxy resin 15-60 part, phenoxy resin 5-30 part, phosphorus containing phenolic resin 20-50 part, inorganic filler 20-60 part, curing agent 1-5 part, promoter 0.3-1.5 part, solvent 20-40 part, solid content is 60-75%.
Further, comprise following component and weight portion: epoxy resin 20-50 part, phenoxy resin 10-20 part, phosphorus containing phenolic resin 25-40 part, inorganic filler 30-50 part, curing agent 1-5 part, promoter 0.5-1.5 part, solvent 20-40 part, solid content is 60%-70%.
Further, epoxy resin: phosphorus containing phenolic resin: the weight ratio of inorganic filler is 57.5:30:34.
Further, total epoxide equivalent is 1:1 with total hydroxyl equivalent ratio, in the time that total epoxide equivalent in system approaches 1:1 with total hydroxyl equivalent ratio, just can make glue system completely curing. The hydroxyl equivalent of described phosphorus containing phenolic resin is 300-600g/eq, and the content of P elements is 3%-10%; Structure is as follows:
Wherein 5≤n≤30;
The molecular weight of described phenoxy resin is 10000-400000; Structure is as follows:
Wherein n=30-120.
Epoxy resin has determined the overall performance of material in whole formula system, as hot property, electrical property also have the Resin Flow of glue entirety in this formula, the collaborative anti-flammability that promotes material of phosphorus containing phenolic resin and inorganic filler, inorganic filler simultaneously also can reduce thermal coefficient of expansion and the cost of material. In epoxy-resin systems, introduce phosphorus containing phenolic resin, P elements can replace halogen in resin system, just can play good flame retardant effect under lower content. Meanwhile, because phosphorus containing phenolic resin is also as one of curing agent of epoxy resin, the crosslink density of enlarged link epoxy resin system, has further improved the electrical insulating property of resin system and has reduced its coefficient of thermal expansion. Using phosphorus containing phenolic resin is mainly that phosphorus element content is higher because will play main fire retardation by P elements in halogen-free system, and the flame retardant effect that uses the resin of equal in quality to play is just better. The amount that P elements will reach the resin that identical flame retardant effect uses is more at least more, and cost increases and the overall performance of material also can be influenced.
Phenoxy resin is a kind of resin of super high molecular weight, and its general molecular weight is between 10000-400000, and the preferred phenoxy resin mean molecule quantity of the present invention is 30000-50000. Macromolecular phenoxy resin plays choked flow in system, and the too small effect of molecular weight is not obvious, and the excessive resin of molecular weight itself is not soluble, and adds glass transition temperature, outward appearance and the heat resistance variation that in system, can make material to. The phenoxy resin of super high molecular weight plays the effect of choked flow in resin system, can effectively reduce the fluidity of resin combination, controls the not object of gummosis of prepreg thereby reach. On molecular backbone due to phenoxy resin, there is phenyl ring, propylidyne and hydroxyl simultaneously, therefore there is phenoxy resin itself and there is good mechanical performance, electrical property, creep resistance and strong adhesive power, can effectively improve the caking property of material and PI film.
Further, described epoxy resin comprises one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type, biphenyl type epoxy resin, benzoxazine colophony, alicyclic based epoxy resin, phenol phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin, linear phenolic epoxy resin, resorcinol type epoxy resin, four-functional group epoxy resin, isocyanate modified epoxy resin, 2-glycidyl amine type epoxy resin, rubber modified epoxy resin.
Further, described inorganic filler is carried out surface treatment through silane coupler before using; Described inorganic filler comprises one or more in silica, aluminium hydroxide, aluminium oxide, magnesia, magnesium hydroxide, boron nitride, aluminium nitride, talcum powder, calcium carbonate, silicon powder and Firebrake ZB, zinc stannate. Before inorganic filler is used, carry out surface treatment with silane coupler, can improve the associativity of organic component.
Further, described curing agent comprises one or more in amine, phenolic resins. Described promoter comprises one or more in imidazolium compounds and derivative and organic metal salt. Preferred imidazolium compounds is glyoxal ethyline, 2-ethyl-4-methylimidazole or 1 benzyl 2 methyl imidazole.
