CN103724997B - A kind of Halogen low water suction thermoset fire-proof resin composition and application - Google Patents
A kind of Halogen low water suction thermoset fire-proof resin composition and application Download PDFInfo
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- CN103724997B CN103724997B CN201310752330.1A CN201310752330A CN103724997B CN 103724997 B CN103724997 B CN 103724997B CN 201310752330 A CN201310752330 A CN 201310752330A CN 103724997 B CN103724997 B CN 103724997B
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2363/00—Epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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
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- 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
Abstract
The invention discloses a kind of Halogen low water suction thermoset fire-proof resin composition, it comprises the component of following parts by weight: many rings benzoxazine colophony 25-75 part; Polyfunctional epoxy resin 10-50 part; Phosphorus containing phenolic resin 15-25 part; Stiffening agent 0.2-20 part.Halogen of the present invention low water suction thermoset fire-proof resin composition can be applied and make bonding sheet and copper-clad plate, this copper-clad plate has high heat resistance, low thermal expansion, low-dielectric loss factor, low water absorbable and good processing characteristics, and flame retardant properties can meet UL94-V0.
Description
Technical field
The present invention relates to Halogen low water suction thermoset fire-proof resin composition and application, especially relate to Halogen low water suction thermoset fire-proof resin composition and apply this Halogen low water suction thermoset fire-proof resin composition and prepare bonding sheet and copper-clad plate.
Background technology
Along with the enforcement of European Union's " electrically, Electronic Wastes instruction " and " special harmful substance uses to limit and makes " these two " european union directives ", electronic product halogen-free and lead-free is trend of the times, copper-clad plate should the inevitable problem of halogen-free and lead-free Yi Shi manufacturers as the base mateiral of electronic product, traditional copper-clad plate utilizes bromide as fire retardant to reach flame retardant effect, and research shows that bromide can discharge carcinogenic dioxin serious environment pollution and affect human body healthy when burning.
In order to meet market demands, industry adopts the fire retardant material of phosphorus series to substitute bromine fire-retardant material.Although conventional phosphorous epoxy resin, Nitrogen-containing Phenolic Resins meet most of requirement of FR-4 copper-clad plate halogen-free flameproof, but still come with some shortcomings, as reached for meeting product the ratio that UL94-V0 flame-retardancy requirements must ensure phosphorus (phosphorus content 3 ± 0.05%) content, it is large to there is water-intake rate in such product, the defects such as poor heat resistance, easily moisture absorption are made moist, wicking poor heat resistance.Water-intake rate is existed for conventional phosphorous epoxy resin series large, poor heat resistance, easily moisture absorption are made moist, method that the defect such as wicking poor heat resistance is general at present introduces benzoxazine colophony.Can generate the structure of similar resol after benzoxazine colophony open loop, effectively can reduce the water-intake rate of the rear system of solidification, improve chemical resistant properties, but the substrate after solidification exists snappiness difference, fragility is large, and wicking thermotolerance is not enough, the defects such as processing characteristics is bad.
Summary of the invention
The object of the invention is to solve above-mentioned technical problem, a kind of Halogen low water suction thermoset fire-proof resin composition and application are provided, apply copper-clad plate prepared by this Halogen low water suction thermoset fire-proof resin composition and there is high heat resistance, low thermal expansion, low-dielectric loss factor, low water absorbable and good processing characteristics, and its flame retardant properties meets the requirement of UL94-V0.
For achieving the above object, the present invention adopts following technical scheme: a kind of Halogen low water suction thermoset fire-proof resin composition, and it comprises the component of following parts by weight:
Wherein, described many rings benzoxazine colophony as shown in the formula (I),
In described formula (I), n is the integer of 2-6;
Described polyfunctional epoxy resin is such as formula shown in (II) or formula (III):
In described formula (II), n be greater than 1 integer; ;
Described phosphorus containing phenolic resin is such as formula shown in (IV);
In described formula (IV), n is the integer of 1-6;
Described stiffening agent is lacquer resins, and described lacquer resins is the one in phenol novolaks, adjacent A type lacquer resins, Bisphenol-A type linear resol, the nitrogenous lacquer resins of triazine modification.
