CN117777663A - Resin composition and application thereof - Google Patents
Resin composition and application thereof Download PDFInfo
- Publication number
- CN117777663A CN117777663A CN202311819361.4A CN202311819361A CN117777663A CN 117777663 A CN117777663 A CN 117777663A CN 202311819361 A CN202311819361 A CN 202311819361A CN 117777663 A CN117777663 A CN 117777663A
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- Prior art keywords
- resin
- resin composition
- butanone
- filler
- acrylic resin
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- 239000011342 resin composition Substances 0.000 title claims abstract description 47
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 44
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 44
- 239000002313 adhesive film Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 claims abstract description 19
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 19
- 239000000113 methacrylic resin Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 3
- 239000000945 filler Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- -1 naphthylene ether Chemical compound 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000012766 organic filler Substances 0.000 claims description 4
- 239000011164 primary particle Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000012756 surface treatment agent Substances 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 239000011163 secondary particle Substances 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 239000004643 cyanate ester Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims 1
- 238000003780 insertion Methods 0.000 abstract description 13
- 230000037431 insertion Effects 0.000 abstract description 13
- 238000007731 hot pressing Methods 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 238000005476 soldering Methods 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a resin composition and application thereof, wherein the resin composition comprises the following components: (A) epoxy resin, (B) curing agent, (C) acrylic resin; the (C) component comprises solid acrylic resin which is soluble in butanone and methacrylic resin which is insoluble in butanone; the solid acrylic resin soluble in butanone is thermoplastic acrylic resin, the Tg of the solid acrylic resin is 50-120 ℃, and the weight average molecular weight of the solid acrylic resin is 60-100 ten thousand. According to the resin composition provided by the invention, the solid acrylic resin soluble in butanone and the methacrylic resin insoluble in butanone are compounded for use, the obtained adhesive film has good thickness uniformity after hot pressing, and the influence of the thickness of the insulating layer on the insertion loss can be inhibited; meanwhile, the adhesive film has high Tg, good toughness and excellent heat resistance and crack resistance.
Description
Technical Field
The invention belongs to the technical field of printed circuit boards, and relates to a resin composition and application thereof.
Background
As a technique for manufacturing a printed wiring board, a manufacturing method based on a stacked (build-up) system in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method based on the stacked mode, generally, the insulating layer is formed by curing a resin composition. Along with the development of electronic information products in the directions of thinness, shortness and smallness and multifunction, a printed circuit substrate as a main support of electronic components is gradually developed in the directions of high-frequency high-speed, high-density wiring, thinness, micro-aperture and high heat dissipation.
In recent years, there has been a growing demand for printed wiring boards corresponding to high-frequency bands (high-frequency bands), but insertion loss (insertion loss) is susceptible to the thickness uniformity of insulating layers in high-frequency regions, and electrical signals become heat and/or noise in severe cases, and signals and information cannot be transmitted accurately. Meanwhile, the printed wiring board is generally exposed to a wide range of temperature environments from a low temperature environment such as room temperature to a high temperature environment such as reflow soldering, and the resin material of the insulating layer is repeatedly expanded and contracted to easily cause cracking of the circuit pattern on the surface thereof.
CN114058236a discloses a resin composition comprising (a) a polyether ether ketone compound having a maleimide group, (B) an epoxy resin, and (C) an active ester-based curing agent, and a resin film produced therefrom is low in dielectric characteristics, excellent in peel strength even if the surface roughness is small, and high in glass transition temperature. However, the thickness uniformity of the adhesive film is poor after hot pressing, the variation of characteristic impedance is large, and the insertion loss is large; meanwhile, the adhesive film has insufficient toughness and poor capability of resisting thermal shock.
