CN102050939A - Thermosetting resin composition with acid anhydride curing - Google Patents
Thermosetting resin composition with acid anhydride curing Download PDFInfo
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- CN102050939A CN102050939A CN2009102091254A CN200910209125A CN102050939A CN 102050939 A CN102050939 A CN 102050939A CN 2009102091254 A CN2009102091254 A CN 2009102091254A CN 200910209125 A CN200910209125 A CN 200910209125A CN 102050939 A CN102050939 A CN 102050939A
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Abstract
The invention relates to a resin composition for a printed circuit board. The composition comprises an epoxy resin or a mixture of more than one epoxy resin, curing agents, an accelerant and an additive, wherein the ratio of the curing agent to the epoxy resin is 1.55 to 2.5; at least one of the epoxy resins is phenolic-benzaldehyde multifunctional epoxy resin; and at least one of the curing agents is styrene-maleic anhydride copolymer. The cured resin composition has good electric property, high glass transition temperature and excellent heat resistance, and can be applied in the lead-free process for the printed circuit board and the field of printed circuit boards of high-frequency and encapsulated support plates.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, have high-vitrification tansition temperature, good heat-resisting character and excellent electrical specification.
The invention still further relates to above-mentioned Resins, epoxy in the application of making preimpregnation material, adhesive film, copper clad laminate, can be applicable to the printed circuit board (PCB) in electronic package and high frequency field, or the carrier plate material of encapsulation usefulness.
Background technology
Resins, epoxy is used on copper clad laminate and the printed circuit board (PCB) existing historical for many years, and major cause is Resins, epoxy and reinforcement material such as glasscloth, glass seat, paper etc., and then intensity is good, and can not produce fugitive constituent during curing, and molding shrinkage is little; The copper clad laminate of manufacturing has good physical strength, electric insulating quality, chemical-resistant, and dimensional precision well is easy to processing again and has been the topmost raw material of printed circuit board (PCB) today.
The present employed copper clad laminate of printed circuit board (PCB) (Copper Clad Laminate, CCL) no matter quantitatively or on the technological layer, all be based on FR-4 sheet material, but the development of electronic industry is advanced by leaps and bounds, the step that the important associated component-printed circuit board (PCB) of relative its also must be kept pace with the times.For system product, light, thin, short, the little power saving of product is durable, for electronic package, be accompanied by that process dwindles and what come is that operating frequency improves constantly, operating voltage continues to reduce, transistor current consumption reduces again and again, and under the effect such as the voltage adaptable noise is more and more little, the problem that need not consider when causing low frequency is originally also all appeared in one's mind one by one, and the printed circuit board (PCB) that only belongs to interconnect lines (interconnection) industry has been produced two main developing direction; One, highdensity printed circuit board (PCB): its major technique is fine rule, aperture, blind hole, buried via hole.Two, the circuit card of high-frequency electronic assembly support plate and high-velocity electrons product: major technique is the sheet material of low dielectric constant, low loss factor and the impedance Control of film dielectric layer sheet material and precision etc.
21 century will become video signal from generation to generation, the application of high-frequency high-speed is one of important development trend of printed circuit board (PCB) (PCB) from now on, though traditional F R-4 substrate still can satisfy the demand of present most of printed circuit board (PCB) industry, and the proportion that occupies the biggest market, but increase gradually with demand, under material property and cost consideration, common product can satisfy the demands with standard type FR-4 substrate (epoxy glass fabric substrate), but product to high-frequency transmission, baseplate material is had relatively high expectations, low dielectric constant, low loss factor substrate cooperates this information products move towards at a high speed just and high frequencyization and communication product move towards can be in a large number transferring voice fast again, requirements such as video signal data.
Copper foil base plate materials mainly is made of reinforcement material and resin combination, and the skin Copper Foil of fitting again will be so resin combination will be to influence one of electrical principal element of substrate.The present invention will illustrate that the exploitation that utilizes resin combination reaches and improve the electrical effect of substrate.
In belgian patent BE627887, once mentioned, use maleic anhydride and cinnamic multipolymer as curing agent for epoxy resin, but the shortcoming of this composition epoxy resin is that vitrifying tansition temperature (Tg) is low and heat-resisting character is poor, makes it be not suitable for being applied to copper clad laminate and printed circuit board (PCB) manufacturing.