In the present invention, many rings benzoxazine colophony is adopted to substitute existing benzoxazine colophony.Because many rings benzoxazine colophony generates except the structure of similar resol except having in good molecular designing, phenyl ring to contain after nitrogen-atoms can provide fire-retardant factor, open loop, small molecules is not produced after also there is polymerization, polymerization density is large, carbon forming rate is high, effectively can reduce the unrelieved stress of polymeric inner, thus improve the thermostability of polymkeric substance, low water absorbable, improve second-order transition temperature and the chemical resistant properties of cured article.Many rings benzoxazine colophony and polyfunctional epoxy resin and resol blended after, effectively reduce the solidification value of blend, improve toughness, there is fine machinability.Many rings benzoxazine colophony ratio in Halogen of the present invention low water suction thermoset fire-proof resin composition will reduce the resistance to wicking of copper-clad plate higher than 75 weight parts, and ratio reduces lower than 25 weight part wet fastnesss.
In the present invention, the easy moisture absorption of phosphorous epoxy resin that the polyfunctional epoxy resin added overcomes in the past is made moist, and molecule crosslinked density is little, have impact on the thermotolerance of cured article.Polyfunctional epoxy resin has multiple epoxide group, and add the cross-linking density of Halogen low water suction thermoset fire-proof resin composition, copper-clad plate prepared by the later stage has good thermotolerance, erosion resistance, dielectricity and mechanical property.Polyfunctional epoxy resin and phosphorus containing phenolic resin blended after except meet fire-retardant except can also increase toughness, improve second-order transition temperature, Heat stability is good.
Although phosphorous epoxy resin in the past meets most of requirement of FR-4 copper-clad plate halogen-free flameproof, but, if thermotolerance, flexible material need be added for meeting other requirements, then cured article flame retardant resistance cannot ensure, if synthesize high phosphorous epoxy resin, then oxirane value is not up to standard, reactionless activity.In the present invention, phosphorus containing phenolic resin is in resol, introduce multiple phosphorus-containing groups, so not only substantially increases flame retardant effect, also improves the thermotolerance of resin.
Further, in preferred the present invention, it is heavy that described many rings benzoxazine colophony is preferably 30-65, and it is heavy that polyfunctional epoxy resin is preferably 15-45, and it is heavy that phosphorus containing phenolic resin is preferably 15-20.
Further, also comprise imidazoles promotor in described stiffening agent, the add-on of described imidazoles promotor in Halogen low water suction thermoset fire-proof resin composition is 0.05-2.5 parts by weight.
Further, described imidazoles promotor is the one in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole.
Further, described Halogen low water suction thermoset fire-proof resin composition, it also comprises the mineral filler that parts by weight are 15-40, is preferably 15-25 weight part.
Further, described mineral filler is one or more the mixing in aluminium hydroxide, silicon dioxide powder, zinc borate, mica powder, talcum powder or magnesium oxide, is preferably aluminium hydroxide, silicon dioxide powder or zinc borate.
Further, in described phosphorus containing phenolic resin, the weight percentage of phosphorus is 2.0-4.0%, ensures the flame retardant resistance of copper-clad plate prepared by this Halogen of application low water suction thermoset fire-proof resin composition.
The Halogen low water suction thermoset fire-proof resin composition that the invention also discloses described in application prepares the preparation method of bonding sheet, and described preparation method comprises the following steps:
1) low for Halogen water suction thermoset fire-proof resin composition and solvent are joined in mixed glue still, and stir, in mixing solutions, solids content is 60-80%; Described solvent is butanone or acetone;
2) inorganic or organic textile material are immersed in the Halogen low water suction thermoset fire-proof resin composition solution that step 1) obtains;
3) the inorganic or organic textile material warp heating, drying 5-8min at 168-172 DEG C will flooded, obtains described bonding sheet.
Further, the invention also discloses the preparation method applying the bonding sheet prepared and prepare copper-clad plate, described preparation method comprises the following steps:
1) by two or two above-described bonding sheet superpositions;
2) single or double of the bonding sheet superposed in step 1) is covered with tinsel;
3) by step 2) bonding sheet that is covered with tinsel is hot-forming.
Containing components such as many rings benzoxazine colophony, polyfunctional epoxy resin and phosphorus containing phenolic resins in Halogen of the present invention low water suction thermoset fire-proof resin composition, apply this resin combination and prepare bonding sheet and copper-clad plate, this copper-clad plate has high heat resistance, low thermal expansion, low-dielectric loss factor, low water absorbable and good processing characteristics, and flame retardant properties can meet UL94-V0.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation:
The invention discloses a kind of Halogen low water suction thermoset fire-proof resin composition, it comprises the component of following parts by weight:
Wherein, described many rings benzoxazine colophony as shown in the formula (I),
In described formula (I), n is the integer of 2-6;
Described polyfunctional epoxy resin is such as formula shown in (II) or formula (III):
In described formula (II), n be greater than 1 integer; ;
Described phosphorus containing phenolic resin is such as formula shown in (IV);
In described formula (IV), n is the integer of 1-6;
Described stiffening agent is lacquer resins, and described lacquer resins is the one in phenol novolaks, adjacent A type lacquer resins, Bisphenol-A type linear resol, the nitrogenous lacquer resins of triazine modification.
