CN103724997A - Halogen-free low water-absorbent thermosetting flame retardant resin composition and application thereof - Google Patents
Halogen-free low water-absorbent thermosetting flame retardant resin composition and application thereof Download PDFInfo
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- 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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- 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
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- 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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- 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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- 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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- 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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- 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
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- 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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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/22—Halogen free composition
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Abstract
The invention discloses a halogen-free low water-absorbent thermosetting flame retardant resin composition. The composition consists of the following components in parts by weight: 25-75 parts of polycyclic benzoxazine resin, 10-50 parts of multi-functional epoxy resin, 15-25 parts of phosphorus containing phenolic resin and 0.2-20 parts of hardening agent. The halogen-free low water-absorbent thermosetting flame retardant resin composition disclosed by the invention can be prepared into a bonding sheet and a copper-clad plate; the copper-clad plate is high in heat resistance, low in expansion rate, low in dielectric dissipation factor, low in water-absorbing quality and good in processing performance, and flame retardant property can satisfy 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 the low water suction thermoset of this Halogen fire-proof resin composition and prepare bonding sheet and copper-clad plate.
Background technology
Along with the < < of European Union is electric, Electronic Wastes instruction > > and < < special harmful substance are used restriction to make the enforcement of > > 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 to reach flame retardant effect as fire retardant, 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 have met 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 the fire-retardant requirement of UL94-V0 must guarantee phosphorus (phosphorus content 3 ± 0.05%) content, product exists water-intake rate large like this, the defects such as poor heat resistance, easy moisture absorption are made moist, wicking poor heat resistance.For conventional phosphorous epoxy resin series, exist water-intake rate large, the defects such as poor heat resistance, easy moisture absorption are made moist, wicking poor heat resistance at present general method are to introduce benzoxazine colophony.After benzoxazine colophony open loop, can generate the structure of similar resol, can effectively reduce the water-intake rate of system after solidifying, improve chemical resistant properties, but the defect such as substrate after solidifying exists snappiness poor, and fragility is large, and wicking thermotolerance is not enough, and 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 the low water suction thermoset of this Halogen 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: the low water suction thermoset of a kind of Halogen fire-proof resin composition, and it comprises the component of following parts by weight:
Wherein, described many ring benzoxazine colophonies as shown in the formula (I),
In described formula (I), the integer that n is 2-6;
Described polyfunctional epoxy resin is suc as formula shown in (II) or formula (III):
In described formula (II), n is greater than 1 integer; ;
Described phosphorus containing phenolic resin is suc as formula shown in (IV);
In described formula (IV), the integer that n is 1-6;
Described stiffening agent is lacquer resins, and described lacquer resins is a kind of in phenol lacquer resins, adjacent A type lacquer resins, bisphenol A-type lacquer resins, the nitrogenous lacquer resins of triazine modification.
In the present invention, adopt many ring benzoxazine colophonies to substitute existing benzoxazine colophony.Because containing after nitrogen-atoms can provide fire-retardant factor, open loop in having good molecular designing, phenyl ring, many ring benzoxazine colophonies generate the structure of similar resol, after also thering is polymerization, do not produce small molecules, polymerization density is large, carbon forming rate is high, can effectively reduce the unrelieved stress of polymkeric substance inside, thereby improved the thermostability of polymkeric substance, low water absorbable, has improved second-order transition temperature and the chemical resistant properties of cured article.After many ring benzoxazine colophonies and polyfunctional epoxy resin and resol blend, effectively reduce the solidification value of blend, improved toughness, there is fine machinability.Many ring benzoxazine colophonies ratio in the low water suction thermoset of Halogen of the present invention 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 polyfunctional epoxy resin adding has overcome the easy moisture absorption of phosphorous epoxy resin in the past and has made moist, and molecule crosslinked density is little, has affected the thermotolerance of cured article.Polyfunctional epoxy resin has a plurality of epoxide groups, has increased the cross-linking density of the low water suction thermoset of Halogen fire-proof resin composition, makes copper-clad plate prepared by the later stage have good thermotolerance, erosion resistance, dielectricity and mechanical property.After polyfunctional epoxy resin and phosphorus containing phenolic resin blend, except meeting fire-retardant, can also increase toughness, improve second-order transition temperature, Heat stability is good.