When anhydride type curing agent and Resins, epoxy used, normal-temperature reaction was quick under interpolation promotor, and is not suitable for being applied to art of printed circuit boards.
The resin system that is used for copper clad laminate and printed circuit board (PCB) at present is a Resins, epoxy, the FR4 substrate of general use standard, its main component is that the made brominated epoxy resin of bisphenol A epoxide resin or tetrabromo-bisphenol is main resinous principle, with dicyandiamide as solidifying agent, add promotor and solvent again, the shortcoming of this kind composition epoxy resin is that low excessively (120-140 ℃) of vitrifying tansition temperature (Tg) and heat-resisting character are poor, if adopt polyfunctional epoxy resin to replace bisphenol A epoxide resin, utilize the raising of cross-linking density can improve the low shortcoming of vitrifying tansition temperature (Tg), but there is no too big contribution for improving thermotolerance and electrical properties.
Prompting uses the multipolymer (SMA) of vinylbenzene and maleic anhydride as resin curing agent in the U.S. Pat 6509414, can make the Resins, epoxy of general difunctionality base improve the thermotolerance of material, utilize the method for co-crosslinker again, for example using the multipolymer and the co-crosslinker of vinylbenzene and maleic anhydride is tetrabromo-bisphenol (TBBA), tetrabromo-bisphenol diglycidylether (TBBADGE), improves sheet material vitrifying tansition temperature (Tg); Wherein acid anhydrides and aromatic hydroxyl group (OH) are 50%～150% with Resins, epoxy equivalent ratio in the mixed with resin.Again by knowing understanding in its suggested example, the equivalent ratio increases at 110% o'clock by 70%, DSC vitrifying tansition temperature (Tg) increases to 155 ℃ by 122 ℃, again the equivalent ratio is increased at 150% o'clock by 110%, and DSC vitrifying tansition temperature (Tg) is reduced to 137 ℃ by 155 ℃ on the contrary.Phenomenon learns that equivalence ratio surpasses about 110% thus, and linking agent can't promote cross-linking density again improves DSC vitrifying tansition temperature (Tg).
Copper clad laminate and printed circuit board (PCB) are made trend and are moved towards non-bromine series (being mainly phosphorus is flame retardant) even halogen system by halogen system (being mainly bromine is anti-right agent TBBA) now; Upgrading type copolymer-maleic anhydride solidifying agent of the present invention synthesizes in response to following environmental protection demand, can be halogen system, phosphorus system or is the halogen system.
Summary of the invention
The object of the present invention is to provide a kind of heat curing-type resin composition, its reasonable price, be applicable to printed circuit board (PCB) with anhydride-cured.
For achieving the above object, compositions of thermosetting resin with anhydride-cured provided by the invention, this constituent comprises one or more epoxy resin composition, solidifying agent, promotor and additive, the ratio of solidifying agent and Resins, epoxy is 1.55～2.5, and wherein Resins, epoxy is at least a is phenol-phenyl aldehyde polyfunctional epoxy resin; Solidifying agent is at least a to be styrene-maleic anhydride copolymer.
Have good electrical properties, high glass transition temp and excellent heat-resisting character after resin combination of the present invention solidifies, can be applicable to the art of printed circuit boards of lead-free process, high frequency and the encapsulating carrier plate of printed circuit board (PCB).
Embodiment
The resin combination that has good electrical properties, high glass transition temp and excellent heat-resisting character after the curing provided by the invention is applicable to the art of printed circuit boards of lead-free process, high frequency and the high laminate of printed circuit board (PCB).This resin combination composition comprises one or more epoxy resin composition, solidifying agent, promotor and additive.
