CN103724936A - Low-dielectric halogen-free epoxy resin composite with improved impact resistance property - Google Patents
Low-dielectric halogen-free epoxy resin composite with improved impact resistance property Download PDFInfo
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Abstract
The invention provides a low-dielectric halogen-free epoxy resin composite with an improved impact resistance property, the low-dielectric halogen-free epoxy resin composite comprises the following components: by weight, 10-20 parts of epoxy resin, 5 -10 parts of benzoxazine resin, 30-50 parts of a phosphorus compound, 25-35 parts of styrene-maleic acid anhydride copolymer and 20-30 parts of carboxyl-terminated nitrile rubber modified epoxy resin. The invention provides low-dielectric halogen-free epoxy resin with the improved impact resistance property and a preparation method thereof. The low-dielectric halogen-free environmentally-friendly epoxy resin composite has good impact resistance property, and a semi-cured piece prepared by using of the epoxy resin composite is non-stick; a copper clad plate prepared by using of the epoxy resin composite has low dielectric coefficient and dielectric loss, and can reduce the distortion rate in a signal transmission process, and the impact resistance property is good.
Description
Technical field
The present invention relates to one for copper-clad plate composition epoxy resin, especially a kind of Halogen low dielectric-epoxy resin combination that improves shock resistance.
Background technology
Epoxy resin is the important thermosetting resin of a class, is one of most widely used matrix resin in polymer composites.Epoxy resin has the performances such as excellent bonding, wear-resisting, mechanical, electrical isolation, chemically stable, high-low temperature resistant, and the advantage such as shrinking percentage is low, easy machine-shaping, in fields such as tackiness agent, coating, electric insulating material and advanced composite materials, be used widely.
In copper-clad plate application, because its specific inductivity and dielectric loss are higher, dielectric properties cannot meet the requirement of high-frequency signal transmission integrity.Adopt the solidifying agent of styrene-maleic anhydride copolymer (SMA) as epoxy resin, can effectively improve the dielectric properties of resin combination, at CN1935896A, CN1955217A, in CN1955219A, mentioned SMA has been applied in cured epoxy resin, this application is simply the structure of the low-dielectric of SMA energy to be introduced in polymer architecture, realize good thermotolerance and dielectric properties, but epoxy resin and SMA have high crosslinking structure after solidifying, exist matter crisp, the adherence of the laminated plates interlayer of preparation is poor, the shortcomings such as toughness is poor, be difficult to meet the requirement of copper-clad plate processing, therefore to the toughening modifying of epoxy resin, be the focus of research.
Traditional method for toughening, adopts the rubber such as paracril or elastomerics to carry out modified epoxy, and by modification, the shock strength of resin can be significantly improved, but making in the process of prepreg, easily causes prepreg to be bonded together, and impact is used.
In sum, this area lacks a kind of halogen-free environment-friendly type, low dielectric, and has the composition epoxy resin of excellent impact resistance energy, and the prepreg that adopts said composition to prepare is non-caked; Prepared copper-clad plate has lower dielectric coefficient and dielectric loss, can reduce the distortion rate in signals transmission, and impact resistance is good.
Therefore, this area is in the urgent need to developing a kind of halogen-free environment-friendly type, low dielectric, and have excellent impact resistance can composition epoxy resin, the prepreg that adopts said composition to prepare is non-caked; Prepared copper-clad plate has lower dielectric coefficient and dielectric loss, can reduce the distortion rate in signals transmission, and impact resistance is good.
Summary of the invention
The first object of the present invention is to obtain a kind of halogen-free environment-friendly type, low dielectric, and has the composition epoxy resin of excellent impact resistance energy, and the prepreg that adopts said composition to prepare is non-caked; Prepared copper-clad plate has lower dielectric coefficient and dielectric loss, can reduce the distortion rate in signals transmission, and impact resistance is good.
The second object of the present invention is to obtain a kind of halogen-free environment-friendly type, low dielectric, and has the epoxy resin of excellent impact resistance energy, and the prepreg that adopts it to prepare is non-caked; Prepared copper-clad plate has lower dielectric coefficient and dielectric loss, can reduce the distortion rate in signals transmission, and impact resistance is good.
The 3rd object of the present invention is to obtain a kind of halogen-free environment-friendly type, low dielectric, and has the goods of the epoxy resin of excellent impact resistance energy.