Therefore, in the art, it is desired to develop a method of suppressing the influence of the thickness of the insulating layer on the insertion loss with good thickness uniformity after hot pressing; meanwhile, the Tg is high, the toughness is good, and the resin composition has excellent heat resistance and crack resistance.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a resin composition and application thereof. The adhesive film prepared by the invention has good thickness uniformity after hot pressing, and can inhibit the influence of the thickness of the insulating layer on the insertion loss; meanwhile, the adhesive film has high Tg, good toughness and excellent heat resistance and crack resistance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a resin composition comprising the following components: (A) epoxy resin, (B) curing agent, (C) acrylic resin;
the (C) component comprises solid acrylic resin which is soluble in butanone and methacrylic resin which is insoluble in butanone;
the solid acrylic resin soluble in butanone is a thermoplastic acrylic resin, and has a Tg of 50-120 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, and specific point values between the above point values, and is limited in space and for the sake of brevity, the present invention does not exhaustively list specific point values included in the range, and has a weight average molecular weight (Mw) of 60-100 ten thousand, for example, 60 ten thousand, 70 ten thousand, 73 ten thousand, 75 ten thousand, 78 ten thousand, 80 ten thousand, 83 ten thousand, 85 ten thousand, 88 ten thousand, 90 ten thousand, 93 ten thousand, 95 ten thousand, 98 ten thousand or 100 ten thousand, and specific point values between the above point values, and is limited in space and for the sake of brevity, the present invention does not exhaustively list specific point values included in the range. If the weight average molecular weight Mw of the butanone-soluble solid acrylic resin is less than 60 ten thousand, it will be tacky and at the same time have a low Tg; if the weight average molecular weight Mw of the butanone-soluble solid acrylic resin is more than 100 ten thousand, the dissolution is difficult and the viscosity is large.
The weight average molecular weight of the invention was measured by gel permeation chromatography based on polystyrene calibration using GB/T21863-2008.
According to the invention, the solid acrylic resin soluble in butanone and the methacrylic resin insoluble in butanone are compounded for use, on one hand, the solid acrylic resin soluble in butanone has higher Tg, so that the problem that the general acrylic resin can deteriorate the Tg of the adhesive film can be solved; meanwhile, the solid acrylic resin with high molecular weight can be fully dissolved in a solvent, and can be matched with methyl acrylic resin which is insoluble in butanone, and the two can respectively form a sea phase and an island phase which are uniformly distributed in the resin composition, so that the flowing of the small molecular resin in the hot pressing process is blocked, the thickness uniformity of the adhesive film after hot pressing is good, and the influence of the thickness of the insulating layer on the insertion loss can be fully restrained. The adhesive film compounded with the acrylic resin has good toughness, excellent heat resistance and crack resistance, and can inhibit the circuit pattern from generating cracks after the resin material of the insulating layer is repeatedly expanded and contracted.
Preferably, the butanone-soluble solid acrylic resin is prepared from methacrylic monomers.
Preferably, the solid butanone-soluble acrylic resin primary particles have a volume average particle diameter of 0.1 to 2 μm (for example, may be 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 1.5 μm or 2 μm, etc.), and the secondary particles have a volume average particle diameter of 20 to 100 μm (for example, may be 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm or 100 μm, etc.). The secondary particles are aggregated particles obtained by aggregating a plurality of primary particles, and if the volume average particle diameter of the acrylic resin primary particles is smaller than 0.1. Mu.m, secondary aggregation is likely to occur, and if the volume average particle diameter is larger than 2. Mu.m, solubility is likely to be affected.
Preferably, the mass ratio of the solid butanone-soluble acrylic resin to the butanone-insoluble methacrylic resin is (0.1-1): 1, which may be, for example, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1:1, and specific point values between the above point values, are limited in length and for brevity, the invention is not exhaustive of the specific point values encompassed by the range.
In the present invention, "butanone-soluble" means that the judgment can be made according to the following method.
1.0g (W) of acrylic resin was accurately weighed in a 50mL sample bottle 0 ) Butanone 40mL was added and dispersed over 1 day. Then, a centrifuge (high-speed cooling centrifuge, trade name: CR22N/CR21N, manufactured by Hitachi Kabushiki Kaisha Co., ltd.) was used at a temperature: 2 ℃, rotation speed: centrifugal separation was carried out at 12000rpm for 60 minutes to separate soluble components and insoluble components, and butanone was added again to the insoluble components to disperse them, and centrifugal separation was carried out similarlyThe soluble and insoluble components are completely separated.