Described epoxy resin composition, at least select a kind of phenol-phenyl aldehyde polyfunctional epoxy resin (formula I) (United States Patent (USP) 6512075) for use, using the purpose of phenol-phenyl aldehyde polyfunctional epoxy resin, is the epoxy functionalized radix that has high-density benzene ring structure and suitable number on the chemical structure of this Resins, epoxy.Therefore have excellent heat resistance and high Tg, the epoxy functionalized radix of this suitable number and benzene ring structure is three-dimensional restricted simultaneously, makes it have suitable reactivity, higher resin melting viscosity, so broad pressing processing interval is arranged.Intensity is followed in lifting and impregnation can be used monofunctional, difunctionality basic ring epoxy resins, and epoxy equivalent (weight) is 150～3000g/eq, is selected from bisphenol A epoxide resin, bisphenol F epoxy resin.It is that Resins, epoxy, phosphorus are that Resins, epoxy or nitrogen are Resins, epoxy that the increase flame retardancy can be selected bromine for use, also can select the brominated resins that contains phenol-phenyl aldehyde polyfunctional epoxy resin for use.In addition, promote electrical specification and can add cyanate ester resin (Cyanate Ester), PPO resin, dicyclopentadiene class (DCPD) Resins, epoxy, for example BA230, the PT60 etc. of the cyanate ester resin with cyanic acid functional group of Lonza production.
Above-mentioned phenol-phenyl aldehyde polyfunctional epoxy resin, for phenol and phenyl aldehyde carry out phenol-phenyl aldehyde resin that condensation reaction gets in the presence of acidic catalyst, continuous again with 1-chloro-2, the 3-epoxy chloropropane synthesizes phenol-phenyl aldehyde polyfunctional epoxy resin in the presence of sodium hydroxide.Synthetic reaction condition is as using 1-chloro-2,3-epoxy chloropropane epoxidation technique, and institute's synthetic phenol-its epoxy equivalent (weight) of phenyl aldehyde polyfunctional epoxy resin is 210～260g/eq, and average sense radix is 2～6, and average molecular weight Mw is 400～2500.The brominated resins that contains phenol-phenyl aldehyde polyfunctional epoxy resin, system comprises (A) phenol-phenyl aldehyde polyfunctional epoxy resin, content 10～70wt%, (B) difunctionality basic ring epoxy resins, content 0～55wt%, epoxy equivalent (weight) is 170～500g/eq, (C) brominated difunctionality basic ring epoxy resins, content 0～20wt%, epoxy equivalent (weight) are 300～500g/eq, brominated amount 30～55%, (D) tetrabromo-bisphenol, content 15～40wt%, molecular weight 544, with (D) with (A), (B), (C) at least a Resins, epoxy of three is reacted into brominated epoxy resin earlier, and then adding (A), (B), (C) remaining part mixes promptly, and its average molecular weight Mw is 1500～4000, molecular weight distributing index (ratio of Mw/Mn) is 1.5～4.0, and epoxy equivalent (weight) is 300～500g/eq.
The selecting for use of described epoxy resin composition can be looked processibility, rerum natura etc. and be selected above-mentioned wherein one or more resin to use.
Described solidifying agent is selected a kind of styrene-maleic anhydride copolymer at least for use, the purpose of selecting anhydride curing agent for use is that anhydride compound has good thermal properties, agent of low hygroscopicity, and add anhydride compound with vinylbenzene structure, because distyryl compound has good electrical specification, but except boosted tree oil/fat composition thermotolerance, but the also electrical properties of boosted tree oil/fat composition.The anhydride curing agent that the present invention selects for use is the phenylethylene-maleic anhydride polymkeric substance with vinylbenzene structure, its structure is suc as formula 2, phenylethylene-maleic anhydride polymkeric substance with vinylbenzene structure, one or more of the optional SMA1000 of commercial goods freely, SMA2000, SMA3000, EF10, EF20, EF30, EF40, EF80 etc.Acid anhydrides and Resins, epoxy equivalent ratio are 1.55～2.5, and the best is 1.55～2.3, and this resin combination has good electrical properties, high Tg and excellent heat resistance after solidifying.
M in the formula 2, n are positive integer, can be identical or different number.
The purpose of adding promotor is for promoting the crosslinking reaction (Crosslinking) between resin and the solidifying agent, and the number of addition can influence its speed of reaction, can be selected from tertiary amine and its esters, quaternary ammonium compound salt compound, imidazoles, list or polyphenolic substance, boron trifluoride and organic complex compound, phosphoric acid or triphenyl phosphite wherein one or more.But be preferably tertiary amine and its esters, imidazoles or its mixture.
