CN105778412A - Epoxy resin composition and prepreg and laminated board using same - Google Patents
Epoxy resin composition and prepreg and laminated board using same Download PDFInfo
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- CN105778412A CN105778412A CN201410831357.4A CN201410831357A CN105778412A CN 105778412 A CN105778412 A CN 105778412A CN 201410831357 A CN201410831357 A CN 201410831357A CN 105778412 A CN105778412 A CN 105778412A
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- 0 CCC(CO)NC(*)OC(C=CC(C(C)(C)C(C=C1)=C=CC=C1O*C(C)CO)=C)=C Chemical compound CCC(CO)NC(*)OC(C=CC(C(C)(C)C(C=C1)=C=CC=C1O*C(C)CO)=C)=C 0.000 description 3
- VMBUUPYAGAQZMM-UHFFFAOYSA-N OC1=CC=CCC1 Chemical compound OC1=CC=CCC1 VMBUUPYAGAQZMM-UHFFFAOYSA-N 0.000 description 2
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/02—Layered products comprising a layer of natural or synthetic rubber with fibres or particles being present as additives in the layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
Abstract
The invention relates to an epoxy resin composition and a prepreg and laminated board using same.The epoxy resin composition is prepared from novolac epoxy resin, core-shell rubber-toughened epoxy resin or/and core-shell rubber, bromized bisphenol A epoxy resin, four-functional-group epoxy resin, active ester and a linear phenolic resin compound curing agent.Adopted novolac epoxy resin has high glass-transition temperature, low water absorption and excellent dielectric property at the same time, core-shell rubber-toughened epoxy resin can improve toughness and technical processablity, bromized bisphenol A epoxy resin provides flame retardance while raising glass-transition temperature, and the active ester and the linear phenolic resin compound curing agent are beneficial for realizing balance among heat resistance, dielectric property and water absorption and reducing cost at the same time.The prepreg and laminated board made of the epoxy resin composition are high in heat resistance, small in dielectric loss value, high in humidity resistance, low in water absorption and good in toughness.
Description
Technical field
The invention belongs to copper-clad plate technical field, be specifically related to a kind of composition epoxy resin and use its prepreg and laminate.
Background technology
Along with electronic devices and components develop towards the direction of small-size light-weight slimming, high performance and multifunction, what bring therewith is high frequency and the transmission of signal at a high speed.This just requires that the dielectric constant of electronic material and dielectric loss are relatively low, these are relevant with the structure of material, and low-k, low dielectric loss tangent resin structurally generally have: big free volume, low polarizable, low water absorption, low-k the feature such as structure existence.
Phenolic resin curing epoxy resin has been a mature technology, but in phenolic resin and epoxy reaction process, has the generation of secondary hydroxyl, cause the water absorption of system and the problem that dielectric properties are poor, and fragility is bigger.
In active ester and epoxy resin course of reaction, it does not have secondary hydroxyl generates, and it is fairly good that it has low water absorbable, humidity resistance and dielectric properties, but its cost is more expensive, and can cause that the glass transition temperature of system is relatively low as independent firming agent use.
CN101323698A adopts bisphenol A-type novolac epoxy resin, brominated bisphenol a type epoxy resin, brominated bisphenol a type epoxy resin and end carbonyl LNBR prepolymer, linear phenolic resin, tetrabromobisphenol A, though having good toughness, but there is high-hydroscopicity in it and its dielectric properties are poor, and brominated bisphenol a type epoxy resin and end carbonyl LNBR prepolymer are easily separated thoroughly or non-optimal conditions, the intrinsic thermostability of epoxy resin and elastic modelling quantity is caused to decline, it is difficult to ensure that improving fragility and impact resistance, do not sacrifice again thermostability, mechanical strength and chemical proofing.
CN103897350A adopts ortho-cresol novolac resin, linear phenolic resin and tetrabromobisphenol A, although the problem that its fragility brought by ortho-cresol novolac resin+linear phenolic resin solidification by adding more tetrabromobisphenol A to improve is excessive, but the thermostability that too much tetrabromobisphenol A introducing can cause sheet material is deteriorated, and humidity resistance, water absorption and dielectric properties cannot be guaranteed.
For this, how to solve the high-hydroscopicity that phenolic resin curing epoxy resin brings, the technical problem that humidity resistance is poor, dielectric properties are poor and fragility is poor, find equilibrium point between which, it is achieved the balance of thermostability and humidity resistance becomes one of technical barrier.