In a first aspect of the present invention, a kind of Halogen low dielectric-epoxy resin combination that improves shock resistance is provided, it comprises following component:
The epoxy resin of 10～20 weight parts,
The benzoxazine resin of 5～10 weight parts,
The P contained compound of 30～50 weight parts,
The styrene-maleic anhydride copolymer of 25～35 weight parts and
The nbr carboxyl terminal modified epoxy of 20～30 weight parts.
In a specific embodiment of the present invention, described epoxy resin comprises 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) modified epoxy of 10-dihydro-9-oxy, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ) modified epoxy, phenol phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin or its combination.
In a preference, adopt 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) modification o-cresol formaldehyde epoxy resin, 9 of 10-dihydro-9-oxy, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) Modified phenolic epoxy resin of 10-dihydro-9-oxy, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ) modification o-cresol formaldehyde epoxy resin, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ) Modified phenolic epoxy resin; Phosphorus content 2.7～4.0%.
In a specific embodiment of the present invention, described benzoxazine resin comprises bisphenol A-type benzoxazine resin, bisphenol S type benzoxazine resin, diamines type benzoxazine resin or its combination.
In a specific embodiment of the present invention, described P contained compound comprises Resorcinol two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester], Resorcinol two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester], 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ), 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy, ring-type phenoxy phosphazene compound, hydroxymethyl phenyl phosphinates, or its combination.
In a specific embodiment of the present invention, the structural formula of described phenylethylene-maleic anhydride resin is:
Wherein, m:n=1:1～14:1, n=8～12, weight-average molecular weight is 5000～50000.
In a specific embodiment of the present invention, described nbr carboxyl terminal modified epoxy adopts following technique preparation: the bisphenol A type epoxy resin of getting 13～15 weight parts is placed in reaction vessel with the nbr carboxyl terminal of 5～7 weight parts and at 150 ± 20 ℃, stirs, reacts 4 ± 2 hours; The epoxy equivalent (weight) of described bisphenol A type epoxy resin is 450～700.
In a specific embodiment of the present invention, also comprise the silane coupling agent of 0.5～1 weight part and the silicon-dioxide of 10～20 weight parts.
In a specific embodiment of the present invention, described silane coupling agent comprises (3-epoxypropoxy) Trimethoxy silane and/or (3-epoxypropoxy) triethoxyl silane.
In a specific embodiment of the present invention, described silicon-dioxide is fusion silicon-dioxide.
A second aspect of the present invention provides a kind of Halogen low dielectric-epoxy resin of resulting improvement shock resistance of the present invention.
A third aspect of the present invention provides the application of Halogen low dielectric-epoxy resin of the present invention aspect copper-clad plate.
Embodiment
The inventor, through extensive and deep research, by improving preparation technology, has obtained a kind of halogen-free environment-friendly type, low dielectric, and has the composition epoxy resin of excellent impact resistance energy, and the prepreg that adopts said composition to prepare is non-caked; Prepared copper-clad plate has lower dielectric coefficient and dielectric loss, can reduce the distortion rate in signals transmission, and impact resistance is good.Completed on this basis the present invention.
Below describe in detail to various aspects of the present invention:
Composition epoxy resin
A kind of Halogen low dielectric-epoxy resin combination that improves shock resistance of the present invention, comprises following component: the epoxy resin of 10～20 weight parts, the benzo of 5～10 weight parts are disliked P contained compound, the styrene-maleic anhydride copolymer of 25～35 weight parts and nbr carboxyl terminal (CTBN) modified epoxy of 20～30 weight parts of (wherein " evil " and " Evil " is general) piperazine resin, 30～50 weight parts.
Inventor's discovery, above-mentioned composition epoxy resin belongs to halogen-free environment-friendly type, has low dielectric and excellent impact resistance energy, and the prepreg that adopts said composition to prepare is non-caked; Prepared copper-clad plate has lower dielectric coefficient and dielectric loss, can reduce the distortion rate in signals transmission, and impact resistance is good.
epoxy resin
" epoxy resin " of the present invention does not comprise another component " nbr carboxyl terminal modified epoxy ".
Preferably, described epoxy resin comprises 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) modified epoxy of 10-dihydro-9-oxy, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ) modified epoxy, phenol phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin or its combination.
In a preference, adopt 9,10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO) modification o-cresol formaldehyde epoxy resin, 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) Modified phenolic epoxy resin of 10-dihydro-9-oxy, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ) modification o-cresol formaldehyde epoxy resin, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ) Modified phenolic epoxy resin.Preferably, phosphorus content 2.7～4.0%, with the total weight of described epoxy resin.