In the present invention, it is heavy that described many rings benzoxazine colophony is preferably 30-65, and it is heavy that polyfunctional epoxy resin is preferably 15-45, and it is heavy that phosphorus containing phenolic resin is preferably 15-20.
Described stiffening agent also comprises imidazoles promotor, and the add-on of described imidazoles promotor in Halogen low water suction thermoset fire-proof resin composition is 0.05-2.5 parts by weight.Described imidazoles promotor is the one in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole.
Described Halogen low water suction thermoset fire-proof resin composition, it also comprises the mineral filler that parts by weight are 15-40, is preferably 15-25 weight part.Described mineral filler is one or more the mixing in aluminium hydroxide, silicon dioxide powder, zinc borate, mica powder, talcum powder or magnesium oxide.Be preferably aluminium hydroxide, silicon dioxide powder or zinc borate.
In described phosphorus containing phenolic resin, the weight percentage of phosphorus is 2.0-4.0%.
The preparation embodiment of Halogen low water suction thermoset fire-proof resin composition
Embodiment 1
Halogen low water suction thermoset fire-proof resin composition comprises:
Many rings benzoxazine colophony, as shown in the formula (I), n is 2;
Trifunctional epoxy resin, as shown in the formula (II),
Phosphorus containing phenolic resin such as formula shown in (IV),
Stiffening agent is the mixing of phenol novolaks and promotor glyoxal ethyline;
Mineral filler is the mixing by weight 1:1 of talcum powder and aluminium hydroxide.
Embodiment 2
Halogen low water suction thermoset fire-proof resin composition comprises:
Many rings benzoxazine colophony, as shown in the formula (I), n is 3;
Trifunctional epoxy resin, as shown in the formula (II), n is 2;
Phosphorus containing phenolic resin is such as formula shown in (IV), and n is 2;
Stiffening agent is the mixing of adjacent A type lacquer resins and promotor glyoxal ethyline;
Mineral filler is aluminium hydroxide.
Embodiment 3
Halogen low water suction thermoset fire-proof resin composition comprises:
Many rings benzoxazine colophony, as shown in the formula (I), n is 4;
Trifunctional epoxy resin, as shown in the formula (II), n is 3;
Phosphorus containing phenolic resin is such as formula shown in (IV), and n is 3;
Stiffening agent is the mixing of Bisphenol-A type linear resol and promotor 2-ethyl-4-methylimidazole;
Mineral filler is silicon dioxide powder.
Embodiment 4
Halogen low water suction thermoset fire-proof resin composition comprises:
Many rings benzoxazine colophony, as shown in the formula (I), n is 5;
Four-functional group epoxy resin, shown in (IIII),
Phosphorus containing phenolic resin is such as formula shown in (IV), and n is 4;
Stiffening agent is the mixing of the nitrogenous lacquer resins of triazine modification and promotor 2-phenylimidazole;
Mineral filler is the mixing by weight 1:1 of zinc borate and mica powder.
Embodiment 5
Halogen low water suction thermoset fire-proof resin composition comprises:
Many rings benzoxazine colophony, as shown in the formula (I), n is 6;
Four-functional group epoxy resin, shown in (IIII),
Phosphorus containing phenolic resin is such as formula shown in (IV), and n is 5;
Stiffening agent is the mixing of phenol novolaks and promotor 2-phenyl-4-methylimidazole.
Embodiment 6
Halogen low water suction thermoset fire-proof resin composition comprises:
Many rings benzoxazine colophony, as shown in the formula (I), n is 2;
Four-functional group epoxy resin, shown in (IIII);
Phosphorus containing phenolic resin is such as formula shown in (IV), and n is 4;
Stiffening agent is the mixing of the nitrogenous lacquer resins of triazine modification and promotor 2-phenyl-4-methylimidazole;
Mineral filler is aluminium hydroxide.
The median size of the mineral filler in embodiment 1 to embodiment 6 is 1-3 μm, purity more than 99%.In embodiment 1 to embodiment 6 each component feed intake as shown in table 1.