Described additive is decided by the characteristic demand of resin combination, adds to reach and improves or strengthen working properties, mechanical properties and sheet material rerum natura.Can select one or more of inorganic powder, incombustible agent or toughner for use.For example improve the rigidity after resin combination solidifies in advance or reduce thermal expansivity, can add inorganic powder, for example add the thermal expansivity that silicon-dioxide can reduce cured article, aluminum oxide, silicon carbide can improve thermal conduction etc.Or select high molecular phenoxy resin (Phenoxy resin), rubber (Rubber) etc. for use, for example add INCHEMREZ PKHS high molecular phenoxy resin (Phenoxyresin) and can improve the obdurability in the prescription system and promote shock strength; For example add
CTBN1300 * 8 rubber can improve and Copper Foil between then intensity.Or select incombustible agent for use, for example add tetrabromo-bisphenol (TBBA) or big eight industrial PX200 incombustible agents can increase the nonflammable characteristic of sheet material etc.
Compositions of thermosetting resin with anhydride-cured of the present invention, said composition can be dissolved fully with solvent at normal temperatures, be deployed into and stablize homogeneous varnish (varnish), preimmersion base material (Prepreg), copper foil base plate materials so that it is made can be used for printed circuit board (PCB).
Described preimmersion base material (Prepreg) is after resin combination of the present invention is deployed into varnish (varnish), utilize the reinforcement material via the composition that contains epoxy resin dipping, by heated oven solvent evaporates while resin combination is carried out the part reaction again and present semicure film (B-stage).This reinforcement material can be glass fibre, carbon fiber, Ke Weila fiber (kelvar), paper fiber, as aromatic polyamide paper etc.; This preimmersion base material (Prepreg) further pressing is made into copper clad laminate, is made up with one or more preimmersion base material, descends the two sides to place Copper Foil thereon, and the pressurized, heated said composition obtains the matrix material of copper clad laminate at last again.Have high-vitrification tansition temperature (Tg), good heat-resisting character and excellent electrical specification after resin combination of the present invention solidifies, can be applicable to the printed circuit board (PCB) in general or high frequency field.The present invention is described further following examples for reference.
Embodiment one
Use multipolymer (EF30) 104 grams of phenol-phenyl aldehyde polyfunctional epoxy resin (the Nan Ya NPPN-433 of company) 100 grams and vinylbenzene and maleic anhydride, elder generation's predissolve forms one 60% solution in methyl ethyl ketone (MEK), and promotor 2MI 0.04 gram, with respect to whole resin solid content, acid anhydrides and Resins, epoxy equivalent ratio are 1.2.
Stirred this resin combination 3 hours, the test gel time is 270 seconds on 170 ℃ hot plate afterwards; This solution sent into contain in the immersion trough, utilize glasscloth (model 7628) continous way impregnation, via heated oven with solvent evaporates simultaneously resin combination carry out part and react and present semicure film (B-stage), go out and after baking oven is cooled to room temperature this semicure film cut into sheet; Copper Foil of each storehouse (specification 1oz) up and down with 8 slim semicure films utilizes 2.5 ℃/minute of thermocompressor temperature rise rates again, rises to 195 ℃ and continues 60 to 120 minutes, and pressure uses 20～30kg/cm
2, will continue reaction via thermocompressor pressing resin combination and finish (C-stage) to solidifying, have 175 ℃ vitrifying tansition temperature (Tg) and good thermotolerance etc. via the physical property measurement proof.The physical property measurement data are listed in table two.
Embodiment two
According to the resin combination of embodiment one, increase acid anhydrides and Resins, epoxy equivalent ratio to 1.75, again according to above-mentioned manufacture method institute solidified resin combination, via the physical property measurement proof except original characteristic, for Tg promote and electrical properties helpful.The physical property measurement data are listed in table two.
Embodiment three
Resin combination ratio according to embodiment two, with respect to outer 20% the incombustible agent PX200 that adds of whole resin solid content, with 10% aluminium hydroxide and 10% silicon-dioxide, again according to above-mentioned manufacture method institute solidified resin combination, except original characteristic, thermal expansivity and flame retardancy are helpful for reducing via the physical property measurement proof.The physical property measurement data are listed in table two.