Although phosphorous epoxy resin has in the past met most of requirement of FR-4 copper-clad plate halogen-free flameproof, but, meet if other requirements and need add thermotolerance, flexible material, cured article flame retardant resistance cannot guarantee, if synthetic high phosphorous epoxy resin, oxirane value is not up to standard, reactionless activity.In the present invention, phosphorus containing phenolic resin is in resol, to have introduced a plurality of phosphorus-containing groups, has so not only greatly improved flame retardant effect, has also improved the thermotolerance of resin.
Further, preferably, in the present invention, it is heavy that described many ring benzoxazine colophonies are 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 the low water suction thermoset of Halogen fire-proof resin composition is 0.05-2.5 parts by weight.
Further, described imidazoles promotor is a kind of in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole.
Further, the low water suction thermoset of described Halogen fire-proof resin composition, it also comprises that parts by weight are the mineral filler of 15-40, are 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%, guarantees the flame retardant resistance of copper-clad plate prepared by the low water suction thermoset of this Halogen of application fire-proof resin composition.
The invention also discloses the described low water suction thermoset of the Halogen fire-proof resin composition of application and prepare the preparation method of bonding sheet, described preparation method comprises the following steps:
1) Halogen low 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 weaving material is immersed in the low water suction thermoset of the Halogen fire-proof resin composition solution that step 1) obtains;
3) by the inorganic or organic weaving material warp heating, drying 5-8min at 168-172 ℃ having flooded, obtain described bonding sheet.
Further, the invention also discloses and apply the preparation method that the bonding sheet preparing is prepared copper-clad plate, described preparation method comprises the following steps:
1) by two or two above-described bonding sheet stacks;
2) on the single or double of the bonding sheet superposeing in step 1), be covered with tinsel;
3) by step 2) bonding sheet that is covered with tinsel is hot-forming.
In the low water suction thermoset of Halogen of the present invention fire-proof resin composition, contain the components such as many ring benzoxazine colophony, polyfunctional epoxy resin and phosphorus containing phenolic resins, 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 can flame retardant properties meet UL94-V0.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation:
The invention discloses the low water suction thermoset of a kind of Halogen fire-proof resin composition, it comprises the component of following parts by weight:
Wherein, described many ring benzoxazine colophonies as shown in the formula (I),
In described formula (I), the integer that n is 2-6;
Described polyfunctional epoxy resin is suc as formula shown in (II) or formula (III):
In described formula (II), n is greater than 1 integer; ;
Described phosphorus containing phenolic resin is suc as formula shown in (IV);
In described formula (IV), the integer that n is 1-6;
Described stiffening agent is lacquer resins, and described lacquer resins is a kind of in phenol lacquer resins, adjacent A type lacquer resins, bisphenol A-type lacquer resins, the nitrogenous lacquer resins of triazine modification.
In the present invention, it is heavy that described many ring benzoxazine colophonies are 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 the low water suction thermoset of Halogen fire-proof resin composition is 0.05-2.5 parts by weight.Described imidazoles promotor is a kind of in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole.
The low water suction thermoset of described Halogen fire-proof resin composition, it also comprises that parts by weight are the mineral filler of 15-40, are 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 Example of the low water suction thermoset of Halogen fire-proof resin composition
Embodiment 1
The low water suction thermoset of Halogen fire-proof resin composition comprises:
Many ring benzoxazine colophonies, as shown in the formula (I), n is 2;
Trifunctional epoxy resin, as shown in the formula (II),
Phosphorus containing phenolic resin is suc as formula shown in (IV),
Stiffening agent is the mixing of phenol lacquer resins and promotor glyoxal ethyline;
Mineral filler is talcum powder and the aluminium hydroxide mixing of 1:1 by weight.