Summary of the invention
For the problem of prior art, it is an object of the invention to provide a kind of composition epoxy resin and use its prepreg and laminate.The laminate using this resin combination manufacture has that better thermostability, low dielectric loss value, humidity resistance be good, the advantage of low water absorption and excellent toughness.
The present inventor has carried out repeatedly deep research for achieving the above object, found that: novolac epoxy resin, core shell rubbers are epoxy resin toughened or/and core shell rubbers, brominated bisphenol a type epoxy resin, tetrafunctional epoxy resin and active ester and novolac firming agent, and other compositionss that component suitably mixes alternatively, above-mentioned purpose can be reached.
A kind of composition epoxy resin, it includes following component:
(A) novolac epoxy resin；
(B) core shell rubbers is epoxy resin toughened or/and core shell rubbers；
(C) brominated bisphenol a type epoxy resin；
(D) tetrafunctional epoxy resin；
(E) active ester and linear phenolic resin composite curing agent.
The present invention adopts novolac epoxy resin so that it is have low water absorption and excellent dielectric properties having higher glass transition temperature simultaneously；Core shell rubbers is epoxy resin toughened or/and core shell rubbers can improve toughness and processes；Brominated bisphenol a type epoxy resin is while promoting glass transition temperature, it is provided that flame-retarding characteristic；Tetrafunctional epoxy resin, is conducive to the follow-up PCB AOI processed to detect, and promotes the glass transition temperature of solidfied material further.Active ester and linear phenolic resin composite curing agent, be advantageously implemented the balance of thermostability, dielectric properties and water absorption rate, reduces cost simultaneously.
The present invention utilizes cooperating and mutually working in coordination with facilitation between above-mentioned five kinds of necessary components, obtains composition epoxy resin as above.Adopt prepreg and laminate that this composition epoxy resin makes, have that better thermostability, low dielectric loss value, humidity resistance be good, low water absorption and an excellent toughness.
Preferably, with the addition sum of group (A), component (B), component (C) and component (D) for 100 parts by weight, the addition of described component (A) novolac epoxy resin is 35～65 weight portions, such as 35 weight portions, 38 weight portions, 46 weight portions, 49 weight portions, 50 weight portions, 53 weight portions, 54 weight portions, 55 weight portions, 56 weight portions, 61 weight portions, 63 weight portions, 64 weight portions or 65 weight portions, it is preferable that 40～65 weight portions.
In the present invention, epoxy resin adopts above-mentioned addition both can be obviously improved solidfied material glass transition temperature and reduce water absorption rate, it is also possible to improve toughness.
Preferably, described novolac epoxy resin is the mixture of any one or at least two in bisphenol A-type novolac epoxy resin, bisphenol-f type novolac epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Dicyclopentadiene-phenol addition reaction-type epoxy resin, naphthol novolac type epoxy resin, naphthols-phenol copolycondensation phenolic resin varnish type epoxy resin, naphthols-cresol copolycondensation phenolic resin varnish type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin epoxy-type epoxy resin or biphenyl modified novolac type epoxy resin.
Preferably, described novolac epoxy resin is the mixture of any one or at least two in the epoxy resin being structured with:
In formula (1), R1Identical or different, independently be the alkyl of hydrogen atom, halogen atom or substituted or unsubstituted C1～C8 (such as C2, C3, C4, C5, C6 or C7), n1Represent repetitive, for the integer be more than or equal to 1, for instance 5,8,10,13 or 15；
In formula (2), R2Identical or different, all independently be hydrogen atom, halogen atom or substituted or unsubstituted C1～C8 (such as C2, C3, C4, C5, C6 or C7) alkyl, n2Represent repetitive, for the integer be more than or equal to 1, for instance 5,8,10,13 or 15；
In formula (3), R3Identical or different, all independently be hydrogen atom, halogen atom or substituted or unsubstituted C1～C8 (such as C2, C3, C4, C5, C6 or C7) alkyl, n3Represent repetitive, for the integer be more than or equal to 1, for instance 5,8,10,13 or 15；
In formula (4), n4Represent repetitive, for the integer be more than or equal to 1, for instance 5,8,10,13 or 15；
In formula (5), R5Identical or different, all independently be hydrogen atom, halogen atom or substituted or unsubstituted C1～C8 alkyl, n5Represent repetitive, for the integer be more than or equal to 1, for instance 5,8,10,13 or 15；
In formula (6), n6Represent repetitive, for the integer be more than or equal to 1, for instance 5,8,10,13 or 15；
More preferably, described novolac epoxy resin has structure shown in formula (6), bisphenol-A in this structure gives its big free volume and good toughness, meanwhile dicyclopentadiene gives its rigidity and low water absorption, makes it have high-fire resistance, low-dielectric energy, low water absorption and good toughness concurrently.