After centrifugal separation, the insoluble matter was heated to 60℃in an oven under a nitrogen atmosphere to remove butanone, and vacuum-dried at 60℃to weigh the insoluble matter (W 1 ) The result was taken as the ratio of butanone insoluble components, i.e., gel fraction. The gel component ratio is calculated by the following formula, and if the gel component ratio is 1 mass% or less, it is considered to be soluble in butanone.
Gel fraction (mass%) =w 1 /W 0 ×100
W 1 : butanone insoluble component amount; w (W) 0 : the amount of acrylic resin in the 50mL sample bottle was accurately weighed.
Preferably, the content of the component (C) is 0.1% -20% by mass of the nonvolatile component in the resin composition, for example, may be 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5% or 20%, and specific point values between the above point values are limited in space and for reasons, and the present invention is not intended to exhaustively list the specific point values included in the range.
Preferably, the (a) component includes any one or a combination of at least two of bisphenol a type epoxy resin, bisxylenol type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, naphthalene type tetrafunctional epoxy resin, or naphthol type epoxy resin.
Preferably, the content of the component (a) is 10% to 40%, for example, 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 33%, 35%, 38% or 40%, and specific point values between the above point values, based on 100% by mass of the nonvolatile components in the resin composition, are limited in space and the present invention is not exhaustive to list the specific point values included in the range for brevity.
Preferably, the (B) component includes any one or a combination of at least two of a phenolic resin, an active ester resin, or a cyanate ester resin.
Preferably, the content of the component (B) is 10% to 30%, for example, 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28% or 30%, based on 100% by mass of the nonvolatile components in the resin composition, and specific point values between the above point values are limited in length and do not exhaustive list the specific point values included in the range for brevity.
Preferably, the resin composition further comprises (D) a filler.
Preferably, the (D) component is present in an amount of 30% to 70%, for example, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%, based on 100% by mass of the nonvolatile components in the resin composition, and specific point values between the above point values are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the filler is an inorganic filler and/or an organic filler, further preferably an inorganic filler.
Preferably, the inorganic filler comprises any one or a combination of at least two of silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, or mica.
Preferably, the organic filler comprises any one or a combination of at least two of polyphenylene oxide filler, polytetrafluoroethylene filler, polyether ether ketone filler, polyphenylene sulfide filler or polyether sulfone filler.
Preferably, the median particle size of the filler is from 0.01 to 50. Mu.m, for example, it may be from 0.01 μm, 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm, and the specific point values between the above point values are limited to a spread and for reasons of brevity, the invention is not intended to exhaustively list the specific point values comprised in the range, more preferably from 0.01 to 20 μm.
In the invention, the particle size is obtained by testing an MS3000 Markov laser particle size analyzer.
Preferably, the filler comprises a surface treated filler.
Preferably, the surface-treated surface treatment agent comprises any one or a combination of at least two of a silane coupling agent, a silicone oligomer and a titanate coupling agent.
Preferably, the surface treatment agent is present in an amount of 0.1 to 5 parts by mass, for example, 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part, 1.5 part, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, and specific point values between the above point values, based on 100 parts by mass of the filler to be treated, and the present invention is not exhaustive of the specific point values included in the range, more preferably 0.5 to 3 parts, still more preferably 0.75 to 2 parts, for reasons of brevity and conciseness.
The "parts" and "parts by weight" according to the present invention are calculated as solid content, and do not include solvents, dispersants, and the like therein.
Preferably, a flame retardant may be further included in the resin composition.
Preferably, the flame retardant is present in an amount of 1% to 50%, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, based on 100% by mass of the nonvolatile components in the resin composition, and specific point values between the above point values are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the flame retardant comprises any one or a combination of at least two of nitrogen flame retardant, halogen flame retardant, phosphorus flame retardant and metal hydroxide flame retardant.