Embodiment 2
The low water suction thermoset of Halogen fire-proof resin composition comprises:
Many ring benzoxazine colophonies, 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 suc 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
The low water suction thermoset of Halogen fire-proof resin composition comprises:
Many ring benzoxazine colophonies, 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 suc as formula shown in (IV), and n is 3;
Stiffening agent is the mixing of bisphenol A-type lacquer resins and promotor 2-ethyl-4-methylimidazole;
Mineral filler is silicon dioxide powder.
Embodiment 4
The low water suction thermoset of Halogen fire-proof resin composition comprises:
Many ring benzoxazine colophonies, as shown in the formula (I), n is 5;
Four-functional group epoxy resin, shown in (IIII),
Phosphorus containing phenolic resin is suc 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 zinc borate and the mica powder mixing of 1:1 by weight.
Embodiment 5
The low water suction thermoset of Halogen fire-proof resin composition comprises:
Many ring benzoxazine colophonies, as shown in the formula (I), n is 6;
Four-functional group epoxy resin, shown in (IIII),
Phosphorus containing phenolic resin is suc as formula shown in (IV), and n is 5;
Stiffening agent is the mixing of phenol lacquer resins and promotor 2-phenyl-4-methylimidazole.
Embodiment 6
The low water suction thermoset of Halogen fire-proof resin composition comprises:
Many ring benzoxazine colophonies, as shown in the formula (I), n is 2;
Four-functional group epoxy resin, shown in (IIII);
Phosphorus containing phenolic resin is suc 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 μ m, and purity is more than 99%.In embodiment 1 to embodiment 6 each component feed intake as shown in table 1.
Each component of the low water suction thermoset of Halogen fire-proof resin composition of table 1 embodiment 1 to embodiment 6 feeds intake.
The low water suction thermoset of Halogen provided by the invention fire-proof resin composition is that conventional preparation method makes, and applies the preparation method that described resin combination is prepared bonding sheet, and described preparation method comprises the following steps:
1) Halogen low 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 weaving material is immersed in the low water suction thermoset of the Halogen fire-proof resin composition solution that step 1) obtains;
3) by the inorganic or organic weaving material warp heating, drying 5-8min at 168-172 ℃ having flooded, obtain described bonding sheet.
The bonding sheet that application prepares is prepared the preparation method of copper-clad plate, and described preparation method comprises the following steps:
1) by two or two above-described bonding sheet stacks;
2) on the single or double of the bonding sheet superposeing in step 1), be 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: when temperature is 80～140 ℃, should control temperature rise rate at 1.5～2.5 ℃/min; Outer material temperature applies full pressure in the time of 80～100 ℃, and full pressure pressure is 350psi left and right; While solidifying, control material temperature at 185 ℃, and be incubated 60min.
The low water suction thermoset of the Halogen fire-proof resin composition of Application Example 1 to embodiment 6 preparation adopts the preparation method of above-mentioned bonding sheet, prepare respectively the bonding sheet of embodiment 1 to embodiment 6, by the bonding sheet of this embodiment 1 to embodiment 6, adopted the preparation method of above-mentioned copper-clad plate, prepare respectively the copper-clad plate of embodiment 1 to embodiment 6, 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), measure according to the DSC method of 2.4.25 defined in IPC-TM-650.
(2) Z axis thermal expansivity CET(α 2) TMA: the method according to 2.4.24 defined in IPC-TM-650 is measured.
(3) heat decomposition temperature Td (5%): the method according to 2.4.26 defined in IPC-TM-650 is measured.
(4) the thermally stratified layer time (T300): the method according to 2.4.24.1 defined in IPC-TM-650 is measured.
(5) stripping strength: according to the experiment condition of " after thermal stresses " in 2.4.8 method in IPC-TM-650, measure the stripping strength of metal cap rock.
(6) wicking thermotolerance: make and be of a size of the sample that 50mmX50mm two sides is covered with Copper Foil, sample is immersed in the solder furnace of 288 ℃ of constant temperature, record the time that sample layering is bubbled.