Preferably, with the addition sum of component (A), component (B), component (C) and component (D) for 100 parts by weight, described core shell rubbers is epoxy resin toughened or/and the addition of core shell rubbers is 20～40 weight portions, for instance 22 weight portions, 24 weight portions, 26 weight portions, 28 weight portions, 30 weight portions, 32 weight portions, 34 weight portions, 36 weight portions or 38 weight portions.
In the present invention, core shell rubbers is epoxy resin toughened or/and core shell rubbers adopts above-mentioned addition both can be obviously improved the toughness of compositions, and does not have and be separated and thermostability declines.
Preferably, the epoxy resin toughened toughener for being scattered in epoxy resin containing nano core-shell particle of described core shell rubbers, it is preferred to be scattered in brominated bisphenol a type epoxy resin or the toughener of bisphenol A-type novolac epoxy resin containing 25 weight % nano core-shell particles.
Preferably, with the addition sum of component (A), component (B), component (C) and component (D) for 100 parts by weight, the addition of described brominated bisphenol a type epoxy resin is 5～15 parts of weight portions, for instance 6 weight portions, 7 weight portions, 8 weight portions, 9 weight portions, 10 weight portions, 11 weight portions, 12 weight portions, 13 weight portions or 14 weight portions.
In the present invention, brominated bisphenol a type epoxy resin adopts above-mentioned addition both can promote the flame-retarding characteristic of compositions, can keep again higher thermostability.
Preferably, described brominated bisphenol a type epoxy resin is structured with:
n7Represent repetitive, for be more than or equal to 1 integer, for instance 5,8,10,13 or 15.
Preferably, with the addition sum of component (A), component (B), component (C) and component (D) for 100 parts by weight, the addition of described tetrafunctional epoxy resin is 5～10 weight portions, for instance 5 weight portions, 6 weight portions, 7 weight portions, 8 weight portions, 9 weight portions, 10 weight portions.In the present invention, four-functional group epoxy resin adopts above-mentioned addition both can promote compositions glass transition temperature, is conducive to again the AOI of follow-up PCB to detect.
Preferably, described tetrafunctional epoxy resin is structured with:
Preferably, with the addition sum of component (A), component (B), component (C) and component (D) for 100 parts by weight, the epoxide equivalent ratio of the ester group equivalent of described active ester and linear phenolic resin hydroxyl equivalent sum and epoxy resin is 1:0.95～1.05, for instance 1:0.96,1:0.97,1:0.98,1:0.99,1:1,1:1.01,1:1.02,1:1.03 or 1:1.04.
Preferably, the ester group equivalent of active ester and the hydroxyl equivalent ratio of novolac are 0.25～4, for instance 0.5,1,1.5,2,2.5,3 or 3.5.Select this equivalent proportion, dielectric properties and the water absorption rate of solidfied material can be improved, it is also possible to keep higher glass transition temperature, it is achieved the balance of thermostability and humidity resistance.
Preferably, described active ester is structured with:
X is phenyl or naphthyl, and j is 0 or 1, k is 0 or 1, n represent that repetitive is 0.25～1.25.Due to the special construction of this active ester, the rigid structure such as phenyl therein, naphthyl and cyclopentadiene gives the thermostability that this active ester is high, simultaneously because the regularity of its structure, also gives its good electrical property.
Preferably, described linear phenolic resin is the mixture of any one or at least two in biphenyl type novolac epoxy resin, dicyclopentadiene phenolic resin, alkylphenol phenolic resin, phenol type phenolic resin, bisphenol A-type phenolic resin or bisphenol-f type phenolic resin.
Preferably, described linear phenolic resin is structured with:
In formula, n8Represent repetitive, for the integer be more than or equal to 1, for instance 5,10,13,15 or 18.
Preferably, described composition epoxy resin also includes curing accelerator, and it makes resin solidify and accelerates resin curing rate.With component (A), component (B), component (C), the addition sum of component (D) and component (E) is 100 parts by weight, the addition of described firming agent accelerator is 0.05～1 weight portion, such as 0.08 weight portion, 0.1 weight portion, 0.15 weight portion, 0.2 weight portion, 0.25 weight portion, 0.3 weight portion, 0.35 weight portion, 0.4 weight portion, 0.45 weight portion, 0.5 weight portion, 0.55 weight, 0.6 weight portion, 0.65 weight portion, 0.7 weight portion, 0.75 weight portion, 0.8 weight portion, 0.85 weight portion, 0.9 weight portion or 0.95 weight portion.