When described epoxy resin is phosphorous epoxy resin, it will be appreciated by those skilled in the art that itself and " P contained compound " are different (described P contained compound are micromolecular compounds).
Described epoxy resin can be used separately or mix use as required.Because the finished product of epoxy resin have good physical and mechanical properties, chemical proofing, electrical insulation properties, is widely used in the fields such as coating, tackiness agent, glass reinforced plastic, veneer sheet, electronics casting, embedding.
benzoxazine resin
In a specific embodiment of the present invention, described benzoxazine resin comprises bisphenol A-type benzoxazine resin, bisphenol S type benzoxazine resin, diamines type benzoxazine resin or its combination.
Benzoxazinyl-resin of the present invention comprises that in bisphenol A-type benzoxazine resin, bisphenol S type benzoxazine resin, diamines type benzoxazine resin, the structural formula of described diamines type benzoxazine resin is as follows:
Benzoxazine resin not only has excellent thermotolerance and flame retardant resistance, and has overcome traditional resol and in shaping solidification process, discharge micromolecular shortcoming, and the shrinking percentage while solidifying is almost nil; Play in the present invention the effect of solidifying agent, can increase the stripping strength of Copper Foil and substrate, described benzoxazinyl-resin can be used separately as required or mix use, and its usage quantity is controlled at 5～10 weight parts, and consumption too much can affect the wicking heat-resisting effect of copper clad laminate.
p contained compound
In a specific embodiment of the present invention, described P contained compound comprises Resorcinol two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester], Resorcinol two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester], 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ), 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy, ring-type phenoxy phosphazene compound, hydroxymethyl phenyl phosphinates, or its combination.
The structural formula of described ring-type phenoxy phosphazene compound is:
Formula is:
It is lasting that described P contained compound has flame retardant effect, high thermal stability, good water-fast and solvent resistance, fire retardant is realized completely non-halogen, improve the flowing property in moulding, suppress the resistates after burning, poisonous gas and the corrosive gases of generation are fewer than halogen flame, can use separately or mix and use according to cooperative flame retardant effect.
phenylethylene-maleic anhydride resin
In a specific embodiment of the present invention, the structural formula of described phenylethylene-maleic anhydride resin is:
Wherein, m:n=1:1～14:1, n=8～12, weight-average molecular weight is 5000～50000.
The maleic anhydride structural unit that comprises nonpolar styrol structural unit and strong polarity in molecular structure, by controlling the copolymerization ratio of two monomers, can obtain the different SMA segmented copolymer of multiple performance.Styrene-maleic anhydride copolymer has the novel high polymer material of excellent heat resistance, rigidity and chemical stability, is widely used in the fields such as emulsifying agent, textile auxiliary agent, printing-ink, the matrix material of properties-correcting agent, the agricultural chemicals of latex coating, water conditioner, tackiness agent, the solidifying agent of epoxy resin.By itself and epoxy resin cure and be applied in copper-clad plate and can make base material reach higher second-order transition temperature, reduce dielectric coefficient and the dielectric loss of copper clad foil substrate simultaneously, meet the demand of electronic material performance.
nbr carboxyl terminal (CTBN) modified epoxy
In the present invention, described " nbr carboxyl terminal " is also CTBN.
Resin combination of the present invention is after solidifying, and CTBN modified epoxy can significantly improve the shock resistance of composition.
CTBN modified epoxy of the present invention is by CTBN and epoxy resin pre-polymerization, carboxyl and the epoxide group of CTBN end react, form block structure, synthetic CTBN-epoxy prepolymer, shearing force and the shock strength that can increase substantially epoxy resin, at room temperature have higher stripping strength and fracture toughness property.CTBN modified epoxy, when improving resin fragility, does not reduce mechanical property and the thermotolerance of resin significantly.
In a specific embodiment of the present invention, described nbr carboxyl terminal modified epoxy adopts following technique preparation: the bisphenol A type epoxy resin of getting 13～15 weight parts is placed in reaction vessel with the CTBN of 5～7 weight parts and at 150 ± 20 ℃, stirs, reacts 4 ± 2 hours; The epoxy equivalent (weight) of described bisphenol A type epoxy resin is 450～700.Products therefrom acid number is below 5mgKOH/g, and epoxy equivalent (weight) is 1250～2300.
other components
In composition of the present invention, can further include the silane coupling agent of 0.5～1 weight part and the silicon-dioxide of 10～20 weight parts.