Embodiment four
Use contains brominated epoxy resin (the Nan Ya NPEB-487A80 of company) 100 grams of phenol-phenyl aldehyde polyfunctional epoxy resin, the first predissolve of multipolymer (EF30) that adds 70.9 gram vinylbenzene and maleic anhydride in this solution forms one 60% solution and promotor 2MI0.04 gram in methyl ethyl ketone (MEK), and acid anhydrides and Resins, epoxy equivalent ratio are 1.65.According to the manufacture method of embodiment one, the physical property measurement proof has 188 ℃ Tg and good thermotolerance etc.The physical property measurement data are listed in table two.
Embodiment five
Resin combination according to embodiment four, increase acid anhydrides and Resins, epoxy equivalent ratio to 2.20, and high molecular phenoxy resin (Phenoxy resin, INCHEMREZ PKHS) 18.9 g, according to the manufacture method of embodiment one, the physical property measurement proof has 195 ℃ Tg and good thermotolerance etc.The physical property measurement data are listed in table two.
Comparative example one
Bisphenol A epoxide resin and the made brominated epoxy resin of tetrabromo-bisphenol of getting 100 grams are main resin composition, also first with dimethyl formamide (DMF) predissolve with dicyandiamide as solidifying agent, with respect to whole resin solid content, Resins, epoxy and solidifying agent equivalence ratio are 0.5, add promotor 2MI again, be adjusted to the resin combination of solid content 65% with solvent methyl ethyl ketone (MEK).According to the manufacture method of embodiment one, physical property measurement Tg140 ℃ and 288 ℃ of tin stove thermotolerances are 2～3 minutes.The physical property measurement data are listed in table two.
Comparative example two
Based on comparative example one, change bisphenol A epoxide resin and the made brominated epoxy resin of tetrabromo-bisphenol into contain phenol-phenyl aldehyde polyfunctional epoxy resin brominated resins (the Nan Ya NPEB-487A80 of company).According to the manufacture method of embodiment one, physical property measurement Tg170 ℃ and 288 ℃ of tin stove thermotolerances are 2-3 minute.The physical property measurement data are listed in table two.
The resin combination equivalence ratio of table one, each embodiment and comparative example
The substrate properties of table two, each embodiment and comparative example
a：after?pressure?cooker?tor?30?mins
Select the resin combination that contains phenol-phenyl aldehyde polyfunctional epoxy resin and phenylethylene-maleic anhydride solidifying agent for use, have high Tg, excellent heat resistance and electrical properties after the curing.Improve acid anhydrides and Resins, epoxy equivalent ratio,, have clear improvement for the dielectric constant and the loss factor that reduce electrical specification except promoting the Tg; Acid anhydrides and Resins, epoxy equivalent ratio are 1.55～2.5, and optimum proportion is 1.55～2.3, can get a resin combination with high Tg, superior electrical character, applicable to printed circuit board (PCB).
Claims (10)
1. heat curing-type resin composition with anhydride-cured comprises:
One or more epoxy resin composition, solidifying agent, promotor and additive, the ratio of solidifying agent and Resins, epoxy is 1.55～2.5; Wherein epoxy resin composition is selected a kind of phenol-phenyl aldehyde polyfunctional epoxy resin that contains at least for use, and solidifying agent is selected a kind of styrene-maleic anhydride copolymer at least for use.
2. the heat curing-type resin composition that has anhydride-cured according to claim 1, wherein, acid anhydrides and Resins, epoxy equivalent ratio are 1.55～2.3.
3. the heat curing-type resin composition that has anhydride-cured according to claim 1, wherein, the epoxy equivalent (weight) of phenol-phenyl aldehyde polyfunctional epoxy resin is 210～260g/eq, average sense radix 2～6, average molecular weight Mw 400～2500.
4. the heat curing-type resin composition that has anhydride-cured according to claim 1, wherein, the brominated resins that contains phenol-phenyl aldehyde polyfunctional epoxy resin, comprise phenol-phenyl aldehyde polyfunctional epoxy resin 10～70%, its epoxy equivalent (weight) is 300-500g/eq, average molecular weight Mw 1500～4000, molecular weight distributing index are 1.5～4.0.