Preferably, described curing accelerator is the mixture of any one or at least two in DMAP, 2-methylimidazole, 2-methyl 4-ethyl imidazol(e) or 2-phenylimidazole.
Preferably, described composition epoxy resin also includes brominated flame-retardant.
Preferably, with the addition sum of component (A), component (B) and component (C) for 100 parts by weight, the addition of described fire retardant is 0～50 weight portion and does not include 0, for instance 5 weight portions, 10 weight portions, 15 weight portions, 20 weight portions, 25 weight portions, 30 weight portions, 35 weight portions, 40 weight portions, 45 weight portions or 50 weight portions.
Preferably, described brominated flame-retardant is the mixture of any one or at least two in the double; two tetrabromo phthalimide of TDE, brominated Polystyrene or ethylene.
Preferably, described composition epoxy resin also comprises filler, and described filler is organic or/and inorganic filler, and its some physical property effects being mainly used to adjust compositions, as reduced thermal coefficient of expansion (CTE), reducing water absorption rate and improve thermal conductivity etc..
Preferably, with the addition sum of component (A), component (B), component (C) and component (D) for 100 parts by weight, the addition of described filler is 0～100 weight portion and does not include 0, it is preferable that 0～50 weight portion and do not include 0.The addition of described filler is such as 0.5 weight portion, 1 weight portion, 5 weight portions, 10 weight portions, 15 weight portions, 20 weight portions, 25 weight portions, 30 weight portions, 35 weight portions, 40 weight portions, 45 weight portions, 50 weight portions, 55 weight portions, 60 weight portions, 65 weight portions, 70 weight portions, 75 weight portions, 80 weight portions, 85 weight portions, 90 weight portions or 95 weight portions.
Preferably, the mixture of the described inorganic filler any one or at least two in fused silica, powdered quartz, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, Pulvis Talci, aluminium nitride, boron nitride, carborundum, barium sulfate, Barium metatitanate., strontium titanates, calcium carbonate, calcium silicates, Muscovitum or glass fiber powder.The mixture of described mixture such as fused silica and powdered quartz, the mixture of spherical silica and hollow silicon dioxide, the mixture of aluminium hydroxide and aluminium oxide, the mixture of Pulvis Talci and aluminium nitride, the mixture of boron nitride and carborundum, the mixture of barium sulfate and Barium metatitanate., the mixture of strontium titanates and calcium carbonate, calcium silicates, the mixture of Muscovitum and glass fiber powder, fused silica, the mixture of powdered quartz and spherical silica, hollow silicon dioxide, the mixture of aluminium hydroxide and aluminium oxide, Pulvis Talci, the mixture of aluminium nitride and boron nitride, carborundum, the mixture of barium sulfate and Barium metatitanate., strontium titanates, calcium carbonate, calcium silicates, the mixture of Muscovitum and glass fiber powder.
Preferably, the mixture of the described organic filler any one or at least two in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder.The mixture of described mixture such as polytetrafluorethylepowder powder and polyphenylene sulfide, the mixture of polyether sulfone powder and polytetrafluorethylepowder powder, the mixture of polyphenylene sulfide and polyether sulfone powder, the mixture of polytetrafluorethylepowder powder, polyphenylene sulfide and polyether sulfone powder.
Preferably, described filler is silicon dioxide, and in the particle diameter of filler, angle value is 1～15 μm, it is preferable that in the particle diameter of filler, angle value is 1～10 μm.
" including " of the present invention, it is intended that it is except described component, it is also possible to include other components, these other components give the characteristic that described composition epoxy resin is different.In addition, " including " of the present invention, it is also possible to replace with enclosed " being " or " by ... composition ".
Such as, described composition epoxy resin can also contain various additives, as concrete example, it is possible to enumerate antioxidant, heat stabilizer, antistatic additive, UV absorbent, pigment, coloring agent or lubricant etc..These various additives can be used alone, it is also possible to two kinds or two or more mixing use.
The conventional manufacture method of the resin combination of the present invention: take a container, first solid constituent is put into, it is subsequently adding liquid flux, stirring is until after being completely dissolved, add liquid resin, filler, fire retardant, curing accelerator, continue to stir, finally adjust liquid solid content with solvent and make glue to 60%～80%.
A kind of prepreg, it includes reinforcing material and by being impregnated with dried attachment composition epoxy resin as above thereon.