Further, described solvent comprises one or more in acetone, butanone, propylene glycol monomethyl ether, dimethyl formamide, methylisobutylketone, cyclohexanone.
Use described halogen-free resin composition to make a not method for flow prepreg, comprise the steps:
(1) take in proportion each component;
(2) each to solvent and all the other component is mixed, the mixed GT that makes resin adhesive liquid is 250-300; Optimum when GT is 270 left and right;
(3) on glue coated glass fiber cloth, in the baking oven of 150-200 DEG C, dry 5-10min by obtaining in step (2), make not flow prepreg.
The gelation time (glue GT value) of resin adhesive liquid also has a certain impact to the fluidity of prepreg, the general more short not characteristic of gummosis of prepreg that more easily realizes of GT value, but when the too short production of GT, can easily cause prepreg aging, affect performance, the long easy gummosis of GT.
A kind of not flow prepreg of making according to said method. Comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric.
Compared with prior art, composition of the present invention is not halogen-containing, according to epoxy resin, P elements, phenoxy resin and inorganic filler synergy, can realize halogen-free flameproof, and anti-flammability reaches UL94V-0 level; And there is good heat resistance and low thermal coefficient of expansion. The not flow prepreg being made by composition of the present invention can be realized halogen-free flameproof, anti-flammability reaches UL94V-0 level, there is environmental protection characteristic, high-fire resistance, low thermal coefficient of expansion, high-flexibility, high bond strength and the premium properties such as gummosis not simultaneously, in rigid/flexible combined printed circuit board processing procedure, use as a kind of special binding material.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below the present invention is described in further detail.
Embodiment 1
A kind of halogen-free resin composition, comprises following component and weight portion: 40 parts of epoxy resin, 30 parts of phosphorus containing phenolic resins, 20 parts of phenoxy resins, 30 parts of inorganic fillers, 30 parts of solvent cyclohexanone, 3 parts of curing agent dicyandiamides, 0.5 part of promoter glyoxal ethyline. Anti-flammability reaches UL94V-0 level. Total epoxide equivalent is 1:1 with total hydroxyl equivalent ratio.
Above-mentioned halogen-free resin composition is made to the not method of flow prepreg, comprise the steps:
(1) take respectively by weight each component of above-mentioned halogen-free resin composition;
(2) each to solvent in composition and all the other component is fully stirred to 2h and mix above, being configured to solid content is the halogen-free low fluidity glue of 60%-70%.
(3) the above-mentioned glue after being uniformly mixed is coated on 1080 glass fabrics, the baking oven of putting into 170 DEG C toasts 6min, obtains not flow prepreg.
According to said method make not flow prepreg: comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric. Anti-flammability reaches UL94V-0 level.
Embodiment 2
A kind of halogen-free resin composition, comprises following component and weight portion: 20 parts of epoxy resin, 50 parts of phosphorus containing phenolic resins, 10 parts of phenoxy resins, 40 parts of inorganic fillers, 30 parts of solvent cyclohexanone, 2 parts of curing agent dicyandiamides, 0.5 part of promoter glyoxal ethyline. Anti-flammability reaches UL94V-0 level. Total epoxide equivalent is 1:1 with total hydroxyl equivalent ratio.
Above-mentioned halogen-free resin composition is made to the not method of flow prepreg, comprise the steps:
(1) take respectively by weight each component of above-mentioned halogen-free resin composition;
(2) each to solvent in composition and all the other component is fully stirred to 2h and mix above, being configured to solid content is the halogen-free low fluidity glue of 60%-70%.
(3) the above-mentioned glue after being uniformly mixed is coated on 1080 glass fabrics, the baking oven of putting into 170 DEG C toasts 6min, obtains not flow prepreg.
According to said method make not flow prepreg: comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric. Anti-flammability reaches UL94V-0 level.
