CN104761870A - Halogen-free low-dielectric-loss epoxy resin composition and prepreg and laminated board prepared by using halogen-free low-dielectric-loss epoxy resin composition - Google Patents
Halogen-free low-dielectric-loss epoxy resin composition and prepreg and laminated board prepared by using halogen-free low-dielectric-loss epoxy resin composition Download PDFInfo
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Abstract
The invention provides a halogen-free low-dielectric-loss epoxy resin composition, which comprises the following components in parts by weight: 5-20 parts of a SMA resin, 150-200 parts of an epoxy resin, 60-90 parts of a curing agent A, 40-70 parts of a curing agent B, 70-100 parts of packing, 0-13 parts of a flame retardant, 0.3-1 part of a curing accelerator, 0.7-1 part of a coupling agent, and 70-100 parts of a solvent, wherein the curing agent A is one or more of diamino sulfobenzide, diamino diphenylmethane, diamino diphenyl ether, amino paraxylene, dicyandiamide, phenolic novolac resin, bisphenol-A phenolic resin, and phosphorus-containing phenolic resin; and the curing agent B is an active ester curing agent. The invention also provides a prepreg and a laminated board prepared by using the composition. The epoxy resin composition and prepreg and laminated board disclosed by the invention can achieve a halogen-free flame retardant effect, and have low dielectric constants and dielectric losses.
Description
Technical field
The present invention relates to the composition of epoxy resin, specifically, relate to a kind of Halogen low dielectric loss type composition epoxy resin, and the prepreg made of this Halogen low dielectric loss type composition epoxy resin and veneer sheet.
Background technology
In recent years, along with the high speed development of computer, communication equipment and mechanics of communication, the reliability of Signal transmissions has been the emphasis that people are concerned about the most, and wherein information distortion control is the key of technology, and the dielectric properties of circuit base material more and more receive the concern of planner.In order to high-speed transfer and process a large amount of information, operation signal trend high frequency, therefore all proposes higher requirement to the dielectric properties of circuit base material and the fineness of wiring board processing and line definition.
Traditional laminate for printed circuits, mainly adopts the brominated flame-retardant such as brominated epoxy resin, tetrabromo-bisphenol to realize the flame retardant properties of sheet material.But brominated flame-retardant can produce the objectionable impuritiess such as hydrogen bromide, dioxin, diphenylene-oxide when burning, and serious environment pollution, is detrimental to health.Therefore, the research of Halogen veneer sheet has become the focus of electron trade.
As the substitute of brominated flame-retardant, the mainly resin of the flame retardant resistance element such as nitrogenous, phosphorus, silicon, and containing the mineral filler (as aluminium hydroxide, magnesium hydroxide etc.) of crystal water, after introducing these components, the flame retardant resistance of sheet material can be improved, but the dielectric properties of sheet material can be reduced.
And, because epoxy resin itself is containing certain polar group, and a certain amount of polar group can be produced again at the solidification process with solidifying agent (as amine curing agent or phenolic resin curative), wherein:
The reaction formula of amine curing agent and epoxy resin generation ring-opening reaction is:
The reaction formula of phenolic resin curative and epoxy resin generation ring-opening reaction is:
Visible, when adopting amine curing agent or phenolic resin curative, in the curing process, ring-opening reaction along with epoxy group(ing) generates secondary hydroxyl group, the generation of secondary hydroxyl group can make the polar group of molecular structure increase, thus cause dielectric material rate and water-intake rate all higher, the dielectric properties of sheet material thus can be caused poor, the requirement of operation signal high frequency can not be met.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Halogen low dielectric loss type composition epoxy resin, the prepreg and veneer sheet that use above-mentioned Halogen low dielectric loss type composition epoxy resin to prepare are provided simultaneously, this composition epoxy resin, prepreg and veneer sheet can realize halogen-free flameproof, and there is lower specific inductivity and dielectric loss, operation signal low distortion and high-speed high frequency can be met to the requirement of circuit base material dielectric properties.The technical scheme adopted is as follows:
A kind of Halogen low dielectric loss type composition epoxy resin, it is characterized in that the component containing following weight proportioning: SMA resin 5-20 part, epoxy resin 150-200 part, solidifying agent A 60-90 part, solidifying agent B 40-70 part, filler 70-100 part, fire retardant 0-13 part, curing catalyst 0.3-1 part, coupling agent 0.7-1 part, solvent 70-100 part; Described solidifying agent A is a kind of or wherein multiple combination in two amido sulfobenzides, two amido ditanes, diaminodiphenyl ether, p-Xylol amine, Dyhard RU 100, linear phenolic resin, bisphenol A-type resol and phosphorus containing phenolic resin; Described solidifying agent B is active ester class solidifying agent.
Above-mentioned SMA resin is the random copolymers of vinylbenzene and maleic anhydride, and its chemical structural formula is as follows:
Wherein, m is the random natural number in 1-5, and n is the random natural number in 8-12.
The molecular weight ranges of preferred above-mentioned SMA resin is 2000-7000.