Described silane coupling agent comprises (3-epoxypropoxy) Trimethoxy silane and/or (3-epoxypropoxy) triethoxyl silane.By using silane coupling agent, can between inorganic substance and the interface of organic substance, erect " molecular bridge ", the material of two kinds of character great disparities is linked together and improves the performance and the effect that increases bonding strength of matrix material.
In described mixture, add silicon-dioxide and make filler, preferred molten type silicon-dioxide, contributes to reduce the dielectric loss of epoxy resin cured product.
As no specific instructions, various raw material of the present invention all can obtain by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, the familiar same meaning of all specialties used herein and scientific words and those skilled in the art.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, measures according to national standard conventionally.If there is no corresponding national standard, according to general international standard, normal condition or the condition of advising according to manufacturer, carry out.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or described herein, the familiar same meaning of all specialties used herein and scientific words and those skilled in the art.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
The reagent that embodiment adopts
In the embodiment of the present invention, nomenclature of drug used and source are listed below, but are not limited only to following listed medicine:
(1) epoxy resin
DOPO modified epoxy: the BEP330A70 that Changchun artificial resin factory sells, epoxy equivalent (weight) 350-390, solid content 70%, phosphorus content 2.7%.
O-cresol formaldehyde epoxy resin: the NPCN-704 that South Asia resin is sold, its epoxy equivalent (weight) is between 190～220, and softening temperature is between 95～100 ℃, solid content 100%.
(2) bisphenol A-type benzoxazine resin
The PX-PN001 (bisphenol A-type benzoxazine resin) that Shanghai Chao Yu chemical company sells, solid.
(3) P contained compound
Ring-type phenoxy phosphazene compound: Fushimi Pharmaceutical Co., the FP-100 type ring-type phenoxy phosphazene compound that Ltd. (volt is shown in pharmacy institute) sells, form is solid, phosphorus content is 13.4%.
Hydroxymethyl phenyl phospho acid aluminium: the FRPAA type hydroxymethyl phenyl phospho acid aluminium that Qingdao Fu Silin Chemical Industry Science Co., Ltd sells, form is solid, phosphorus content is 17.2%.
Resorcinol two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester]: the PX-200 that large eight chemical companies of Japan sell, phosphorus content 9.0%, solid.
(4) styrene-maleic anhydride copolymer
The SMA EF-30 that U.S. Sartomer company sells, m:n=3:1, Mw:9500, Tg:125 ℃.
(5) (3-epoxypropoxy) Trimethoxy silane
The KH-560 that the excellent general chemical industry in Nanjing is sold, liquid.
(6) silicon-dioxide
The MEGA-SIL that sells of Bao Lin Industries, Inc (Sibelco Bao Lin)
tM525, fused silica.
(7) CTBN modified bisphenol A type epoxy resin
The U.S. Emerald Performance Materials sell HyPox RA840, elastomer content 40%, epoxy equivalent (weight) 325～360.
(8) CTBN Modified phenolic epoxy resin
The U.S. Emerald Performance Materials sell HyPox RF928, elastomer content 20%, epoxy equivalent (weight) 210～225.
(9) dimer acid modified epoxy resin
The U.S. Emerald Performance Material s sell HyPox DA323, elastomer content 40%, epoxy equivalent (weight) 600～725.
Specific embodiment of the present invention is as follows:
(1) CTBN modified bisphenol A type epoxy resin (CTBN-EP-1) is synthetic
Get the NPES-901 (Nanya Plastic Cement Industry Co., Ltd of 1.3kg, epoxy equivalent (weight) 450～500) be placed in reaction vessel with the CTBN (Hycar CTBN 1300 × 13) of 0.7kg and at 150 ℃, stir, react 4 hours, after having reacted, add again 2kg 1-Methoxy-2-propyl acetate (PMA) to make solvent, will consolidate part and be adjusted to 50%.
(2) CTBN modified bisphenol A type epoxy resin (CTBN-EP-2) is synthetic
Get the EPIKOTE of 1.4kg
tMresin 1001 (Momentive Specialty Chemicals Inc., epoxy equivalent (weight) 450～500) be placed in reaction vessel with the CTBN (Hycar CTBN 1300 × 13) of 0.6kg and at 150 ℃, stir, react 4 hours, after having reacted, add again 2kg 1-Methoxy-2-propyl acetate (PMA) to make solvent, will consolidate part and be adjusted to 50%.