The each component of Halogen low water suction thermoset fire-proof resin composition of table 1 embodiment 1 to embodiment 6 feeds intake.
Halogen provided by the invention low water suction thermoset fire-proof resin composition is that conventional preparation method obtains, and apply the preparation method that described resin combination prepares bonding sheet, described preparation method comprises the following steps:
1) low for Halogen water suction thermoset fire-proof resin composition and appropriate solvent are joined in mixed glue still, stir, and slaking 5-8 hour, in mixing solutions, solid content is 60-80%; Described solvent is acetone or butanone;
2) inorganic or organic textile material are immersed in the Halogen low water suction thermoset fire-proof resin composition solution that step 1) obtains;
3) the inorganic or organic textile material warp heating, drying 5-8min at 168-172 DEG C will flooded, obtains described bonding sheet.
Apply the preparation method that the bonding sheet prepared prepares copper-clad plate, described preparation method comprises the following steps:
1) by two or two above-described bonding sheet superpositions;
2) single or double of the bonding sheet superposed in step 1) is covered with tinsel;
3) by step 2) bonding sheet that is covered with tinsel is hot-forming.
In described step 3), hot-forming condition is: should control temperature rise rate when temperature is 80 ~ 140 DEG C at 1.5 ~ 2.5 DEG C/min; Outer material temperature applies full pressure 80 ~ 100 DEG C time, and full pressure pressure is about 350psi; During solidification, control material temperature at 185 DEG C, and be incubated 60min.
Halogen low water suction thermoset fire-proof resin composition prepared by Application Example 1 to embodiment 6 adopts the preparation method of above-mentioned bonding sheet, prepare the bonding sheet of embodiment 1 to embodiment 6 respectively, the preparation method of above-mentioned copper-clad plate is adopted by the bonding sheet of this embodiment 1 to embodiment 6, prepare the copper-clad plate of embodiment 1 to embodiment 6 respectively, after testing, it is as shown in table 2 that it detects data in the copper-clad plate of embodiment 1 to embodiment 6.
The testing method of each performance in table 2 is as follows:
(1) glass transition temperature Tg: according to differential scanning calorimetry (DSC), measures according to the DSC method of 2.4.25 defined in IPC-TM-650.
(2) Z axis thermal expansivity CET(α 2) TMA: measure according to the method for 2.4.24 defined in IPC-TM-650.
(3) heat decomposition temperature Td (5%): measure according to the method for 2.4.26 defined in IPC-TM-650.
(4) the thermally stratified layer time (T300): measure according to the method for 2.4.24.1 defined in IPC-TM-650.
(5) stripping strength: according to the experiment condition of " after the thermal stresses " in 2.4.8 method in IPC-TM-650, measures the stripping strength of metallic cover layer.
(6) wicking thermotolerance: make and be of a size of the sample that 50mmX50mm two sides is covered with Copper Foil, immerses in the solder furnace of 288 DEG C of constant temperature by sample, the time that the layering of record sample is bubbled.
(7) resistance to flame UL94: measure according to UL94 vertical combustion.
(8) specific inductivity (1GHZ): use the specific inductivity under flat band method mensuration 1MHZ according to 2.5.5.9 in IPC-TM-650.
(9) dielectric loss angle tangent Df1MHZ: use the dielectric loss factor under flat band method mensuration 1MHZ according to 2.5.5.9 in IPC-TM-650.
(10) water-intake rate: measure according to 2.6.2.1 method in IPC-TM-650.
(11) content of halogen (Cl, Br): measure according to 2.3.41 method in IPC-TM-650.
The bonding sheet that Halogen low water absorbable thermoset fire-proof resin composition of the present invention is obtained and printed electronic circuit copper-clad plate, have high heat resistance, low thermal expansion, low-dielectric loss factor, low water absorbable and good processing characteristics, its flame retardant properties meets the requirement of UL94-V0.
The restriction of above embodiment not to the present composition, all equivalence changes done by the principle of the invention, technical spirit, trickle amendment and modification, all belong to protection scope of the present invention.
Claims (9)
1. a Halogen low water suction thermoset fire-proof resin composition, is characterized in that: it comprises the component of following parts by weight:
Wherein, described many rings benzoxazine colophony such as formula shown in (I),
In described formula (I), n is the integer of 2-6;
Described polyfunctional epoxy resin is such as formula shown in (II) or formula (III):
In described formula (II), n be greater than 1 integer;
Described phosphorus containing phenolic resin is such as formula shown in (IV);
In described formula (IV), n is the integer of 1-6;
Described stiffening agent is lacquer resins, and described lacquer resins is the one in phenol novolaks, adjacent A type lacquer resins, Bisphenol-A type linear resol, the nitrogenous lacquer resins of triazine modification.