Exemplary reinforcing material such as adhesive-bonded fabric is or/and other fabrics, for instance natural fiber, organic synthetic fibers and inorfil.
Use fabric or the organic fabrics such as this glue impregnation reinforcing material such as glass cloth, the reinforcing material being impregnated with heat drying in the baking oven of 155 DEG C can be obtained prepreg in 5～10 minutes.
A kind of laminate, it includes at least one prepreg as above.
A kind of printed circuit board, it includes at least one prepreg as above.
Compared with prior art, there is advantages that
The present invention adopts novolac epoxy resin so that it is have low water absorption and excellent dielectric properties having higher glass transition temperature simultaneously；
Core shell rubbers is epoxy resin toughened or/and core shell rubbers can improve toughness and processes: improves end carbonyl LNBR prepolymer and is easily separated thoroughly or non-optimal conditions, the intrinsic thermostability of epoxy resin and elastic modelling quantity is caused to decline, it is difficult to ensure that improving fragility and impact resistance, do not sacrifice again thermostability, mechanical strength and chemical proofing；
Brominated bisphenol a type epoxy resin, providing flame-retarding characteristic simultaneously, keeps higher glass transition temperature；
Tetrafunctional epoxy resin, is conducive to the follow-up PCB AOI processed to detect, and promotes the glass transition temperature of solidfied material further；
Active ester and linear phenolic resin composite curing agent are advantageously implemented thermostability and the balance of dielectric properties, water absorption rate, reduce cost simultaneously；
Use prepreg, laminate and metal-clad laminate that this composition epoxy resin makes, have that better thermostability, low dielectric loss value, humidity resistance be good, low water absorption and an excellent toughness.
Detailed description of the invention
Technical scheme is further illustrated below by detailed description of the invention.
According to above-mentioned made composition epoxy resin metal-clad laminate, test its glass transition temperature, dielectric loss factor, PCT and PCT water absorption rate, drop impact toughness, as following embodiment is added on detailed description and describes, wherein the mass parts of organic resin is by organic solid quality part.
Preparation example: there is the synthesis of the novolac epoxy resin of formula (6) structure
Equipped with agitator, thermometer, condensation reflux device four-hole bottle (500mL) in add 200g bisphenol-A and dissolve in heating in water bath, weigh boron trifluoride diethyl etherate 2.0g, add in 500mL four-hole boiling flask, Dropping funnel adds 60g dicyclopentadiene, controls rate of addition well, in order in 2h, drip all of dicyclopentadiene, it is warming up to 100 DEG C, insulation 4h, reaction terminates, washing, filter, recrystallization, vacuum drying, obtain the phenolic resin of following structure.
The phenolic resin that obtained for previous step 25g has dicyclopentadiene structure of bisphenol A is put in four-hole boiling flask, weigh 100.0g epoxychloropropane again to be slowly added to, after it dissolves, start to warm up, and in Dropping funnel, add the NaOH solution that mass fraction is 33% of 1mol, control speed, it is made to drip in 1h, control reaction temperature at 100 DEG C, 5h it is incubated after dripping, wash after cooling, it is warming up to 120 DEG C of distillations again, steam excess epoxy chloropropane, reaction terminates, washing, filter, recrystallization, vacuum drying, obtain the epoxy resin with dicyclopentadiene structure of bisphenol A shown in following chemical structural formula:
Embodiment 1
Take a container, add the NC-3000H of 60 weight portions, add appropriate MEK, after stirring and dissolving, add the 25 epoxy resin toughened MX-395 of weight portion core shell rubbers, the 10 weight portion parts by weight of activated esters of tetrabromobisphenol A type epoxy resin 153,5 weight portion four-functional group modified epoxy 1031,14 solidify HPC-8000-65T and 26 weight portion linear phenolic resin 2812, stirring, add appropriate curing accelerator DMAP and 2-methyl-4-ethyl imidazol(e), continue to stir, finally adjust liquid solid content with solvent and make glue to 60%～80%.With glass fabric impregnate above-mentioned glue, glue.Impregnate above-mentioned glue with glass fabric, and control to suitable thickness, then dry removing solvent and obtain prepreg.Use several obtained prepregs to be superimposed with each other, cover a Copper Foil in its both sides respectively, put into hot press solidifies and make described epoxy resin copper-clad plate lamination plate.Physical data is as shown in table 1.
Implement row 2～8
Processing technology is identical with implementing row 1, and formula composition and physical index thereof are as shown in table 1.
Comparative example 1～6:
Processing technology is identical with embodiment 1, and formula composition and physical index thereof are as shown in table 2.