The above-mentioned resin composition may be further added with a solvent, and the amount of the solvent to be added may be selected by those skilled in the art according to experience and process requirements, so that the resin composition may have a viscosity suitable for use, to facilitate coating of the resin composition, and the like. The solvent in the resin composition may be partially or completely volatilized during the subsequent drying, semi-curing or complete curing steps.
The solvent of the present invention is not particularly limited, and generally, ketones such as acetone, butanone, and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol, and butanol, alcohols such as ethylcellosolve, butylcellosolve, ethylene glycol monomethyl ether, carbitol, and butylcarbitol, and nitrogen-containing compounds such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; the solvent may be used alone or in combination of two or more. Ketones such as acetone, butanone and cyclohexanone and aromatic hydrocarbons such as toluene and xylene are preferable.
The resin composition provided by the invention is prepared by the following method, and the preparation method comprises the following steps: the components in the resin composition are mixed and uniformly dispersed to obtain the resin composition.
In a second aspect, the present invention provides a film of a material comprising the resin composition according to the first aspect.
Preferably, the adhesive film is prepared by coating the resin composition on a release material and drying and/or semi-curing the same.
In a third aspect, the present invention provides a metal foil-clad laminate comprising one or at least two laminated adhesive films according to the second aspect, and a metal foil on one or both sides of the laminated adhesive films.
Preferably, the metal foil is copper foil.
In a fourth aspect, the present invention provides a multilayer printed wiring board, the multilayer printed wiring board comprising at least one adhesive film as described in the second aspect, and circuit substrates located on one side or both sides of the adhesive film after lamination, or circuit substrates located on one side of the adhesive film after lamination, and metal foils located on the other side.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the resin composition provided by the invention, the solid acrylic resin soluble in butanone and the methacrylic resin insoluble in butanone are compounded for use, the thickness uniformity of the obtained adhesive film after hot pressing is good, and the influence of the thickness of the insulating layer on the insertion loss is inhibited; meanwhile, the adhesive film has high Tg, good toughness, excellent heat resistance and crack resistance, and the circuit pattern has no crack after being subjected to 1000 times of thermal shock cycles at-65 ℃ and 125 ℃.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The raw materials used in the following examples and comparative examples are as follows:
(A) Epoxy resin:
a1 biphenyl aralkyl type epoxy resin: NC-3000H (Japanese chemical drug);
(B) Curing agent:
b1 phenolic resin: SN-485 (Japanese New Japanese iron);
b2 active ester: HP-8000-65T (DIC in Japan);
b3 cyanate: XU-371 (HUNTSMAN);
(C) Acrylic resin:
c1 butanone-soluble solid acrylic resin: LP-3104, manufactured by Mitsubishi chemical Co., ltd., weight average molecular weight: 70 ten thousand, tg is 71 ℃;
c2 butanone-soluble solid acrylic resin: ME-3498DR, manufactured by Gen industries Co., ltd., weight average molecular weight: 35 ten thousand, tg is-10 ℃;
c3 butanone-soluble solid acrylic resin: SG-P3, manufactured by Nagase ChemteX, inc., has a weight average molecular weight of: 85 ten thousand, tg is 12 ℃;
c4 butanone insoluble methacrylic resin: AC-3816N, ai Ke corporation;
c5 butanone insoluble core shell rubber: methyl methacrylate-butadiene-styrene graft copolymer, M-521, brillouin chemical industry, inc;
(D) And (3) filling:
silica: SC2500-SQ (Admatechs).
Example 1
A resin composition, the specific components and amounts (parts by weight) of which are shown in Table 1.
A laminated printed wiring board is prepared by the following steps:
the epoxy resin and curing agent were dissolved with an appropriate amount of butanone solvent and stirred for 2 hours.
Then adding solid acrylic resin which is dissolved by a proper amount of butanone solvent and is soluble in butanone in advance and methacrylic resin which is not dissolved in butanone and is pre-dispersed by a proper amount of butanone solvent, and stirring for 4 hours.
Adding silicon dioxide, stirring for 4 hours, and mixing thoroughly to form a solution with 70% solid content.