(3) CTBN modified bisphenol A type epoxy resin (CTBN-EP-3) is synthetic
Get the EPIKOTE of 1.5kg
tMresin 1002 (Momentive Specialty Chemicals Inc., epoxy equivalent (weight) 575～700) be placed in reaction vessel with the CTBN (Hycar CTBN 1300 × 13) of 0.5kg and at 150 ℃, stir, react 4 hours, after having reacted, add again 2kg 1-Methoxy-2-propyl acetate (PMA) to make solvent, will consolidate part and be adjusted to 50%.
Embodiment 1
Get the BEP330A70 (DOPO modified epoxy) of 100g, the NPCN-704 (o-cresol formaldehyde epoxy resin) (70% solid content is in PMA) of 100g, the PX-PN001 (bisphenol A-type benzoxazine resin) (70% solid content is in methylethylketone) of 75g, KH-560 (3-epoxypropoxy) Trimethoxy silane of 5g, the FP-100 type ring-type phenoxy phosphazene compound of 350g, the SMA EF-30(styrene-maleic anhydride copolymer of 500g) (50% solid content is in butanone), the CTBN-EP-1 (50% solid content is in PMA) of 400g and the MEGA-SIL of 100g
tM525 mix after strong stirring 6 hours, then with PMA, will consolidate part and be diluted to 65%.Then with screen cloth (100～200mesh), filter, utilize impregnation machine to carry out the impregnation of glasscloth, glue content is controlled at 50 ± 2%, then makes prepreg through baking procedure.By 6 above-mentioned prepreg storehouses, and after bilateral is put Copper Foil, carry out pressing, pressing-in temp is 220 ℃ again, and pressing time is 3 hours, and pressing pressure is 200psi, makes copper clad laminate.
Embodiment 2
Get the PX-200 Resorcinol two [two (2 of PX-PN001 (bisphenol A-type benzoxazine resin) (70% solid content is in methylethylketone), the 500g of BEP330A70 (DOPO modified epoxy), the 100g of 220g, 6-3,5-dimethylphenyl) phosphoric acid ester], the SMA EF-30(styrene-maleic anhydride copolymer of 540g) CTBN-EP-2 (50% solid content is in PMA) of (50% solid content is in butanone), 450g mix after strong stirring 6 hours, then with PMA, will consolidate part and be diluted to 65%.Then with screen cloth (100～200mesh), filter, utilize impregnation machine to carry out the impregnation of glasscloth, glue content is controlled at 50 ± 2%, then makes prepreg through baking procedure.By 6 above-mentioned prepreg storehouses, and after bilateral is put Copper Foil, carry out pressing, pressing-in temp is 220 ℃ again, and pressing time is 3 hours, and pressing pressure is 200psi, makes copper clad laminate.
Embodiment 3
Get the BEP330A70 (DOPO modified epoxy) of 260g, the PX-PN001 (bisphenol A-type benzoxazine resin) (bisphenol A-type benzoxazine resin) (70% solid content is in methylethylketone) of 120g, the KH-560 (component is (3-epoxypropoxy) Trimethoxy silane) of 8g, the FRPAA type hydroxymethyl phenyl phospho acid aluminium of 300g, the SMA EF-30(styrene-maleic anhydride copolymer of 600g) (50% solid content is in butanone), the CTBN-EP-3 (50% solid content is in PMA) of 500g and the MEGA-SIL of 150g
tM525 mix after strong stirring 6 hours, then with PMA, will consolidate part and be diluted to 65%.Then with screen cloth (100～200mesh), filter, utilize impregnation machine to carry out the impregnation of glasscloth, glue content is controlled at 50 ± 2%, then makes prepreg through baking procedure.By 6 above-mentioned prepreg storehouses, and after bilateral is put Copper Foil, carry out pressing, pressing-in temp is 220 ℃ again, and pressing time is 3 hours, and pressing pressure is 200psi, makes copper clad laminate.
Embodiment 4
Get the NPCN-704 (o-cresol formaldehyde epoxy resin) (70% solid content is in PMA) of 280g, the PX-PN001 (bisphenol A-type benzoxazine resin) (70% solid content is in methylethylketone) of 90g, the FP-100 type ring-type phenoxy phosphazene compound of 100g, the FRPAA type hydroxymethyl phenyl phospho acid aluminium of 150g, the PX-200 Resorcinol two [two (2 of 150g, 6-3,5-dimethylphenyl) phosphoric acid ester], the SMA EF-30(styrene-maleic anhydride copolymer of 700g) (50% solid content is in butanone), strong stirring 6 hours after the CTBN-EP-2 (50% solid content is in PMA) of 550g mixes, with PMA, will consolidate part again and be diluted to 65%.Then with screen cloth (100～200mesh), filter, utilize impregnation machine to carry out the impregnation of glasscloth, glue content is controlled at 50 ± 2%, then makes prepreg through baking procedure.By 6 above-mentioned prepreg storehouses, and after bilateral is put Copper Foil, carry out pressing, pressing-in temp is 220 ℃ again, and pressing time is 3 hours, and pressing pressure is 200psi, makes copper clad laminate.