The formula composition of each embodiment of table 1. and physical data thereof.
The formula composition of each comparative example of table 2. and physical data thereof.
| Material | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| 164 | - | - | 55 | - | ||
| 627 | 47 | 52 | - | 66 | 58 | 58 |
| MX-395 | 27 | 27 | ||||
| 153 | 10 | 10 | ||||
| 1031 | 5 | 5 | ||||
| HPC-8000-65T | 53 | - | - | 88 | ||
| 2812 | - | 14 | 13 | 34 | 41 | |
| Tetrabromobisphenol A | - | 34 | 32 | - | ||
| DMAP | In right amount | - | - | - | In right amount |
| 2E4MI | - | In right amount | In right amount | In right amount | In right amount | |
| Tg(DSC)/℃ | 158 | 155 | 162 | 180 | 179 | 156 |
| Df(1GHZ) | 0.0100 | 0.0188 | 0.0190 | 0.0220 | 0.0225 | 0.0102 |
| PCT water absorption rate | 0.25% | 0.43% | 0.46% | 0.45% | 0.46% | 0.26% |
| PCT | >300s | >300s | >300s | >300s | >300s | >300s |
| Drop impact toughness | △ | △ | △ | △ | ◎ | ◎ |
Note: all with solid constituent parts by weight in table.
The material that table 1 and table 2 are enumerated is specific as follows:
7200-3H: dicyclopentadiene type novolac epoxy resin, epoxide equivalent is 285g/eq (Japan's DIC trade name).
NC-3000H: biphenyl type novolac epoxy resin, epoxide equivalent is 288g/eq (Japanization pharmacist's name of an article).
NC-2000H: alkylidene novolac epoxy resin, epoxide equivalent is 273g/eq (Japanization pharmacist's name of an article).
627: bisphenol A-type novolac epoxy resin, epoxide equivalent is 205g/eq (U.S.'s Hexion trade name).
EEPN-501HY: trifunctional epoxy resin, epoxide equivalent is 166g/eq (Japanization pharmacist's name of an article).
The novolac epoxy resin of preparation example: having the epoxy resin of dicyclopentadiene structure of bisphenol A, epoxide equivalent is 283g/eq.
164: Study On O-cresol Epoxy Resin, epoxide equivalent is 225g/eq (Korea S's Momentive trade name).
MX-395: refer to be scattered in brominated bisphenol a type epoxy resin toughener containing 25 weight % nano core-shell particles, epoxide equivalent is 433g/eq (U.S.'s Hexion trade name).
153: High Bromine epoxy Resin, epoxide equivalent is 400g/eq (Wuxi Di Aisheng trade name).
1031: tetrafunctional epoxy resin, epoxide equivalent is 400g/eq (Korea S's Momentive trade name).
HPC-8000-65T: active ester, ester group equivalent is 223g/eq (Japan's DIC trade name).
2812: linear phenolic resin, hydroxyl equivalent is 105g/eq (Korea S's Momentive trade name).
Tetrabromobisphenol A, hydroxyl equivalent is 272g/eq (the refined precious trade name of the U.S.).
DMAP, DMAP (wide flourish commodity chemical name).
2E4MI, 2-methyl 4-ethyl imidazol(e) (four countries of Japan chemical conversion trade name).
The method of testing of above characteristic is as follows:
(1) glass transition temperature (Tg): according to differential scanning calorimetry (DSC), be measured according to the DSC method of IPC-TM-6502.4.25 defined.
(2) dielectric constant and dielectric loss factor: test according to the method for IPC-TM-6502.5.5.9 defined, test frequency is 1GHZ.
(3) PCT and PCT water absorption rate: after the Copper Foil etching that copper-clad plate is shown, evaluate substrate: by substrate placement force pot, 120 DEG C, 150KPa when, process two hours: after impregnated in the stannum stove of 288 DEG C, when base material is layered, record the corresponding time: can terminate to evaluate when bubble or layering also do not occur more than 5min in stannum stove when substrate.
(4) drop impact toughness: using drop impact instrument, Apparatus for Impacting at low-temp height of the fall 40cm, whereabouts weight weight is 1Kg, toughness quality is evaluated: cross is clear, illustrates that toughness of products is more good, represents with character ◎；Cross obscures, and illustrates that the poor toughness of product, fragility are big, represents with character △；Cross readability between clear and fuzzy, illustrate that the toughness of product is general, represents with character zero.