Embodiment 3
A kind of halogen-free resin composition, comprises following component and weight portion: 25 parts of epoxy resin, 35 parts of phosphorus containing phenolic resins, 25 parts of phenoxy resins, 30 parts of inorganic fillers, 25 parts of solvent cyclohexanone, 1.5 parts of curing agent dicyandiamides, 0.3 part of promoter glyoxal ethyline. Anti-flammability reaches UL94V-0 level.
Above-mentioned halogen-free resin composition is made to the not method of flow prepreg, comprise the steps:
(1) take respectively by weight each component of above-mentioned halogen-free resin composition;
(2) each to solvent in composition and all the other component is fully stirred to 2h and mix above, being configured to solid content is the halogen-free low fluidity glue of 60%-70%.
(3) the above-mentioned glue after being uniformly mixed is coated on 1080 glass fabrics, the baking oven of putting into 170 DEG C toasts 6min, obtains not flow prepreg.
According to said method make not flow prepreg: comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric. Anti-flammability reaches UL94V-0 level.
Embodiment 4
A kind of halogen-free resin composition, comprises following component and weight portion: 50 parts of epoxy resin, 25 parts of phosphorus containing phenolic resins, 25 parts of phenoxy resins, 28 parts of inorganic fillers, 35 parts of solvent cyclohexanone, 3 parts of curing agent dicyandiamides, 0.7 part of promoter glyoxal ethyline, anti-flammability reaches UL94V-0 level.
Above-mentioned halogen-free resin composition is made to the not method of flow prepreg, comprise the steps:
(1) take respectively by weight each component of above-mentioned halogen-free resin composition;
(2) each to solvent in composition and all the other component is fully stirred to 2h and mix above, being configured to solid content is the halogen-free low fluidity glue of 60%-70%.
(3) the above-mentioned glue after being uniformly mixed is coated on 1080 glass fabrics, the baking oven of putting into 170 DEG C toasts 6min, obtains not flow prepreg.
According to said method make not flow prepreg: comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric. Anti-flammability reaches UL94V-0 level.
Embodiment 5
A kind of halogen-free resin composition, comprises following component and weight portion: 35 parts of epoxy resin, 35 parts of phosphorus containing phenolic resins, 30 parts of inorganic fillers, 40 parts of solvent cyclohexanone, 3 parts of curing agent dicyandiamides, 0.5 part of promoter glyoxal ethyline. Anti-flammability reaches UL94V-0 level.
Above-mentioned halogen-free resin composition is made to the not method of flow prepreg, comprise the steps:
(1) take respectively by weight each component of above-mentioned halogen-free resin composition;
(2) each to solvent in composition and all the other component is fully stirred to 2h and mix above, being configured to solid content is the halogen-free low fluidity glue of 60%-70%.
(3) the above-mentioned glue after being uniformly mixed is coated on 1080 glass fabrics, the baking oven of putting into 170 DEG C toasts 6min, obtains not flow prepreg.
According to said method make not flow prepreg: comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric. Anti-flammability reaches UL94V-0 level.
Embodiment 6
A kind of halogen-free resin composition, comprises following component and weight portion: 40 parts of epoxy resin, 30 parts of phosphorus containing phenolic resins, 20 parts of phenoxy resins, 30 parts of inorganic fillers, 30 parts of solvent cyclohexanone, 3 parts of curing agent dicyandiamides, 0.5 part of promoter glyoxal ethyline. Anti-flammability reaches UL94V-0 level.
Above-mentioned halogen-free resin composition is made to the not method of flow prepreg, comprise the steps:
(1) take respectively by weight each component of above-mentioned halogen-free resin composition;
(2) each to solvent in composition and all the other component is fully stirred to 2h and mix above, being configured to solid content is the halogen-free low fluidity glue of 60%-70%.
(3) the above-mentioned glue after being uniformly mixed is coated on 1080 glass fabrics, the baking oven of putting into 170 DEG C toasts 6min, obtains not flow prepreg.
According to said method make not flow prepreg: comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric. Anti-flammability reaches UL94V-0 level.