Embodiment 5
Get the BEP330A70 (DOPO modified epoxy) of 50g, the NPCN-704 (o-cresol formaldehyde epoxy resin) (70% solid content is in PMA) of 100g, KH-560 (3-epoxypropoxy) Trimethoxy silane of 10g, the PX-PN001 (bisphenol A-type benzoxazine resin) (70% solid content is in methylethylketone) of 140g, the FP-100 type ring-type phenoxy phosphazene compound of 350g, the PX-200 Resorcinol two [two (2 of 100g, 6-3,5-dimethylphenyl) phosphoric acid ester], the SMA EF-30(styrene-maleic anhydride copolymer of 680g) (50% solid content is in butanone), the CTBN-EP-1 (50% solid content is in PMA) of 600g and the MEGA-SIL of 200g
tM525 mix after strong stirring 6 hours, then with PMA, will consolidate part and be diluted to 65%.Then with screen cloth (100～200mesh), filter, utilize impregnation machine to carry out the impregnation of glasscloth, glue content is controlled at 50 ± 2%, then makes prepreg through baking procedure.By 6 above-mentioned prepreg storehouses, and after bilateral is put Copper Foil, carry out pressing, pressing-in temp is 220 ℃ again, and pressing time is 3 hours, and pressing pressure is 200psi, makes copper clad laminate.
Comparative example 1
Get the PX-200 Resorcinol two [two (2 of PX-PN001 (bisphenol A-type benzoxazine resin) (70% solid content is in methylethylketone), the 500g of NPCN-704 (70% solid content is in PMA), the 130g of 200g, 6-3,5-dimethylphenyl) phosphoric acid ester], the SMA EF-30(styrene-maleic anhydride copolymer of 650g) the HYPOX RA840(CTBN modified bisphenol A type epoxy resin of (50% solid content is in butanone), 300g) mix after strong stirring 6 hours, then with PMA, will consolidate part and be diluted to 65%.Then with screen cloth (100～200mesh), filter, utilize impregnation machine to carry out the impregnation of glasscloth, glue content is controlled at 50 ± 2%, then makes prepreg through baking procedure.By 6 above-mentioned prepreg storehouses, and after bilateral is put Copper Foil, carry out pressing, pressing-in temp is 220 ℃ again, and pressing time is 3 hours, and pressing pressure is 200psi, makes copper clad laminate.
Comparative example 2
Get the PX-200 Resorcinol two [two (2 of PX-PN001 (bisphenol A-type benzoxazine resin) (70% solid content is in methylethylketone), the 500g of NPCN-704 (70% solid content is in PMA), the 130g of 200g, 6-3,5-dimethylphenyl) phosphoric acid ester], the SMA EF-30(styrene-maleic anhydride copolymer of 700g) the RF928(CTBN Modified phenolic epoxy resin of (50% solid content is in butanone), 300g) mix after strong stirring 6 hours, then with PMA, will consolidate part and be diluted to 65%.Then with screen cloth (100～200mesh), filter, utilize impregnation machine to carry out the impregnation of glasscloth, glue content is controlled at 50 ± 2%, then makes prepreg through baking procedure.By 6 above-mentioned prepreg storehouses, and after bilateral is put Copper Foil, carry out pressing, pressing-in temp is 220 ℃ again, and pressing time is 3 hours, and pressing pressure is 200psi, makes copper clad laminate.
Comparative example 3
Get the PX-200 Resorcinol two [two (2 of PX-PN001 (bisphenol A-type benzoxazine resin) (70% solid content is in methylethylketone), the 500g of NPCN-704 (70% solid content is in PMA), the 130g of 200g, 6-3,5-dimethylphenyl) phosphoric acid ester], the SMA EF-30(styrene-maleic anhydride copolymer of 500g) the dimer acid modified epoxy resin of HYPOX DA323(of (50% solid content is in butanone), 300g) mix after strong stirring 6 hours, then with PMA, will consolidate part and be diluted to 65%.Then with screen cloth (100～200mesh), filter, utilize impregnation machine to carry out the impregnation of glasscloth, glue content is controlled at 50 ± 2%, then makes prepreg through baking procedure.By 6 above-mentioned prepreg storehouses, and after bilateral is put Copper Foil, carry out pressing, pressing-in temp is 220 ℃ again, and pressing time is 3 hours, and pressing pressure is 200psi, makes copper clad laminate.