Preferred above-mentioned epoxy resin is a kind of or wherein multiple combination in bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac type epoxy resin, bisphenol-A phenolic type epoxy resin, o-cresol aldehyde type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, isocyanate-based epoxy resin, tetrafunctional epoxy resin and phosphorus-containing phenolic aldehyde epoxy resin.Wherein, preferred above-mentioned phosphorus-containing phenolic aldehyde epoxy resin is 10-(2,5-dihydroxy phenyl)-9,10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide modifying novolac epoxy, 10-(2,5-dihydroxyl naphthyl)-9, a kind of or the wherein multiple combination that the assorted-10-phosphine phenanthrene-10-oxide modifying novolac epoxy of 10-dihydro-9-oxy and 9,10-dihydro-9-oxy are mixed in-10-phosphine phenanthrene-10-oxide modifying novolac epoxy.
The structural formula of above-mentioned active ester class solidifying agent is as follows:
Wherein R
1for aliphatic group, aromatic group or alicyclic group, R
2for aliphatic group, aromatic group or alicyclic group.
Preferred above-mentioned filler is a kind of or wherein multiple combination in silicon-dioxide, mica powder, kaolin, talcum powder and aluminium hydroxide.
Preferred above-mentioned fire retardant is phosphonium flame retardant, as polycondenseng phosphate, phosphonitrile, 10-(2,5-dihydroxy phenyl)-9,10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 10-(2,5-dihydroxyl naphthyl)-9, a kind of or the wherein multiple combination that the assorted-10-phosphine phenanthrene-10-oxide compound of 10-dihydro-9-oxy and 9,10-dihydro-9-oxy are mixed in-10-phosphine phenanthrene-10-oxide compound.Material property looked by fire retardant needs and supplements interpolation, need add phosphonium flame retardant when phosphorus containing phenolic resin comparision contents is few in composition epoxy resin time.
Above-mentioned curing catalyst is imidazoles promotor (as 2-ethyl-4-methylimidazole, glyoxal ethyline etc.) or organic metal salt (as aluminium acetylacetonate, acetylacetone cobalt etc.), or the mixture of imidazoles promotor and organic metal salt.
Preferred above-mentioned coupling agent is silane coupling agent.
Preferred above-mentioned solvent is a kind of or wherein multiple combination in acetone, butanone, pimelinketone, toluene, dimethylbenzene, DMF, N,N-dimethylacetamide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and 1-Methoxy-2-propyl acetate.
Above-mentioned Halogen low dielectric loss type composition epoxy resin can adopt ordinary method to prepare, such as: first take SMA resin, epoxy resin, solidifying agent A, solidifying agent B, filler, fire retardant, curing catalyst, coupling agent and solvent in proportion; Then SMA resin is put into mixed glue bottle, then in mixed glue bottle, add the solvent that weight is SMA resin 2-3 times, stir until SMA resin dissolves completely; Then in mixed glue bottle, add epoxy resin, solidifying agent A, solidifying agent B, fire retardant, curing catalyst and coupling agent, then add filler and remaining solvent, and be stirred to and mix, Halogen low dielectric loss type composition epoxy resin can be obtained.
The present invention also provides a kind of prepreg using above-mentioned Halogen low dielectric loss type composition epoxy resin to make, and it is characterized in that described prepreg comprises glasscloth and by flooding and drying the Halogen low dielectric loss type epoxy resin composition thing of postadhesion on glasscloth.The concrete making method of prepreg is as follows: after being flooded in above-mentioned Halogen low dielectric loss type composition epoxy resin by glasscloth, toast 4-8 minute, can obtain prepreg in the baking oven of 160-175 DEG C.
And, the present invention also provides a kind of veneer sheet using above-mentioned Halogen low dielectric loss type composition epoxy resin to make, and it is characterized in that described veneer sheet is suppressed under following temperature and pressure condition by one or more above-mentioned prepreg to form: the temperature rise rate of (1) lamination controls at 1.1-2.5 DEG C/min (DEG C/min); (2) pressure condition of lamination: apply peak pressure when the temperature of prepreg reaches 90-120 DEG C, described peak pressure is 350-450psi (pound/square inch); (3), during solidification, control the temperature of prepreg between 195-210 DEG C, and be incubated 90-140min (minute).Described veneer sheet at its one or both sides bonding metal paper tinsel, thus can obtain metal-clad laminate, and described tinsel can be Copper Foil, aluminium foil and nickel foil etc., the preferred Copper Foil of the present invention.
Compared with prior art, tool has the following advantages in the present invention:
1. Halogen low dielectric loss type composition epoxy resin of the present invention is not halogen-containing, and can realize halogen-free flameproof, flame retardant resistance reaches UL 94V-0 grade; And with the addition of the random copolymers of part styrene and maleic anhydride in Halogen low dielectric loss type composition epoxy resin of the present invention, and employ active ester class solidifying agent, greatly reduce the existence of system polar groups, therefore there is lower specific inductivity and dielectric loss, operation signal low distortion and high-speed high frequency can be met to the requirement of circuit base material dielectric properties.
The reaction formula of active ester class solidifying agent and epoxy resin generation ring-opening reaction is:
After active ester class solidifying agent and epoxy resin generation ring-opening reaction, form the spatial grid structure not producing secondary hydroxyl group, thus molecular structure and resin system polar groups are tailed off, therefore, it is possible to improve the dielectric properties of material.
2. select phenolic resin curative that composition epoxy resin can be made to have excellent humidity resistance and thermotolerance, add more filler and make composition epoxy resin have low-expansion coefficient.