Physical Property Analysis:
Physical data from table 1 and table 2, in comparative example, adopt phenolic resin and tetrabromobisphenol A as composite curing agent, glass transition temperature is low, poor electrical performance, water absorption rate high and poor toughness, when same epoxy resin adopts active ester to solidify, its dielectric properties are more excellent, water absorption rate is lower, but its glass transition temperature is relatively low and poor toughness, and same epoxy resin is when individually adopting phenolic cure, glass transition temperature is higher, but its problem that there is dielectric properties difference, water absorption rate height and poor toughness.Embodiment 1～8 adopt active ester and linear phenolic resin as composite curing agent, its equivalent proportion is defined, and add that core shell rubbers is epoxy resin toughened, brominated bisphenol a type epoxy resin and tetrafunctional epoxy resin, have that better thermostability, low dielectric loss value, humidity resistance be good, low water absorption and an excellent toughness.
As it has been described above, compared with general laminate, the epoxy circuit substrate of the present invention has that better thermostability, low dielectric loss value, humidity resistance be good, low water absorption and excellent toughness.
The above, it is only presently preferred embodiments of the present invention, for the person of ordinary skill of the art, it is possible to conceive according to technical scheme and technology and make other various corresponding changes and deformation, and all these change and deform the scope that all should belong to the claims in the present invention.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the invention is not limited in above-mentioned method detailed, does not namely mean that the present invention has to rely on above-mentioned method detailed and could implement.The equivalence of each raw material of product of the present invention, it will be clearly understood that any improvement in the present invention, is replaced and the interpolation of auxiliary element, concrete way choice etc. by person of ordinary skill in the field, all falls within protection scope of the present invention and open scope.
Claims (10)
1. a composition epoxy resin, it is characterised in that described composition epoxy resin includes following component:
(A) novolac epoxy resin；
(B) core shell rubbers is epoxy resin toughened or/and core shell rubbers；
(C) brominated bisphenol a type epoxy resin；
(D) tetrafunctional epoxy resin；
(E) active ester and linear phenolic resin composite curing agent.
2. composition epoxy resin as claimed in claim 1, it is characterized in that, with the addition sum of group (A), component (B), component (C) and component (D) for 100 parts by weight, the addition of described component (A) novolac epoxy resin is 35～65 weight portions, it is preferable that 40～65 weight portions；
Preferably, described novolac epoxy resin is the mixture of any one or at least two in the epoxy resin being structured with:
In formula (1), R1Identical or different, independently be the alkyl of hydrogen atom, halogen atom or substituted or unsubstituted C1～C8, n1Represent repetitive, for the integer be more than or equal to 1；
In formula (2), R2Identical or different, all independently be hydrogen atom, halogen atom or substituted or unsubstituted C1～C8 alkyl, n2Represent repetitive, for the integer be more than or equal to 1；
In formula (3), R3Identical or different, all independently be hydrogen atom, halogen atom or substituted or unsubstituted C1～C8 alkyl, n3Represent repetitive, for the integer be more than or equal to 1；
In formula (4), n4Represent repetitive, for the integer be more than or equal to 1；
In formula (5), R5Identical or different, all independently be hydrogen atom, halogen atom or substituted or unsubstituted C1～C8 alkyl, n5Represent repetitive, for the integer be more than or equal to 1；
In formula (6), n6Represent repetitive, for the integer be more than or equal to 1；
It is highly preferred that described novolac epoxy resin is for having the novolac epoxy resin of structure shown in formula (6).
3. composition epoxy resin as claimed in claim 1 or 2, it is characterized in that, with the addition sum of component (A), component (B), component (C) and component (D) for 100 parts by weight, described core shell rubbers is epoxy resin toughened or/and the addition of core shell rubbers is 20～40 weight portions；
Preferably, the epoxy resin toughened toughener for being scattered in epoxy resin containing nano core-shell particle of described core shell rubbers, it is preferred to be scattered in brominated bisphenol a type epoxy resin or the toughener of bisphenol A-type novolac epoxy resin containing 25 weight % nano core-shell particles；
Preferably, with the addition sum of component (A), component (B), component (C) and component (D) for 100 parts by weight, the addition of described brominated bisphenol a type epoxy resin is 5～15 parts of weight portions；
Preferably, described brominated bisphenol a type epoxy resin is structured with:
n7Represent repetitive, for be more than or equal to 1 integer.