Performance embodiment
Testing method of the present invention is as follows:
Second-order transition temperature (Tg) testing method adopts U.S.'s electronic circuit moulding standard (IPC standard), IPC-TM-650-2.4.25 method (DSC method).
Cracking temperature (Td) testing method is to adopt thermogravimetry (TGA).Choose the square sample that size is about 6.35 × 6.35mm, sample minimum weight is 30mg.Before test, sample should dry 24 hours at 110 ± 2 ℃, and is placed on and in moisture eliminator, is cooled to room temperature.Test should be tested under dry nitrogen atmosphere, and nitrogen flow is 55cc/min.Temperature rise rate with 10 ℃/min rises to 550 ℃ from room temperature, records sample with temperature rise weight loss per-cent, temperature during report weight loss 5%.
288 ℃ of thermotolerance tests (thermomechanical analyzer)
The copper clad laminate of 1mm × 1mm size is placed in to thermomechanical analyzer, temperature is maintained to 288 ℃ after room temperature is warming up to 288 ℃ with the heating rate of 10 ℃/min.Observe dimensional change (having large variation to represent plate bursting) and record the time that after 288 ℃, plate bursting produces.
Stripping strength (PS) test adopts U.S.'s electronic circuit moulding standard (IPC standard), " after the thermal stresses " experiment condition in IPC-TM-650-2.4.8 method, the stripping strength of test metal cap rock.
Wicking thermotolerance test: use the two sides band copper sample of 50 × 50mm, immerses in the scolding tin of 288 ℃, record the time of sample layering foaming.
Shock-resistant test: adopt Du Pont's formula Apparatus for Impacting at low-temp, weight of impact 500g, impact head diameter 12.7mm, laminated plates is lain on anvil, the test plate (panel) part that is hit is no less than 15mm apart from edge, and the edge of each shock point is at a distance of being less than 15mm, and weight borrows control device to be fixed on slide cartridge apart from test plate (panel) 200mm At The Height, press control knob, weight freely falls within on drift.Same test plate (panel) carries out shock test three times, mentions weight and takes out test plate (panel), with 4 times of magnifying glasses, observes, and occurs that cross pattern is qualified, otherwise be defective depending on laminated plates.
Viscosity test: by 5 prepreg storehouses together, apply the pressure of 3Kg on the area of 30cm × 30cm, standing 4hr, removes external force at room temperature, and separable depending on prepreg is qualified, is bonded as defective.
Table 1 is the formula of embodiment 1-5 and comparative example 1-3 and prepared prepreg, the performance table of copper clad laminate.
Table 1
As seen from Table 1, the composition epoxy resin of gained of the present invention is that not halogen-containing, safety and environmental protection, dielectric properties are good; Wherein embodiment is compared with comparative example 1, and prepared prepreg is non-caked, is convenient to processing and uses; Compare with comparative example 3 with comparative example 2, gained laminated plates has excellent shock resistance, and prepared prepreg is non-caked, is convenient to processing and uses.
The foregoing is only preferred embodiment of the present invention, not in order to limit essence technology contents scope of the present invention, essence technology contents of the present invention is to be broadly defined in the claim scope of application, any technology entity or method that other people complete, if defined identical with the claim scope of application, also or a kind of change of equivalence, all by being regarded as, be covered by among this claim scope.
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document, are quoted separately as a reference.In addition should be understood that, after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a Halogen low dielectric-epoxy resin combination that improves shock resistance, is characterized in that, comprises following component:
The epoxy resin of 10～20 weight parts,
The benzoxazine resin of 5～10 weight parts,
The P contained compound of 30～50 weight parts,
The styrene-maleic anhydride copolymer of 25～35 weight parts and
The nbr carboxyl terminal modified epoxy of 20～30 weight parts.
2. composition as claimed in claim 1, it is characterized in that, described epoxy resin comprises 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) modified epoxy of 10-dihydro-9-oxy, 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ) modified epoxy, phenol phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin or its combination.
3. composition as claimed in claim 1, is characterized in that, described benzoxazine resin comprises bisphenol A-type benzoxazine resin, bisphenol S type benzoxazine resin, diamines type benzoxazine resin or its combination.