3. the prepreg obtained by Halogen low dielectric loss type composition epoxy resin of the present invention and veneer sheet can realize halogen-free flameproof, and there is lower specific inductivity and dielectric loss, there is excellent humidity resistance and thermotolerance, there is low-expansion coefficient, the requirement of high-performance printed wiring plate substrate can be met, be applicable to the field such as high-speed high frequency and high density interconnect, have broad application prospects.
Embodiment
Embodiment 1
First, take SMA resin 15g (trade mark is SMA-1000 ((n/m=8/1))), epoxy resin 193g (wherein DCPD-containing epoxy resin 30g, phosphorus-containing phenolic aldehyde epoxy resin 60g, isocyanate-based epoxy resin 100g, tetrafunctional epoxy resin 3g), solidifying agent A 90g (wherein Dyhard RU 100 0.5g, bisphenol A-type resol 20g, phosphorus containing phenolic resin 69.5g), solidifying agent B (i.e. active ester class solidifying agent) 70g, filler 100g (wherein aluminium hydroxide 70g, silicon-dioxide 30g), curing catalyst 0.31g (being glyoxal ethyline), coupling agent 1g (is silane coupling agent, its trade mark is Z-6020), solvent 100g (wherein propylene glycol monomethyl ether 90g, butanone 10g).
The structural formula of above-mentioned active ester class solidifying agent is as follows:
Wherein R
1for aliphatic group, R
2for aromatic group.The trade mark of the active ester class solidifying agent that the present embodiment adopts is HPC-8000.
Then, prepare Halogen low dielectric loss type composition epoxy resin in the steps below: SMA resin is put into mixed glue bottle, then add 45g solvent (being propylene glycol monomethyl ether) in mixed glue bottle, stir until SMA resin dissolves completely; Then in mixed glue bottle, add epoxy resin, solidifying agent A, solidifying agent B, curing catalyst and coupling agent, then add filler and remaining solvent, and be stirred to and mix, Halogen low dielectric loss type composition epoxy resin can be obtained.Also can prepare Halogen low dielectric loss type composition epoxy resin in the steps below: Dyhard RU 100, bisphenol A-type resol and propylene glycol monomethyl ether are added in mixed glue bottle, stir and make Dyhard RU 100 and bisphenol A-type resol be dissolved completely in propylene glycol monomethyl ether; Then successively SMA resin and DCPD-containing epoxy resin are added in mixed glue bottle, stir and SMA resin and DCPD-containing epoxy resin are dissolved; Then in mixed glue bottle, add phosphorus-containing phenolic aldehyde epoxy resin, isocyanate-based epoxy resin, tetrafunctional epoxy resin, phosphorus containing phenolic resin, active ester class solidifying agent, curing catalyst, coupling agent successively, be stirred to and mix; Add aluminium hydroxide, silicon-dioxide and butanone in the most backward mixed glue bottle, be stirred to after mixing, obtained Halogen low dielectric loss type composition epoxy resin.
Obtained Halogen low dielectric loss type composition epoxy resin contains: SMA resin 15g, epoxy resin 193g (wherein DCPD-containing epoxy resin 30g, phosphorus-containing phenolic aldehyde epoxy resin 60g, isocyanate-based epoxy resin 100g, tetrafunctional epoxy resin 3g), solidifying agent A 90g (wherein Dyhard RU 100 0.5g, bisphenol A-type resol 20g, phosphorus containing phenolic resin 69.5g), solidifying agent B (i.e. active ester class solidifying agent) 70g, filler 100g (wherein aluminium hydroxide 70g, silicon-dioxide 30g), curing catalyst 0.31g (being glyoxal ethyline), coupling agent 1g, solvent 100g (wherein propylene glycol monomethyl ether 90g, butanone 10g).
During batch production Halogen low dielectric loss type composition epoxy resin, be equipped with various raw material by above-mentioned part by weight.
The prepreg of the present embodiment comprises glasscloth and by flooding and drying the Halogen low dielectric loss type epoxy resin composition thing of postadhesion on glasscloth.The concrete making method of prepreg is as follows: after being flooded in above-mentioned Halogen low dielectric loss type composition epoxy resin by glasscloth, toasts 6 minutes, can obtain prepreg in the baking oven of 170 DEG C.
The veneer sheet of the present embodiment stacks neatly by 6 above-mentioned prepregs, and two sides is covered with the Copper Foil of 35 μm, is placed in heating oil in vacuum press, suppresses forming under following temperature and pressure condition: the temperature rise rate of (1) lamination controls at 1.5 DEG C/min; (2) pressure condition of lamination: apply peak pressure when the temperature of prepreg reaches 100 DEG C, described peak pressure is 400psi; (3), during solidification, control the temperature of prepreg at 205 DEG C, and be incubated 120min.The copper-clad laminate performance of gained is as shown in table 1.
Embodiment 2
First, take SMA resin 15g (trade mark is SMA-3000 (n/m=10/3)), epoxy resin 193g (wherein DCPD-containing epoxy resin 30g, bisphenol A type epoxy resin 60g, bisphenol f type epoxy resin 100g, adjacent Jia Ji Fen Chuo type epoxy resin 3g), solidifying agent A 87.5g (wherein two amido ditane 0.5g, bisphenol A-type resol 23g, p-Xylol amine 64g), solidifying agent B (i.e. active ester class solidifying agent) 60g, filler 92g (wherein kaolin 65g, silicon-dioxide 27g), curing catalyst 0.38g (being glyoxal ethyline), coupling agent 0.92g (is silane coupling agent, its trade mark is Z-6020), solvent 95g (wherein propylene glycol monomethyl ether 90g, butanone 5g).