Embodiment 7
A kind of halogen-free resin composition, comprises following component and weight portion: 15 parts of epoxy resin, and 5 parts of phenoxy resins, 20 parts of phosphorus containing phenolic resins, 20 parts of inorganic fillers, 1 part, curing agent, 0.3 part of promoter, 20 parts of solvents, solid content is 60%. Wherein the hydroxyl equivalent of phosphorus containing phenolic resin is 600g/eq, and in described phosphorus containing phenolic resin, the content of P elements is 10%. The molecular weight of phenoxy resin is 400000. Anti-flammability reaches UL94V-0 level.
Above-mentioned halogen-free resin composition is made to the not method of flow prepreg, comprise the steps:
(1) take in proportion each component;
(2) each to solvent and all the other component is mixed, mix and make low fluidity glue;
(3) on glue coated glass fiber cloth, in the baking oven of 150 DEG C, dry 5min by obtaining in step (2), make not flow prepreg.
According to said method make not flow prepreg: comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric. Anti-flammability reaches UL94V-0 level.
Embodiment 8
A kind of halogen-free resin composition, comprises following component and weight portion: 60 parts of epoxy resin, and 30 parts of phenoxy resins, 50 parts of phosphorus containing phenolic resins, 60 parts of inorganic fillers, 5 parts, curing agent, 1.5 parts of promoter, 40 parts of solvents, solid content is 75%. Wherein the hydroxyl equivalent of phosphorus containing phenolic resin is 300g/eq, and the content of P elements is 3%. The molecular weight of phenoxy resin is 10000. Anti-flammability reaches UL94V-0 level.
Above-mentioned halogen-free resin composition is made to the not method of flow prepreg, comprise the steps:
(1) take in proportion each component;
(2) each to solvent and all the other component is mixed, mix and make low fluidity glue, the GT of glue is 300;
(3) on glue coated glass fiber cloth, in the baking oven of 200 DEG C, dry 10min by obtaining in step (2), make not flow prepreg.
According to said method make not flow prepreg: comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric. Anti-flammability reaches UL94V-0 level.
Embodiment 9
A kind of halogen-free resin composition, comprises following component and weight portion: 20 parts of epoxy resin, and 10 parts of phenoxy resins, 25 parts of phosphorus containing phenolic resins, 30 parts of inorganic fillers, 1 part, curing agent, 0.5 part of promoter, 20 parts of solvents, solid content is 60%. Wherein the hydroxyl equivalent of phosphorus containing phenolic resin is 400g/eq, and the content of P elements is 5%. The molecular weight of phenoxy resin is 30000. Anti-flammability reaches UL94V-0 level.
Above-mentioned halogen-free resin composition is made to the not method of flow prepreg, comprise the steps:
(1) take in proportion each component;
(2) each to solvent and all the other component is mixed, mix and make low fluidity glue, the GT of glue is 250;
(3) on glue coated glass fiber cloth, in the baking oven of 200 DEG C, dry 5min by obtaining in step (2), make not flow prepreg.
According to said method make not flow prepreg: comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric. Anti-flammability reaches UL94V-0 level.
Embodiment 10
A kind of halogen-free resin composition, comprises following component and weight portion: 50 parts of epoxy resin, and 20 parts of phenoxy resins, 40 parts of phosphorus containing phenolic resins, 50 parts of inorganic fillers, 5 parts, curing agent, 1.5 parts of promoter, 40 parts of solvents, solid content is 70%. Wherein the hydroxyl equivalent of phosphorus containing phenolic resin is 500g/eq, and the content of P elements is 8%; The molecular weight of described phenoxy resin is 50000. Anti-flammability reaches UL94V-0 level.
Above-mentioned halogen-free resin composition is made to the not method of flow prepreg, comprise the steps:
(1) take in proportion each component;
(2) each to solvent and all the other component is mixed, mix and make low fluidity glue, the GT of glue is 270;
(3) on glue coated glass fiber cloth, in the baking oven of 150 DEG C, dry 10min by obtaining in step (2), make not flow prepreg.
According to said method make not flow prepreg: comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric. Anti-flammability reaches UL94V-0 level.