4. composition as claimed in claim 1, it is characterized in that, described P contained compound comprises Resorcinol two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester], Resorcinol two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester], 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ), 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy, ring-type phenoxy phosphazene compound, hydroxymethyl phenyl phosphinates, or its combination.
5. composition as claimed in claim 1, is characterized in that, the structural formula of described phenylethylene-maleic anhydride resin is:
Wherein, m:n=1:1～14:1, n=8～12, weight-average molecular weight is 5000～50000.
6. composition as claimed in claim 1, it is characterized in that, described nbr carboxyl terminal modified epoxy adopts following technique preparation: the bisphenol A type epoxy resin of getting 13～15 weight parts is placed in reaction vessel with the nbr carboxyl terminal of 5～7 weight parts and at 150 ± 20 ℃, stirs, reacts 4 ± 2 hours; The epoxy equivalent (weight) of described bisphenol A type epoxy resin is 450～700.
7. composition as claimed in claim 1, is characterized in that, also comprises the silane coupling agent of 0.5～1 weight part and the silicon-dioxide of 10～20 weight parts;
Preferably, described silicon-dioxide is fusion silicon-dioxide.
8. composition as claimed in claim 7, is characterized in that, described silane coupling agent comprises (3-epoxypropoxy) Trimethoxy silane and/or (3-epoxypropoxy) triethoxyl silane.
9. the Halogen low dielectric-epoxy resin of a composition resulting improvement shock resistance as claimed in claim 1.
10. a Halogen low dielectric-epoxy resin as claimed in claim 9 application aspect copper-clad plate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN105419277A (en) * | 2015-12-11 | 2016-03-23 | 南京华格电汽塑业有限公司 | Low-dielectric-property composite material |
| CN106536658A (en) * | 2014-07-31 | 2017-03-22 | 东亚合成株式会社 | Adhesive layer-equipped laminate, and flexible copper-clad laminate sheet and flexible flat cable using same |
| CN107603552A (en) * | 2017-09-12 | 2018-01-19 | 广东生益科技股份有限公司 | Halogen-free resin composition, cover layer and the method for preparing cover layer |
| CN111978684A (en) * | 2020-09-18 | 2020-11-24 | 林州致远电子科技有限公司 | Glue solution for improving toughness of medium-loss halogen-free copper-clad plate and preparation method and application thereof |
| CN112063113A (en) * | 2020-09-18 | 2020-12-11 | 林州致远电子科技有限公司 | Glue solution for copper-clad plate applied to HDI (high Density interconnect) multilayer plate and preparation method and application thereof |
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| CN101302327A (en) * | 2007-05-10 | 2008-11-12 | 广科工业股份有限公司 | Halogen-free fire-resistant epoxy resin composition, film and copper clad laminate |
| TWI311568B (en) * | 2005-11-03 | 2009-07-01 | Elite Material Co Ltd | |
| CN102250447A (en) * | 2010-05-21 | 2011-11-23 | 台燿科技股份有限公司 | Halogen-free fire resistance epoxy resin composite as well as prepreg material and printed circuit board therefrom |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN106536658A (en) * | 2014-07-31 | 2017-03-22 | 东亚合成株式会社 | Adhesive layer-equipped laminate, and flexible copper-clad laminate sheet and flexible flat cable using same |
| CN106536658B (en) * | 2014-07-31 | 2021-02-26 | 东亚合成株式会社 | Laminate with adhesive layer, and flexible copper-clad laminate and flexible flat cable using same |
| CN105419277A (en) * | 2015-12-11 | 2016-03-23 | 南京华格电汽塑业有限公司 | Low-dielectric-property composite material |
| CN107603552A (en) * | 2017-09-12 | 2018-01-19 | 广东生益科技股份有限公司 | Halogen-free resin composition, cover layer and the method for preparing cover layer |
| CN107603552B (en) * | 2017-09-12 | 2020-07-28 | 广东生益科技股份有限公司 | Halogen-free resin composition, cover film and method for preparing cover film |
| CN111978684A (en) * | 2020-09-18 | 2020-11-24 | 林州致远电子科技有限公司 | Glue solution for improving toughness of medium-loss halogen-free copper-clad plate and preparation method and application thereof |
| CN112063113A (en) * | 2020-09-18 | 2020-12-11 | 林州致远电子科技有限公司 | Glue solution for copper-clad plate applied to HDI (high Density interconnect) multilayer plate and preparation method and application thereof |
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| CN103724936B (en) | 2016-08-03 |
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