The structural formula of above-mentioned active ester class solidifying agent is as follows:
Wherein R
1for aliphatic group, R
2for aromatic group.The trade mark of the active ester class solidifying agent that the present embodiment adopts is HPC-8000.
Then, prepare Halogen low dielectric loss type composition epoxy resin in the steps below: SMA resin is put into mixed glue bottle, then add 30g solvent (being propylene glycol monomethyl ether) in mixed glue bottle, stir until SMA resin dissolves completely; Then in mixed glue bottle, add epoxy resin, solidifying agent A, solidifying agent B, curing catalyst and coupling agent, then add filler and remaining solvent, and be stirred to and mix, Halogen low dielectric loss type composition epoxy resin can be obtained.Also can prepare Halogen low dielectric loss type composition epoxy resin in the steps below: two amido ditanes, bisphenol A-type resol, p-Xylol amine and propylene glycol monomethyl ether are added in mixed glue bottle, stir and make two amido ditanes, bisphenol A-type resol and p-Xylol amine be dissolved completely in propylene glycol monomethyl ether; Then in mixed glue bottle, add SMA resin and DCPD-containing epoxy resin successively, stir and SMA resin and DCPD-containing epoxy resin are dissolved; Then in mixed glue bottle, add bisphenol A type epoxy resin, bisphenol f type epoxy resin, adjacent Jia Ji Fen Chuo type epoxy resin, active ester class solidifying agent, curing catalyst, coupling agent successively, be stirred to and mix; Add kaolin, silicon-dioxide and butanone in the most backward mixed glue bottle, be stirred to after mixing, obtained Halogen low dielectric loss type composition epoxy resin.
Obtained Halogen low dielectric loss type composition epoxy resin contains: SMA resin 15g, epoxy resin 193g (wherein DCPD-containing epoxy resin 30g, bisphenol A type epoxy resin 60g, bisphenol f type epoxy resin 100g, adjacent Jia Ji Fen Chuo type epoxy resin 3g), solidifying agent A 87.5g (wherein two amido ditane 0.5g, bisphenol A-type resol 23g, p-Xylol amine 64g), solidifying agent B (i.e. active ester class solidifying agent) 60g, filler 92g (wherein kaolin 65g, silicon-dioxide 27g), curing catalyst 0.38g (being glyoxal ethyline), coupling agent 0.92g (being silane coupling agent), solvent 95g (wherein propylene glycol monomethyl ether 90g, butanone 5g).
During batch production Halogen low dielectric loss type composition epoxy resin, be equipped with various raw material by above-mentioned part by weight.
The prepreg of the present embodiment comprises glasscloth and by flooding and drying the Halogen low dielectric loss type epoxy resin composition thing of postadhesion on glasscloth.The concrete making method of prepreg is as follows: after being flooded in above-mentioned Halogen low dielectric loss type composition epoxy resin by glasscloth, toasts 4 minutes, can obtain prepreg in the baking oven of 175 DEG C.
The veneer sheet of the present embodiment stacks neatly by 5 above-mentioned prepregs, and two sides is covered with the Copper Foil of 35 μm, is placed in heating oil in vacuum press, suppresses forming under following temperature and pressure condition: the temperature rise rate of (1) lamination controls at 2.5 DEG C/min; (2) pressure condition of lamination: apply peak pressure when the temperature of prepreg reaches 120 DEG C, described peak pressure is 350psi; (3), during solidification, control the temperature of prepreg at 210 DEG C, and be incubated 90min.Obtained copper-clad laminate performance is as shown in table 1.
Embodiment 3
First, take SMA resin 15g (trade mark is EF60 (12/5)), epoxy resin 193g (biphenyl type epoxy resin 33g, bisphenol-A phenolic type epoxy resin 60g, isocyanate-based epoxy resin 100g), solidifying agent A 86.5g (wherein two amido sulfobenzide 0.5g, two amido ditane 26g, phosphorus containing phenolic resin 60g), solidifying agent B (i.e. active ester class solidifying agent) 50g, filler 84g (wherein mica powder 61g, silicon-dioxide 23g), fire retardant 3g (is 10-(2, 5-dihydroxy phenyl)-9, 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound), curing catalyst 0.83g (being 2-ethyl-4-methylimidazole), coupling agent 0.84g (is silane coupling agent, its trade mark is Z-6020), solvent 95g (wherein propylene glycol monomethyl ether 90g, N, dinethylformamide 5g).
The structural formula of above-mentioned active ester class solidifying agent is as follows:
Wherein R
1for aliphatic group, R
2for aliphatic group.The trade mark of the active ester class solidifying agent that the present embodiment adopts is SHC-5100T65.