Embodiment 11
A kind of halogen-free resin composition, comprises following component and weight portion: 57.5 parts of epoxy resin, and 20 parts of phenoxy resins, 30 parts of phosphorus containing phenolic resins, 34 parts of inorganic fillers, 5 parts, curing agent, 1.5 parts of promoter, 40 parts of solvents, solid content is 70%. Wherein the hydroxyl equivalent of phosphorus containing phenolic resin is 500g/eq, and the content of P elements is 8%; The molecular weight of described phenoxy resin is 50000. Anti-flammability reaches UL94V-0 level.
Above-mentioned halogen-free resin composition is made to the not method of flow prepreg, comprise the steps:
(1) take in proportion each component;
(2) each to solvent and all the other component is mixed, mix and make low fluidity glue, the GT of glue is 270;
(3) on glue coated glass fiber cloth, in the baking oven of 150 DEG C, dry 10min by obtaining in step (2), make not flow prepreg.
According to said method make not flow prepreg: comprise glass fabric and by flood and dry after be attached to the resin combination on glass fabric. Anti-flammability reaches UL94V-0 level.
In embodiment 1-11, epoxy resin comprises one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type, biphenyl type epoxy resin, benzoxazine colophony, alicyclic based epoxy resin, phenol phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin, linear phenolic epoxy resin, resorcinol type epoxy resin, four-functional group epoxy resin, isocyanate modified epoxy resin, 2-glycidyl amine type epoxy resin, rubber modified epoxy resin.
Inorganic filler is carried out surface treatment through silane coupler; Comprise one or more in silica, aluminium hydroxide, aluminium oxide, magnesia, magnesium hydroxide, boron nitride, aluminium nitride, talcum powder, calcium carbonate, silicon powder and Firebrake ZB, zinc stannate.
Curing agent comprises one or more in amine, phenolic resins.
Promoter comprises one or more in glyoxal ethyline, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, organic metal salt.
Solvent comprises one or more in acetone, butanone, propylene glycol monomethyl ether, dimethyl formamide, methylisobutylketone, cyclohexanone.
The not flow prepreg that embodiment 1-6 is prepared carries out performance test, and test result is as shown in table 1.
Table 1 not flow prepreg carries out performance test data contrast
As can be seen from Table 1, the not flow prepreg making can be realized halogen-free flameproof, also there is environmental protection characteristic, high-fire resistance, low thermal coefficient of expansion, high-flexibility, high bond strength and the premium properties such as gummosis not, in rigid/flexible combined printed circuit board processing procedure, use as a kind of special binding material.
Above disclosed is only preferred embodiment of the present invention, certainly can not limit with this interest field of the present invention, and the equivalent variations of therefore doing according to the claims in the present invention, still belongs to the scope that the present invention is contained.
Claims (10)
1. a halogen-free resin composition, is characterized in that, comprises following component and weight portion: epoxy treeFat 15-60 part, phenoxy resin 5-30 part, phosphorus containing phenolic resin 20-50 part, inorganic filler 20-60 part,Curing agent 1-5 part, promoter 0.3-1.5 part, solvent 20-40 part, solid content is 60-75%.
2. halogen-free resin composition according to claim 1, is characterized in that, comprise following component andWeight portion: epoxy resin 20-50 part, phenoxy resin 10-20 part, phosphorus containing phenolic resin 25-40 part, nothingMachine filler 30-50 part, curing agent 1-5 part, promoter 0.5-1.5 part, solvent 20-40 part, solid content is60％-70％。
3. according to halogen-free resin composition described in claim 1 or 2, it is characterized in that epoxy resin:Phosphorus containing phenolic resin: the weight ratio of inorganic filler is 57.5:30:34.
4. halogen-free resin composition according to claim 3, is characterized in that, total epoxide equivalent is with totalHydroxyl equivalent ratio is 1:1, and in described phosphorus containing phenolic resin, the content of P elements is 3%-10%; Described benzeneThe molecular weight of epoxy resins is 10000-400000.