Coating the solution on a release film, airing, and then placing the release film in a 100 ℃ oven for baking for 5 minutes to obtain a semi-cured adhesive film; and (3) pressing and curing the semi-cured adhesive film (with the thickness of 40 mu m) and the browned PCB, tearing off the release film, performing surface treatment, and electroplating copper, thereby forming the laminated printed circuit board with the circuit.
The performance of the adhesive film and the laminated printed circuit board is tested, and the specific method is as follows:
(1) Glass transition temperature Tg: the films were tested with a Dynamic Mechanical Analyzer (DMA) Rheometric RSAIII.
(2) Toughness: the adhesive film was folded in half 180 ° to see if the break occurred, the break was "poor", the crack was "good" but the break was not, and the no crack was "good".
(3) Number of reflow soldering: and (3) carrying out reflow soldering (the peak temperature of reflow soldering is 260+/-3 ℃) on the laminated printed circuit board with the circuit, observing the layering condition of the board surface after each reflow soldering, and recording the times of reflow soldering during layering.
(4) Thickness uniformity after baking and curing of the pressing plate: and (3) pressing and curing the semi-cured adhesive film and the browned PCB, taking samples at 5 positions of the cured PCB, namely, the middle of the cured PCB, the upper left of the cured PCB, the lower left of the cured PCB, the upper right of the cured PCB and the lower right of the cured PCB, and taking the samples as slices to measure the thickness, wherein the thickness is extremely poor, and the absolute value of the thickness is smaller and more excellent.
(5) Crack after TCT:
the circuit pattern was observed for cracking after 1000 thermal shock cycles at-65 ℃ and 125 ℃.
(6) Insertion loss:
an evaluation printed wiring board was produced, and the impedance was set to 50Ω, and VNA (Agilent technology PNA-X) was set to 34mm wiring length: 10MHz to 50GHz, TDR/TDT System (Tektronix DSA 8200) was used: characteristic impedance (characteristic impedance)/eye-pattern (eye pattern), the insertion loss value (dB) at 30GHz at test 3 was measured, and the average value was calculated, with the absolute value of the average value being smaller and more excellent.
The test results are shown in Table 1.
Examples 2 to 5, comparative examples 1 to 5
The difference between the resin composition and the adhesive film and the laminated printed wiring board containing the same and the difference from example 1 is that the resin composition has a different formula, and the formula is shown in tables 1 and 2; wherein the dosage unit of each component is part; the preparation method and performance test method of the adhesive film and the laminated printed wiring board were the same as those of example 1.
TABLE 1
As can be seen from Table 1, the adhesive films provided by the embodiment of the invention have higher Tg (160-180 ℃), better flexibility (excellent), good heat resistance (reflow soldering times are more than 20 times), good thickness uniformity (thickness extremely poor after baking and curing of the pressing plate is less than 2 mu m), no crack of circuit patterns after TCT, good reliability, small insertion loss and contribution to signal transmission.
As can be seen from tables 1 and 2, comparative example 1 does not contain a butanone-soluble solid acrylic resin, and provides a film having a reduced Tg, a reduced number of reflow soldering times, poor thickness uniformity, cracking after circuit pattern TCT, and poor insertion loss, as compared with example 1; comparative example 2, which does not contain methyl acrylic resin insoluble in butanone, provides a film with poor toughness, significantly reduced reflow times, and cracking after TCT; the solid acrylic resin soluble in butanone in comparative example 3 had Tg and weight average molecular weight outside the scope of the present invention, and provided a film having significantly reduced Tg, poor toughness, reduced number of reflow times, and cracks after TCT of the circuit pattern; the solid butanone-soluble acrylic resin of comparative example 4 had a Tg outside the scope of the present invention, and provided a film with significantly reduced Tg, significantly reduced reflow times, and cracking after TCT of the circuit pattern; in comparative example 5, using a butanone-insoluble core-shell rubber, the thickness uniformity of the provided adhesive film was deteriorated, and the circuit pattern TCT was cracked and the insertion loss was also deteriorated.