Then, prepare Halogen low dielectric loss type composition epoxy resin in the steps below: SMA resin is put into mixed glue bottle, then add 40g solvent (propylene glycol monomethyl ether) in mixed glue bottle, stir until SMA resin dissolves completely; Then in mixed glue bottle, add epoxy resin, solidifying agent A, solidifying agent B, fire retardant, curing catalyst and coupling agent, then add filler and remaining solvent, and be stirred to and mix, Halogen low dielectric loss type composition epoxy resin can be obtained.Also can prepare Halogen low dielectric loss type composition epoxy resin in the steps below: two amido sulfobenzides, two amido ditanes, phosphorus containing phenolic resin and propylene glycol monomethyl ether add in mixed glue bottle, stir and make two amido sulfobenzides, two amido ditanes and phosphorus containing phenolic resin be dissolved completely in propylene glycol monomethyl ether; Then in mixed glue bottle, add SMA resin, biphenyl type epoxy resin successively, stir and SMA resin and biphenyl type epoxy resin are dissolved; Then in mixed glue bottle, add bisphenol-A phenolic type epoxy resin, isocyanate-based epoxy resin, active ester class solidifying agent, fire retardant, curing catalyst, coupling agent successively, be stirred to and mix; Add mica powder, silicon-dioxide and DMF in the most backward mixed glue bottle, be stirred to after mixing, obtained Halogen low dielectric loss type composition epoxy resin.
Obtained Halogen low dielectric loss type composition epoxy resin contains: SMA resin 15g, epoxy resin 193g (biphenyl type epoxy resin 33g, bisphenol-A phenolic type epoxy resin 60g, isocyanate-based epoxy resin 100g), solidifying agent A 86.5g (wherein two amido sulfobenzide 0.5g, two amido ditane 26g, phosphorus containing phenolic resin 60g), solidifying agent B (i.e. active ester class solidifying agent) 50g, filler 84g (wherein mica powder 61g, silicon-dioxide 23g), fire retardant 3g, curing catalyst 0.83g (being 2-ethyl-4-methylimidazole), coupling agent 0.84g (being silane coupling agent), solvent 95g (wherein propylene glycol monomethyl ether 90g, N, dinethylformamide 5g).
During batch production Halogen low dielectric loss type composition epoxy resin, be equipped with various raw material by above-mentioned part by weight.
The prepreg of the present embodiment comprises glasscloth and by flooding and drying the Halogen low dielectric loss type epoxy resin composition thing of postadhesion on glasscloth.The concrete making method of prepreg is as follows: after being flooded in above-mentioned Halogen low dielectric loss type composition epoxy resin by glasscloth, toasts 8 minutes, can obtain prepreg in the baking oven of 160 DEG C.
The veneer sheet of the present embodiment stacks neatly by 4 above-mentioned prepregs, and two sides is covered with the Copper Foil of 35 μm, is placed in heating oil in vacuum press, suppresses forming under following temperature and pressure condition: the temperature rise rate of (1) lamination controls at 1.1 DEG C/min; (2) pressure condition of lamination: apply peak pressure when the temperature of prepreg reaches 90 DEG C, described peak pressure is 450psi; (3), during solidification, control the temperature of prepreg at 195 DEG C, and be incubated 140min.Obtained copper-clad laminate performance is as shown in table 1.
Embodiment 4
First, take SMA resin 20g (trade mark is EF60 (12/5)), epoxy resin 152g (wherein DCPD-containing epoxy resin 17g, phosphorus-containing phenolic aldehyde epoxy resin 50g, bisphenol A type epoxy resin 83g, o-cresol aldehyde type epoxy resin 2g), solidifying agent A 61.4g (wherein two amido sulfobenzide 0.4g, linear phenolic resin 16g, phosphorus containing phenolic resin 45g), solidifying agent B (i.e. active ester class solidifying agent) 40g, filler 70g (wherein talcum powder 50g, mica powder 20g), fire retardant 10g (being phosphonitrile), curing catalyst 0.97g (wherein 2-ethyl-4-methylimidazole 0.73g, aluminium acetylacetonate 0.24g), coupling agent 0.7g (is silane coupling agent, its trade mark is Z-6020), solvent 75g (propylene glycol monomethyl ether 73g, 1-Methoxy-2-propyl acetate 2g).
The structural formula of above-mentioned active ester class solidifying agent is as follows:
Wherein R
1for aromatic group, R
2for aliphatic group.The trade mark of the active ester class solidifying agent that the present embodiment adopts is HP-9900.
Then, prepare Halogen low dielectric loss type composition epoxy resin in the steps below: SMA resin is put into mixed glue bottle, then add 50g solvent (propylene glycol monomethyl ether) in mixed glue bottle, stir until SMA resin dissolves completely; Then in mixed glue bottle, add epoxy resin, solidifying agent A, solidifying agent B, fire retardant, curing catalyst and coupling agent, then add filler and remaining solvent, and be stirred to and mix, Halogen low dielectric loss type composition epoxy resin can be obtained.Also can prepare Halogen low dielectric loss type composition epoxy resin in the steps below: two amido sulfobenzides, linear phenolic resin and propylene glycol monomethyl ether are added in mixed glue bottle, stir and make two amido sulfobenzides and linear phenolic resin be dissolved completely in propylene glycol monomethyl ether; Then successively SMA resin and DCPD-containing epoxy resin are added in mixed glue bottle, stir and SMA resin and DCPD-containing epoxy resin are dissolved; Then in mixed glue bottle, add phosphorus-containing phenolic aldehyde epoxy resin, bisphenol A type epoxy resin, o-cresol aldehyde type epoxy resin, phosphorus containing phenolic resin, active ester class solidifying agent, fire retardant, curing catalyst, coupling agent successively, be stirred to and mix; Add talcum powder, mica powder and 1-Methoxy-2-propyl acetate in the most backward mixed glue bottle, be stirred to after mixing, obtained Halogen low dielectric loss type composition epoxy resin.