5. halogen-free resin composition according to claim 4, is characterized in that described epoxy resin bagDraw together bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type, biphenyl type epoxy resin, benzoOxazine resin, alicyclic based epoxy resin, phenol phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin,Linear phenolic epoxy resin, resorcinol type epoxy resin, four-functional group epoxy resin, isocyanate-modifiedOne or more in epoxy resin, 2-glycidyl amine type epoxy resin, rubber modified epoxy resin.
6. halogen-free resin composition according to claim 4, is characterized in that described inorganic filler warpCross silane coupler and carry out surface treatment; Described inorganic filler comprises silica, aluminium hydroxide, oxidationAluminium, magnesia, magnesium hydroxide, boron nitride, aluminium nitride, talcum powder, calcium carbonate, silicon powder and boric acidOne or more in zinc, zinc stannate.
7. halogen-free resin composition according to claim 4, is characterized in that, described curing agent comprisesOne or more in amine, phenolic resins; Described promoter comprises glyoxal ethyline, 2-ethyl-4-methylOne or more in imidazoles, 1 benzyl 2 methyl imidazole, organic metal salt.
8. halogen-free resin composition according to claim 4, is characterized in that, described solvent comprises thirdOne in ketone, butanone, propylene glycol monomethyl ether, dimethyl formamide, methylisobutylketone, cyclohexanone or manyKind.
9. a use is made and is not flowed according to halogen-free resin composition described in claim 1,2,4-8 any oneThe method of glue prepreg, is characterized in that, comprises the steps:
(1) take in proportion each component;
(2) each to solvent and all the other component is mixed, the mixed GT that makes resin adhesive liquid is 250-300;
(3) will in step (2), obtain on glue coated glass fiber cloth, in the baking oven of 150-200 DEG CDry 5-10min, make not flow prepreg.
10. the not flow prepreg that method is made according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610055607.9A CN105585821B (en) | 2016-01-26 | 2016-01-26 | A kind of halogen-free resin composition and not flow prepreg and preparation method thereof using its making |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610055607.9A CN105585821B (en) | 2016-01-26 | 2016-01-26 | A kind of halogen-free resin composition and not flow prepreg and preparation method thereof using its making |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105585821A true CN105585821A (en) | 2016-05-18 |
| CN105585821B CN105585821B (en) | 2018-02-27 |
Family
ID=55925745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610055607.9A Active CN105585821B (en) | 2016-01-26 | 2016-01-26 | A kind of halogen-free resin composition and not flow prepreg and preparation method thereof using its making |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105585821B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107953630A (en) * | 2017-12-21 | 2018-04-24 | 浙江华正新材料股份有限公司 | Heated flexible molding copper-clad plate of one kind and preparation method thereof |
| CN109504033A (en) * | 2018-10-30 | 2019-03-22 | 广东翔思新材料有限公司 | A kind of flexibility prepreg and preparation method thereof |
| CN110121532A (en) * | 2017-04-07 | 2019-08-13 | 松下知识产权经营株式会社 | Resin combination, prepreg, metal-clad, printed circuit board and flexible rigid print circuit board |
| CN110818930A (en) * | 2019-11-20 | 2020-02-21 | 青岛威奥时代新材料有限公司 | Preparation method of novel phenolic-group SMC (sheet molding compound) material |
| CN112048155A (en) * | 2020-09-18 | 2020-12-08 | 林州致远电子科技有限公司 | Glue solution for halogen-free medium-Tg loss copper-clad plate and preparation method and application thereof |
| CN112250995A (en) * | 2020-10-16 | 2021-01-22 | 江苏联鑫电子工业有限公司 | Halogen-free high-flexibility semi-shading insulating plate and preparation method thereof |