5. the heat curing-type resin composition that has anhydride-cured according to claim 1, wherein, promotor select for use tertiary amine and its esters, quaternary ammonium compound salt compound, imidazoles, list or polyphenolic substance, boron trifluoride and organic complex compound, phosphoric acid or triphenyl phosphite wherein one or more.
6. the heat curing-type resin composition that has anhydride-cured according to claim 1, wherein, the characteristic demand that additive is looked resin combination is selected one or more of inorganic powder, incombustible agent or toughner for use.
7. the described heat curing-type resin composition with anhydride-cured of claim 1 is used, through impregnation or be coated on and make the preimpregnation material on the supporting material.
8. use as the heat curing-type resin composition that has anhydride-cured as described in the claim 7, wherein, the preimpregnation material makes copper foil laminates after hot pressing.
9. the described application with heat curing-type resin composition of anhydride-cured of claim 1 is through impregnation or be coated on and make adhesive film on the supporting material.
10. use as the heat curing-type resin composition that has anhydride-cured as described in claim 8 or 9, wherein, copper foil laminates or adhesive film make printed circuit board (PCB) through hot pressing and wet technology.
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| CN102417758A (en) * | 2011-08-09 | 2012-04-18 | 江门市阪桥电子材料有限公司 | Liquid photoreceptive solder resist ink |
| CN102964567A (en) * | 2012-12-11 | 2013-03-13 | 南通市福来特化工有限公司 | Epoxy resin curing agent |
| CN103642446A (en) * | 2013-12-10 | 2014-03-19 | 上海南亚覆铜箔板有限公司 | Lead-free high heat-resisting copper-clad board and preparation method thereof |
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| CN102277062A (en) * | 2011-06-30 | 2011-12-14 | 浙江天女集团制漆有限公司 | Production method of environment friendly recycled high-insulation coating for electronic components |
| CN102352150B (en) * | 2011-08-09 | 2014-04-02 | 江门市阪桥电子材料有限公司 | Liquid photosensitive solder resist white oil and manufacturing method thereof |
| CN102352150A (en) * | 2011-08-09 | 2012-02-15 | 江门市阪桥电子材料有限公司 | Liquid photosensitive solder resist white oil and manufacturing method thereof |
| CN102417758A (en) * | 2011-08-09 | 2012-04-18 | 江门市阪桥电子材料有限公司 | Liquid photoreceptive solder resist ink |
| CN102417758B (en) * | 2011-08-09 | 2014-04-16 | 江门市阪桥电子材料有限公司 | Liquid photoreceptive solder resist ink |
| CN102964567A (en) * | 2012-12-11 | 2013-03-13 | 南通市福来特化工有限公司 | Epoxy resin curing agent |
| CN103642446A (en) * | 2013-12-10 | 2014-03-19 | 上海南亚覆铜箔板有限公司 | Lead-free high heat-resisting copper-clad board and preparation method thereof |
| US10815372B2 (en) | 2017-03-27 | 2020-10-27 | Nan Ya Plastics Corporation | Process for the preparation of a flame-retardant modified styrene-maleic anhydride resin and a composition of epoxy resins and their application to copper clad laminate and prepreg |
| JP7459901B2 (en) | 2017-03-30 | 2024-04-02 | 株式会社レゾナック | Prepreg and its manufacturing method, laminate, printed wiring board, and semiconductor package |
| CN108727775A (en) * | 2017-04-21 | 2018-11-02 | 南亚塑胶工业股份有限公司 | It is resistance to combustion modification type styrene maleic resin curing agent preparation method and epoxy resin composition and its in copper clad laminate and film application |
| CN108727775B (en) * | 2017-04-21 | 2020-12-25 | 南亚塑胶工业股份有限公司 | Preparation method of flame-retardant modified styrene maleic anhydride resin hardener, epoxy resin composition and application of epoxy resin composition in copper foil substrate and film |
| CN107266858A (en) * | 2017-06-13 | 2017-10-20 | 南亚新材料科技股份有限公司 | A kind of middle Tg compositions of thermosetting resin and preparation method thereof |
| CN108127994A (en) * | 2017-08-07 | 2018-06-08 | 南亚新材料科技股份有限公司 | A kind of compositions of thermosetting resin copper-clad plate and preparation method thereof |
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Application publication date: 20110511 |