Obtained Halogen low dielectric loss type composition epoxy resin contains: SMA resin 20g, epoxy resin 152g (wherein DCPD-containing epoxy resin 17g, phosphorus-containing phenolic aldehyde epoxy resin 50g, bisphenol A type epoxy resin 83g, o-cresol aldehyde type epoxy resin 2g), solidifying agent A 61.4g (wherein two amido sulfobenzide 0.4g, linear phenolic resin 16g, phosphorus containing phenolic resin 45g), solidifying agent B (i.e. active ester class solidifying agent) 40g, filler 70g (wherein talcum powder 50g, mica powder 20g), fire retardant 10g (being phosphonitrile), curing catalyst 0.97g (wherein 2-ethyl-4-methylimidazole 0.73g, aluminium acetylacetonate 0.24g), coupling agent 0.7g (is silane coupling agent, its trade mark is Z-6020), solvent 75g (propylene glycol monomethyl ether 73g, 1-Methoxy-2-propyl acetate 2g).
During batch production Halogen low dielectric loss type composition epoxy resin, be equipped with various raw material by above-mentioned part by weight.
The prepreg of the present embodiment comprises glasscloth and by flooding and drying the Halogen low dielectric loss type epoxy resin composition thing of postadhesion on glasscloth.The concrete making method of prepreg is as follows: after being flooded in above-mentioned Halogen low dielectric loss type composition epoxy resin by glasscloth, toasts 7 minutes, can obtain prepreg in the baking oven of 165 DEG C.
The veneer sheet of the present embodiment is stacked neatly by 6 above-mentioned prepregs, and two sides is covered with Copper Foil, is placed in heating oil in vacuum press, suppresses forming under following temperature and pressure condition: the temperature rise rate of (1) lamination controls at 2 DEG C/min; (2) pressure condition of lamination: apply peak pressure when the temperature of prepreg reaches 110 DEG C, described peak pressure is 420psi; (3), during solidification, control the temperature of prepreg at 200 DEG C, and be incubated 120min.Obtained copper-clad laminate performance is as shown in table 1.
Embodiment 5
First, take SMA resin 5g (trade mark is SMA-6000 (n/m=20/4)), epoxy resin 184g (wherein bisphenol f type epoxy resin 28g, phosphorus-containing phenolic aldehyde epoxy resin 58g, isocyanate-based epoxy resin 95g, bisphenol-A phenolic type epoxy resin 3g), solidifying agent A 83.5g (wherein diaminodiphenyl ether 0.5g, p-Xylol amine 18g, phosphorus containing phenolic resin 65g), solidifying agent B (i.e. active ester class solidifying agent) 70g, filler 90g (wherein aluminium hydroxide 64g, kaolin 26g), fire retardant 5g (is 9, 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound), curing catalyst 0.45g (being acetylacetone cobalt), coupling agent 0.9g (is silane coupling agent, its trade mark is Z-6020), solvent 100g (wherein propylene glycol monomethyl ether 88g, pimelinketone 12g).
The structural formula of above-mentioned active ester class solidifying agent is as follows:
Wherein R
1for aliphatic group, R
2for aliphatic group.The trade mark of the active ester class solidifying agent that the present embodiment adopts is HP-9900.
Then, prepare Halogen low dielectric loss type composition epoxy resin in the steps below: SMA resin is put into mixed glue bottle, then add 12g solvent in mixed glue bottle, stir until SMA resin dissolves completely; Then in mixed glue bottle, add epoxy resin, solidifying agent A, solidifying agent B, fire retardant, curing catalyst and coupling agent, then add filler and remaining solvent, and be stirred to and mix, Halogen low dielectric loss type composition epoxy resin can be obtained.Also can prepare Halogen low dielectric loss type composition epoxy resin in the steps below: diaminodiphenyl ether, p-Xylol amine, phosphorus containing phenolic resin and propylene glycol monomethyl ether are added in mixed glue bottle, stir and make diaminodiphenyl ether, p-Xylol amine and phosphorus containing phenolic resin be dissolved completely in propylene glycol monomethyl ether; Then successively SMA resin and bisphenol f type epoxy resin are added in mixed glue bottle, stir and SMA resin and bisphenol f type epoxy resin are dissolved; Then in mixed glue bottle, add phosphorus-containing phenolic aldehyde epoxy resin, isocyanate-based epoxy resin, bisphenol-A phenolic type epoxy resin, active ester class solidifying agent, fire retardant, curing catalyst, coupling agent successively, be stirred to and mix; Add aluminium hydroxide, kaolin and pimelinketone in the most backward mixed glue bottle, be stirred to after mixing, obtained Halogen low dielectric loss type composition epoxy resin.
Obtained Halogen low dielectric loss type composition epoxy resin contains: SMA resin 5g, epoxy resin 184g (wherein bisphenol f type epoxy resin 28g, phosphorus-containing phenolic aldehyde epoxy resin 58g, isocyanate-based epoxy resin 95g, bisphenol-A phenolic type epoxy resin 3g), solidifying agent A 83.5g (wherein diaminodiphenyl ether 0.5g, p-Xylol amine 18g, phosphorus containing phenolic resin 65g), solidifying agent B (i.e. active ester class solidifying agent) 70g, filler 90g (wherein aluminium hydroxide 64g, kaolin 26g), fire retardant 5g (is 9, 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound), curing catalyst 0.45g (being acetylacetone cobalt), coupling agent 0.9g (is silane coupling agent, its trade mark is Z-6020), solvent 100g (wherein propylene glycol monomethyl ether 88g, pimelinketone 12g).