| CN113121955A (en) * | 2019-12-30 | 2021-07-16 | 浙江华正新材料股份有限公司 | Ultrathin halogen-free flame-retardant glass fiber plate with low roughness and preparation method thereof |
| CN115353718A (en) * | 2022-09-22 | 2022-11-18 | 湖南亿润新材料科技有限公司 | High-flame-retardant high-temperature-resistant epoxy resin composite board and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412840A (en) * | 2008-11-24 | 2009-04-22 | 广东汕头超声电子股份有限公司覆铜板厂 | Epoxy resin glue for manufacturing copper clad laminate |
| CN101717481A (en) * | 2009-10-30 | 2010-06-02 | 镇江市电子化工材料工程技术研究中心 | Phosphorus-containing phenolic aldehyde and preparation method thereof |
| CN103013046A (en) * | 2012-12-13 | 2013-04-03 | 广东生益科技股份有限公司 | Halogen-free flame retardant resin composition and use thereof |
| CN104497271A (en) * | 2014-12-24 | 2015-04-08 | 济南圣泉集团股份有限公司 | Modified epoxy resin and modified epoxy resin composition |
| CN104592467A (en) * | 2014-08-15 | 2015-05-06 | 江苏雅克科技股份有限公司 | Phosphorus-containing phenol formaldehyde resin compound and phosphorus-containing fire retardation epoxy resin cured product prepared by adopting phosphorus-containing phenol formaldehyde resin compound as raw material |
| CN104610708A (en) * | 2015-01-19 | 2015-05-13 | 珠海全宝电子科技有限公司 | High-temperature-resistant and aging-resistant substrate and production method thereof |
-
2016
- 2016-01-26 CN CN201610055607.9A patent/CN105585821B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412840A (en) * | 2008-11-24 | 2009-04-22 | 广东汕头超声电子股份有限公司覆铜板厂 | Epoxy resin glue for manufacturing copper clad laminate |
| CN101717481A (en) * | 2009-10-30 | 2010-06-02 | 镇江市电子化工材料工程技术研究中心 | Phosphorus-containing phenolic aldehyde and preparation method thereof |
| CN103013046A (en) * | 2012-12-13 | 2013-04-03 | 广东生益科技股份有限公司 | Halogen-free flame retardant resin composition and use thereof |
| CN104592467A (en) * | 2014-08-15 | 2015-05-06 | 江苏雅克科技股份有限公司 | Phosphorus-containing phenol formaldehyde resin compound and phosphorus-containing fire retardation epoxy resin cured product prepared by adopting phosphorus-containing phenol formaldehyde resin compound as raw material |
| CN104497271A (en) * | 2014-12-24 | 2015-04-08 | 济南圣泉集团股份有限公司 | Modified epoxy resin and modified epoxy resin composition |
| CN104610708A (en) * | 2015-01-19 | 2015-05-13 | 珠海全宝电子科技有限公司 | High-temperature-resistant and aging-resistant substrate and production method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李广宇等: "《环氧胶黏剂与应用技术》", 31 July 2007 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110121532A (en) * | 2017-04-07 | 2019-08-13 | 松下知识产权经营株式会社 | Resin combination, prepreg, metal-clad, printed circuit board and flexible rigid print circuit board |
| CN107953630A (en) * | 2017-12-21 | 2018-04-24 | 浙江华正新材料股份有限公司 | Heated flexible molding copper-clad plate of one kind and preparation method thereof |
| CN109504033A (en) * | 2018-10-30 | 2019-03-22 | 广东翔思新材料有限公司 | A kind of flexibility prepreg and preparation method thereof |
| CN109504033B (en) * | 2018-10-30 | 2021-01-01 | 广东翔思新材料有限公司 | Flexible prepreg and preparation method thereof |
| CN110818930A (en) * | 2019-11-20 | 2020-02-21 | 青岛威奥时代新材料有限公司 | Preparation method of novel phenolic-group SMC (sheet molding compound) material |
| CN113121955A (en) * | 2019-12-30 | 2021-07-16 | 浙江华正新材料股份有限公司 | Ultrathin halogen-free flame-retardant glass fiber plate with low roughness and preparation method thereof |
| CN113121955B (en) * | 2019-12-30 | 2022-06-21 | 浙江华正新材料股份有限公司 | Ultrathin halogen-free flame-retardant glass fiber plate with low roughness and preparation method thereof |
| CN112048155A (en) * | 2020-09-18 | 2020-12-08 | 林州致远电子科技有限公司 | Glue solution for halogen-free medium-Tg loss copper-clad plate and preparation method and application thereof |
| CN112250995A (en) * | 2020-10-16 | 2021-01-22 | 江苏联鑫电子工业有限公司 | Halogen-free high-flexibility semi-shading insulating plate and preparation method thereof |