The applicant states that the present invention is described by way of the above examples as to the resin composition of the present invention and its use, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A resin composition, characterized in that the resin composition comprises the following components: (A) epoxy resin, (B) curing agent, (C) acrylic resin;
the (C) component comprises solid acrylic resin which is soluble in butanone and methacrylic resin which is insoluble in butanone;
the solid acrylic resin soluble in butanone is thermoplastic acrylic resin, the Tg of the solid acrylic resin is 50-120 ℃, and the weight average molecular weight of the solid acrylic resin is 60-100 ten thousand.
2. The resin composition of claim 1, wherein the butanone-soluble solid acrylic resin is prepared from methacrylic monomers;
preferably, the solid butanone-soluble acrylic resin primary particles have a volume average particle diameter of 0.1 to 2 μm, and the secondary particles have a volume average particle diameter of 20 to 100 μm.
3. The resin composition according to claim 1 or 2, wherein the mass ratio of the butanone-soluble solid acrylic resin to the butanone-insoluble methacrylic resin is (0.1-1): 1;
preferably, the content of the (C) component is 0.1% to 20% based on 100% by mass of the nonvolatile component in the resin composition.
4. The resin composition according to any one of claims 1 to 3, wherein the (a) component comprises any one or a combination of at least two of bisphenol a type epoxy resin, bisxylenol type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, naphthalene type tetrafunctional epoxy resin, or naphthol type epoxy resin;
preferably, the content of the (a) component is 10% to 40% based on 100% by mass of the nonvolatile component in the resin composition.
5. The resin composition according to any one of claims 1 to 4, wherein the (B) component comprises any one or a combination of at least two of a phenolic resin, an active ester resin, or a cyanate ester resin;
preferably, the content of the (B) component is 10% to 30% based on 100% by mass of the nonvolatile component in the resin composition.
6. The resin composition according to any one of claims 1 to 5, further comprising (D) a filler;
preferably, the content of the (D) component is 30% to 70% based on 100% by mass of the nonvolatile component in the resin composition.
7. The resin composition according to claim 6, wherein the filler is an inorganic filler and/or an organic filler, further preferably an inorganic filler;
preferably, the inorganic filler comprises any one or a combination of at least two of silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, or mica;
preferably, the organic filler comprises any one or a combination of at least two of polyphenyl ether filler, polytetrafluoroethylene filler, polyether ether ketone filler, polyphenylene sulfide filler or polyether sulfone filler;
preferably, the median particle diameter of the filler is from 0.01 to 50 μm, more preferably from 0.01 to 20 μm;
preferably, the filler comprises a surface-treated filler;
preferably, the surface-treated surface treatment agent comprises any one or a combination of at least two of a silane coupling agent, a silicone oligomer and a titanate coupling agent;
preferably, the surface treatment agent is 0.1 to 5 parts by mass based on 100 parts by mass of the filler to be treated.
8. A film, characterized in that the film material comprises the resin composition according to any one of claims 1 to 7;
preferably, the adhesive film is prepared by coating the resin composition on a release material and drying and/or semi-curing the same.
9. A metal foil-clad laminate comprising one or at least two laminated adhesive films according to claim 8, and metal foils on one or both sides of the laminated adhesive films.
10. A multilayer printed wiring board comprising at least one adhesive film according to claim 8 laminated, and wiring substrates on one side or both sides of the laminated adhesive film, or wiring substrates on one side of the laminated adhesive film and metal foils on the other side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311819361.4A CN117777663A (en) | 2023-12-27 | 2023-12-27 | Resin composition and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311819361.4A CN117777663A (en) | 2023-12-27 | 2023-12-27 | Resin composition and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117777663A true CN117777663A (en) | 2024-03-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311819361.4A Pending CN117777663A (en) | 2023-12-27 | 2023-12-27 | Resin composition and application thereof |
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| Country | Link |
|---|---|
| CN (1) | CN117777663A (en) |
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2023
- 2023-12-27 CN CN202311819361.4A patent/CN117777663A/en active Pending
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