During batch production Halogen low dielectric loss type composition epoxy resin, be equipped with various raw material by above-mentioned part by weight.
The prepreg of the present embodiment comprises glasscloth and by flooding and drying the Halogen low dielectric loss type epoxy resin composition thing of postadhesion on glasscloth.The concrete making method of prepreg is as follows: after being flooded in above-mentioned Halogen low dielectric loss type composition epoxy resin by glasscloth, toasts 5 minutes, can obtain prepreg in the baking oven of 175 DEG C.
The veneer sheet of the present embodiment is stacked neatly by 5 above-mentioned prepregs, and two sides is covered with Copper Foil, is placed in heating oil in vacuum press, suppresses forming under following temperature and pressure condition: the temperature rise rate of (1) lamination controls at 1.5 DEG C/min; (2) pressure condition of lamination: apply peak pressure when the temperature of prepreg reaches 110 DEG C, described peak pressure is 400psi; (3), during solidification, control the temperature of prepreg at 205 DEG C, and be incubated 120min.Obtained copper-clad laminate performance is as shown in table 1.
Comparative example
1.5g Dyhard RU 100,22g bisphenol A-type resol and 90g propylene glycol monomethyl ether are added in mixed glue bottle, makes Dyhard RU 100 and bisphenol A-type resol be dissolved completely in propylene glycol monomethyl ether; Then successively 15g o-cresol aldehyde type epoxy resin (trade mark is N-690) and 30g DCPD-containing epoxy resin (trade mark is HP-7200HHH) are added in mixed glue bottle, stir and o-cresol aldehyde type epoxy resin and DCPD-containing epoxy resin are dissolved; Then (trade mark is PE-315 in mixed glue bottle, to add 60g phosphorus-containing phenolic aldehyde epoxy resin successively,), the isocyanate-based epoxy resin of 110g (trade mark is XZ-97103), 3g polyfunctional epoxy resin, 65g phosphorus containing phenolic resin (trade mark is XZ-92741), 0.36g curing catalyst (being 2-ethyl-4-methylimidazole), 0.9g coupling agent (trade mark is Z-6020), be stirred to and mix; Add 64g aluminium hydroxide, 26g improved silica and 10g butanone in the most backward mixed glue bottle, be stirred to after mixing, obtained Halogen low dielectric loss type composition epoxy resin.
The preparation method of prepreg, copper-clad laminate is with embodiment 1.Obtained copper-clad laminate performance is as shown in table 1.
Table 1: the copper-clad laminate performance of each embodiment and comparative example
In table 1, the testing method of properties is as follows:
A, stripping strength: under the test conditions according to " normality " in IPC-TM-650 test method 2.4.8, the stripping strength of test metal cladding;
B, thermal shocking: investigate the layering cream time that it floats tin in 288 DEG C of tin stoves according to IPC-TM-650 test method 2.4.13.1;
C, second-order transition temperature: the DSC method specified according to IPC-TM-650 test method 2.4.25 is tested;
D, Z axis thermal expansivity: the TMA method specified according to IPC-TM-650 test method 2.4.24, the thermal expansivity (z-CTE) of Z axis when probe temperature is raised to 250 DEG C from 50 DEG C;
E, specific inductivity, dielectric loss: use flat band method according to IPC-TM-650 test method 2.5.5.9, the specific inductivity under test 1GHz and dielectric loss factor;
F, flame retardant resistance: test according to UL94 method;
G, humidity resistance: investigate after pressure kettle cooking test (PCT) according to IPC-TM-650 test method 2.6.16, the layering cream time of wicking in 288 DEG C of tin stoves.
From above test result, the prepreg obtained by Halogen low dielectric loss type composition epoxy resin of the present invention and veneer sheet can realize halogen-free flameproof, and there is lower specific inductivity and dielectric loss, there is excellent humidity resistance and thermotolerance, there is low-expansion coefficient, the requirement of high-performance printed wiring plate substrate can be met, be applicable to the field such as high-speed high frequency and high density interconnect, have broad application prospects.
The above, be only preferred embodiment of the present invention, not composition components of the present invention or content are imposed any restrictions, every according to technical spirit of the present invention or composition components or content to any amendment made for any of the above embodiments, equivalent variations and modification, all still belong to the scope of technical solution of the present invention.
Claims (10)
1. a Halogen low dielectric loss type composition epoxy resin, it is characterized in that the component containing following weight proportioning: SMA resin 5-20 part, epoxy resin 150-200 part, solidifying agent A 60-90 part, solidifying agent B 40-70 part, filler 70-100 part, fire retardant 0-13 part, curing catalyst 0.3-1 part, coupling agent 0.7-1 part, solvent 70-100 part; Described solidifying agent A is a kind of or wherein multiple combination in two amido sulfobenzides, two amido ditanes, diaminodiphenyl ether, p-Xylol amine, Dyhard RU 100, linear phenolic resin, bisphenol A-type resol and phosphorus containing phenolic resin; Described solidifying agent B is active ester class solidifying agent.