2. Halogen according to claim 1 low water suction thermoset fire-proof resin composition, is characterized in that: described many rings benzoxazine colophony is 30-65 part; Described polyfunctional epoxy resin 15-45 part; Described phosphorus containing phenolic resin 15-20 part.
3. Halogen according to claim 1 low water suction thermoset fire-proof resin composition, it is characterized in that: described stiffening agent also comprises imidazoles promotor, the add-on of described imidazoles promotor in Halogen low water suction thermoset fire-proof resin composition is 0.05-2.5 parts by weight.
4. Halogen according to claim 3 low water suction thermoset fire-proof resin composition, is characterized in that: described imidazoles promotor is the one in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole.
5. Halogen according to claim 1 low water suction thermoset fire-proof resin composition, is characterized in that: it also comprises the mineral filler that parts by weight are 15-40.
6. Halogen according to claim 5 low water suction thermoset fire-proof resin composition, is characterized in that: described mineral filler is one or more the mixing in aluminium hydroxide, silicon dioxide powder, zinc borate, mica powder, talcum powder or magnesium oxide.
7. Halogen according to claim 1 low water suction thermoset fire-proof resin composition, is characterized in that: in described phosphorus containing phenolic resin, the weight percentage of phosphorus is 2.0-4.0%.
8. application rights requires that the described Halogen low water suction thermoset fire-proof resin composition of one of 1-7 prepares the preparation method of bonding sheet, it is characterized in that: described preparation method comprises the following steps:
1) low for Halogen water suction thermoset fire-proof resin composition and solvent are joined in mixed glue still, and stir, in mixing solutions, solids content is 60-80%; Described solvent is butanone or acetone;
2) inorganic or organic textile material are immersed in step 1) in the Halogen low water suction thermoset fire-proof resin composition solution that obtains;
3) the inorganic or organic textile material warp heating, drying 5-8min at 168-172 DEG C will flooded, obtains described bonding sheet.
9. the bonding sheet of application as claim 8 prepares prepares the preparation method of copper-clad plate, it is characterized in that: described preparation method comprises the following steps:
1) by two or two above-described bonding sheet superpositions;
2) in step 1) single or double of bonding sheet that superposed is covered with tinsel;
3) by step 2) bonding sheet that is covered with tinsel is hot-forming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310752330.1A CN103724997B (en) | 2013-12-31 | 2013-12-31 | A kind of Halogen low water suction thermoset fire-proof resin composition and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310752330.1A CN103724997B (en) | 2013-12-31 | 2013-12-31 | A kind of Halogen low water suction thermoset fire-proof resin composition and application |
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| Publication Number | Publication Date |
|---|---|
| CN103724997A CN103724997A (en) | 2014-04-16 |
| CN103724997B true CN103724997B (en) | 2016-01-06 |
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| CN201310752330.1A Expired - Fee Related CN103724997B (en) | 2013-12-31 | 2013-12-31 | A kind of Halogen low water suction thermoset fire-proof resin composition and application |
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| CN104804377B (en) * | 2015-01-28 | 2017-05-24 | 广东生益科技股份有限公司 | Halogen-free resin composition, and prepreg and laminated boards which are prepared from halogen-free resin composition |
| CN105542396A (en) * | 2016-01-26 | 2016-05-04 | 广东汕头超声电子股份有限公司覆铜板厂 | High-modulus epoxy resin composition, preparation method thereof, prepreg and laminated board manufactured from same and preparation method of prepreg and laminated board |
| CN106751821B (en) * | 2016-12-29 | 2019-07-26 | 广东生益科技股份有限公司 | A kind of halogen-free flame resistance resin composite and bonding sheet and copper-clad laminate using it |
| CN109836778B (en) * | 2019-02-26 | 2021-05-28 | 金安国纪科技（杭州）有限公司 | Epoxy resin composition, preparation method and application thereof |
| CN111253709A (en) * | 2020-04-02 | 2020-06-09 | 厦门英勒威新材料科技有限公司 | Copper-clad plate glue solution and black low-transmittance copper-clad plate |
| CN112194881A (en) * | 2020-10-09 | 2021-01-08 | 付鹏 | Manufacturing method of double-sided circuit board with embedded copper block |
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