| CN115353718A (en) * | 2022-09-22 | 2022-11-18 | 湖南亿润新材料科技有限公司 | High-flame-retardant high-temperature-resistant epoxy resin composite board and preparation method thereof |
| CN115353718B (en) * | 2022-09-22 | 2024-01-26 | 湖南亿润新材料科技有限公司 | High-flame-retardance high-temperature-resistant epoxy resin composite board and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105585821B (en) | 2018-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105585821A (en) | Halogen-free resin composition, no-flow prepreg prepared from halogen-free resin composition and manufacturing method of prepreg | |
| TWI476244B (en) | Halogen-free resin composition | |
| US9187635B2 (en) | Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same | |
| JP3613724B2 (en) | Phosphorus-containing epoxy resin composition | |
| CN102369227B (en) | Phosphorus-containing phenol novolac resin, hardener comprising the same and epoxy resin composition | |
| CN106832226B (en) | A kind of halogen-free epoxy resin composition and prepreg, laminate and printed circuit board containing it | |
| CN103131131B (en) | Halogen-free resin composition and copper clad laminate and printed circuit board applying the same | |
| US20050159516A1 (en) | Halogen-free flame-retardant resin composition and prepreg and laminate using the same | |
| TWI646142B (en) | Resin composition and copper foil substrate and printed circuit board using same | |
| WO2015149449A1 (en) | Halogen-free resin composition and use thereof | |
| US20140322541A1 (en) | Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same | |
| CN101851480A (en) | Halogen-free and phosphorous-free flame-retardant synthetic resin adhesive used for flexible copper clad laminate | |
| CN102975430A (en) | Flame-retarding copper clad laminate coated with solid content containing phosphorous and no halogen and preparation method thereof | |
| EP3040358B1 (en) | Halogen-free thermosetting resin composition, and prepreg and laminate for printed circuits using the same | |
| TWI548667B (en) | A halogen-free thermosetting resin composition, and a prepreg for use and a laminate for printed circuit | |
| WO2015184652A1 (en) | Zero-halogen resin composition and prepreg and printed circuit laminate using same | |
| JP5441477B2 (en) | Flame retardant phosphorus-containing epoxy resin composition and cured product thereof | |
| JP5399733B2 (en) | Flame retardant phosphorus-containing epoxy resin composition and cured product thereof | |
| CN109439257A (en) | A kind of preparation method of the low dielectric type copper coated foil plate of the high Tg of Halogen | |
| CN106146803A (en) | Low dielectric phosphor-containing flame-proof curing agent and application thereof | |
| TWI382055B (en) | Thermosetting resin composition | |
| WO2017148127A1 (en) | Halogen-free thermosetting resin composition, and prepreg and laminate for printed circuits using same | |
| TW201835208A (en) | A process for the preparation of a flame retardant modified styrene-maleic anhydride resins and a composition of epoxy resins and their applying use to copper clad laminate and prepreg | |
| KR20020047333A (en) | Phosphorus-containing epoxy resin, flame-retardant highly heat-resistant epoxy resin composition containing the resin, and laminate | |
| JP2008013773A (en) | Flame-retardant non-halogen epoxy resin composition, prepreg using it and laminate for electric wiring boards |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230320 Address after: No. 28, Guangshun Road, Haojiang District, Shantou City, Guangdong Province, 515000 Patentee after: Shantou Ultrasonic Copper Clad Plate Technology Co.,Ltd. Address before: 515000 Plot E04, Haojiang Free Trade Zone, Shantou City, Guangdong Province Patentee before: GUANGDONG SHANTOU ULTRASONIC ELECTRONIC CO.,LTD. COPPER CLAD FACTORY |
|
| TR01 | Transfer of patent right |