2. Halogen low dielectric loss type composition epoxy resin according to claim 1, is characterized in that: described SMA resin is the random copolymers of vinylbenzene and maleic anhydride, and its chemical structural formula is as follows:
Wherein, m is the random natural number in 1-5, and n is the random natural number in 8-12.
3. Halogen low dielectric loss type composition epoxy resin according to claim 1, is characterized in that: described epoxy resin is a kind of or wherein multiple combination in bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac type epoxy resin, bisphenol-A phenolic type epoxy resin, o-cresol aldehyde type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, isocyanate-based epoxy resin, tetrafunctional epoxy resin and phosphorus-containing phenolic aldehyde epoxy resin;
Described phosphorus-containing phenolic aldehyde epoxy resin is 10-(2,5-dihydroxy phenyl)-9,10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide modifying novolac epoxy, 10-(2,5-dihydroxyl naphthyl)-9, a kind of or the wherein multiple combination that the assorted-10-phosphine phenanthrene-10-oxide modifying novolac epoxy of 10-dihydro-9-oxy and 9,10-dihydro-9-oxy are mixed in-10-phosphine phenanthrene-10-oxide modifying novolac epoxy.
4. Halogen low dielectric loss type composition epoxy resin according to claim 1, is characterized in that: the structural formula of described active ester class solidifying agent is as follows:
Wherein R
1for aliphatic group, aromatic group or alicyclic group, R
2for aliphatic group, aromatic group or alicyclic group.
5. Halogen low dielectric loss type composition epoxy resin according to claim 1, is characterized in that: described filler is a kind of or wherein multiple combination in silicon-dioxide, mica powder, kaolin, talcum powder and aluminium hydroxide.
6. Halogen low dielectric loss type composition epoxy resin according to claim 1, it is characterized in that: described fire retardant is polycondenseng phosphate, phosphonitrile, 10-(2,5-dihydroxy phenyl)-9,10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 10-(2,5-dihydroxyl naphthyl)-9, a kind of or the wherein multiple combination that the assorted-10-phosphine phenanthrene-10-oxide compound of 10-dihydro-9-oxy and 9,10-dihydro-9-oxy are mixed in-10-phosphine phenanthrene-10-oxide compound.
7. Halogen low dielectric loss type composition epoxy resin according to claim 1, is characterized in that: described curing catalyst is imidazoles promotor or organic metal salt, or the mixture of imidazoles promotor and organic metal salt.
8. Halogen low dielectric loss type composition epoxy resin according to claim 1, it is characterized in that: described solvent is acetone, butanone, pimelinketone, toluene, dimethylbenzene, N, a kind of or wherein multiple combination in dinethylformamide, N,N-dimethylacetamide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and 1-Methoxy-2-propyl acetate.
9. the prepreg using the Halogen low dielectric loss type composition epoxy resin described in claim 1 to make, is characterized in that described prepreg comprises glasscloth and by flooding and drying the Halogen low dielectric loss type epoxy resin composition thing of postadhesion on glasscloth.
10. a veneer sheet, is characterized in that described veneer sheet is suppressed under following temperature and pressure condition by one or more prepreg according to claim 9 to form: the temperature rise rate of (1) lamination controls at 1.1-2.5 DEG C/min; (2) pressure condition of lamination: apply peak pressure when the temperature of prepreg reaches 90-120 DEG C, described peak pressure is 350-450psi; (3), during solidification, control the temperature of prepreg between 195-210 DEG C, and be incubated 90-140min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585808A (en) * | 2016-01-26 | 2016-05-18 | 广东汕头超声电子股份有限公司覆铜板厂 | Low-dielectric-loss high-heat-conductivity resin composition and preparation method thereof, and prepreg and laminated board prepared from resin composition |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964775A (en) * | 2012-10-16 | 2013-03-13 | 广东生益科技股份有限公司 | Thermosetting resin composition and use thereof |
| CN103965624A (en) * | 2014-05-28 | 2014-08-06 | 苏州生益科技有限公司 | Halogen-free resin composition, and prepreg and laminated board prepared from same |
| CN103980667A (en) * | 2014-05-28 | 2014-08-13 | 苏州生益科技有限公司 | Thermosetting resin composition of integrated circuit, prepreg and laminate |
| WO2015001764A1 (en) * | 2013-07-04 | 2015-01-08 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg and laminate board |
-
2015
- 2015-04-03 CN CN201510160606.6A patent/CN104761870A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964775A (en) * | 2012-10-16 | 2013-03-13 | 广东生益科技股份有限公司 | Thermosetting resin composition and use thereof |
| WO2015001764A1 (en) * | 2013-07-04 | 2015-01-08 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg and laminate board |
| CN103965624A (en) * | 2014-05-28 | 2014-08-06 | 苏州生益科技有限公司 | Halogen-free resin composition, and prepreg and laminated board prepared from same |
| CN103980667A (en) * | 2014-05-28 | 2014-08-13 | 苏州生益科技有限公司 | Thermosetting resin composition of integrated circuit, prepreg and laminate |
Non-Patent Citations (1)
| Title |
|---|
| 李子东等: "《胶黏剂助剂》", 28 February 2005, 化学工业工业出版社，材料科学与工程出版中心 * |
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