(7) resistance to flame UL94: measure according to UL94 vertical combustion method.
(8) specific inductivity (1GHZ): use flat band method to measure the specific inductivity under 1MHZ according to 2.5.5.9 in IPC-TM-650.
(9) dielectric loss angle tangent Df1MHZ: use flat band method to measure the dielectric loss factor under 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.
Bonding sheet and printed electronic circuit copper-clad plate that Halogen low water absorbable thermoset fire-proof resin composition of the present invention makes, 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.
Above embodiment is the restriction to the present composition not, and all equivalences of doing by the principle of the invention, technical spirit change, and trickle modification and modification, all belong to protection scope of the present invention.
Claims (9)
1. the low water suction thermoset of a Halogen fire-proof resin composition, is characterized in that: it comprises the component of following parts by weight:
Wherein, described many ring benzoxazine colophonies as shown in the formula (I),
In described formula (I), the integer that n is 2-6;
Described polyfunctional epoxy resin is suc as formula shown in (II) or formula (III):
In described formula (II), n is greater than 1 integer;
Described phosphorus containing phenolic resin is suc as formula shown in (IV);
In described formula (IV), the integer that n is 1-6;
Described stiffening agent is lacquer resins, and described lacquer resins is a kind of in phenol lacquer resins, adjacent A type lacquer resins, bisphenol A-type lacquer resins, the nitrogenous lacquer resins of triazine modification.
2. the low water suction thermoset of Halogen according to claim 1 fire-proof resin composition, is characterized in that: described many ring benzoxazine colophonies are 30-65 part; Described polyfunctional epoxy resin 15-45 part; Described phosphorus containing phenolic resin 15-20 part.
3. the low water suction thermoset of Halogen according to claim 1 fire-proof resin composition, it is characterized in that: described stiffening agent also comprises imidazoles promotor, the add-on of described imidazoles promotor in the low water suction thermoset of Halogen fire-proof resin composition is 0.05-2.5 parts by weight.
4. the low water suction thermoset of Halogen according to claim 3 fire-proof resin composition, is characterized in that: described imidazoles promotor is a kind of in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole.
5. the low water suction thermoset of Halogen according to claim 1 fire-proof resin composition, is characterized in that: it also comprises that parts by weight are the mineral filler of 15-40.
6. the low water suction thermoset of Halogen according to claim 4 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. the low water suction thermoset of Halogen according to claim 1 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 the described low water suction thermoset of the Halogen fire-proof resin composition of one of 1-7 to prepare the preparation method of bonding sheet, it is characterized in that: described preparation method comprises the following steps:
1) Halogen low 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 weaving material is immersed in the low water suction thermoset of the Halogen fire-proof resin composition solution that step 1) obtains;
3) by the inorganic or organic weaving material warp heating, drying 5-8min at 168-172 ℃ having flooded, obtain described bonding sheet.
9. the bonding sheet that application prepares as claim 8 is prepared 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 stacks;
2) on the single or double of the bonding sheet superposeing in step 1), be 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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| CN104804377A (en) * | 2015-01-28 | 2015-07-29 | 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 |
| CN106751821A (en) * | 2016-12-29 | 2017-05-31 | 广东生益科技股份有限公司 | A kind of halogen-free flame resistance resin composite and use its bonding sheet and copper-clad laminate |
| CN109836778A (en) * | 2019-02-26 | 2019-06-04 | 金安国纪科技（杭州）有限公司 | A kind of composition epoxy resin, preparation method and application |
| 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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| 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 |
| CN106751821A (en) * | 2016-12-29 | 2017-05-31 | 广东生益科技股份有限公司 | A kind of halogen-free flame resistance resin composite and use its bonding sheet and copper-clad laminate |
| CN109836778A (en) * | 2019-02-26 | 2019-06-04 | 金安国纪科技（杭州）有限公司 | A kind of composition epoxy resin, preparation method and application |
| 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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| CN103724997B (en) | 2016-01-06 |
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