4. the composition epoxy resin as described in one of claim 1-3, it is characterized in that, with the addition sum of component (A), component (B), component (C) and component (D) for 100 parts by weight, the addition of described tetrafunctional epoxy resin is 5～10 weight portions；
Preferably, described tetrafunctional epoxy resin is structured with:
Preferably, the ester group equivalent of described active ester and the epoxide equivalent ratio of linear phenolic resin hydroxyl equivalent sum and epoxy resin are 1:0.95～1.05；
Preferably, the ester group equivalent of active ester and the hydroxyl equivalent ratio of novolac are 0.25～4；
Preferably, described active ester is structured with:
X is phenyl or naphthyl, and j is 0 or 1, k is 0 or 1, n represent that repetitive is 0.25～1.25；
Preferably, described linear phenolic resin is structured with:
In formula, n8Represent repetitive, for the integer be more than or equal to 1.
5. the composition epoxy resin as described in one of claim 1-4, it is characterised in that described composition epoxy resin also includes curing accelerator；
Preferably, with the addition sum of component (A), component (B), component (C), component (D) and component (E) for 100 parts by weight, the addition of described firming agent accelerator is 0.05～1 weight portion；
Preferably, described curing accelerator is the mixture of any one or at least two in DMAP, 2-methylimidazole, 2-methyl 4-ethyl imidazol(e) or 2-phenylimidazole.
6. the composition epoxy resin as described in one of claim 1-5, it is characterised in that described composition epoxy resin also includes brominated flame-retardant；
Preferably, with the addition sum of component (A), component (B) and component (C) for 100 parts by weight, the addition of described fire retardant is 0～50 weight portion and does not include 0；
Preferably, described brominated flame-retardant is the mixture of any one or at least two in the double; two tetrabromo phthalimide of TDE, brominated Polystyrene or ethylene.
7. the composition epoxy resin as described in one of claim 1-6, it is characterised in that described composition epoxy resin also comprises filler, described filler is organic or/and inorganic filler；
Preferably, with the addition sum of component (A), component (B), component (C) and component (D) for 100 parts by weight, the addition of described filler is 0～100 weight portion and does not include 0, it is preferable that 0～50 weight portion and do not include 0；
Preferably, the mixture of the described inorganic filler any one or at least two in fused silica, powdered quartz, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, Pulvis Talci, aluminium nitride, boron nitride, carborundum, barium sulfate, Barium metatitanate., strontium titanates, calcium carbonate, calcium silicates, Muscovitum or glass fiber powder；
Preferably, the mixture of the described organic filler any one or at least two in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder；
Preferably, described filler is silicon dioxide, and in the particle diameter of filler, angle value is 1～15 μm, it is preferable that in the particle diameter of filler, angle value is 1～10 μm.
8. a prepreg, it includes reinforcing material and by being impregnated with the dried attachment composition epoxy resin as described in one of claim 1-7 thereon.
9. a laminate, it includes at least one prepreg as claimed in claim 8.
10. a printed circuit board, it includes at least one prepreg as claimed in claim 8.
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| CN201410831357.4A CN105778412B (en) | 2014-12-26 | 2014-12-26 | A kind of composition epoxy resin and use its prepreg and laminate |
| PCT/CN2015/078781 WO2016101497A1 (en) | 2014-12-26 | 2015-05-12 | Epoxy resin composition as well as prepreg and laminated plate using same |
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| CN201410831357.4A CN105778412B (en) | 2014-12-26 | 2014-12-26 | A kind of composition epoxy resin and use its prepreg and laminate |
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| CN110554567A (en) * | 2019-08-28 | 2019-12-10 | 浙江福斯特新材料研究院有限公司 | resin composition and use thereof |
| WO2020252681A1 (en) * | 2019-06-19 | 2020-12-24 | Dow Global Technologies Llc | Flame retardant composition |
| CN116875151A (en) * | 2023-08-10 | 2023-10-13 | 江苏云湖新材料科技有限公司 | Halogen-free flame-retardant epoxy fireproof coating for battery pack shell and preparation method thereof |
| CN117124666A (en) * | 2023-09-20 | 2023-11-28 | 江苏耀鸿电子有限公司 | Ageing-resistant flame-retardant epoxy resin-based copper-clad plate and preparation method thereof |
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| CN113493668A (en) * | 2021-08-02 | 2021-10-12 | 东莞市邦盛电子材料有限公司 | Formula and preparation method of high-toughness and non-toxic epoxy resin adhesive |
| CN114479362B (en) * | 2022-02-09 | 2023-09-15 | 建滔电子材料（江阴）有限公司 | Preparation method of FR-4 copper-clad plate with high CAF reliability for automobile |
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| CN117124666B (en) * | 2023-09-20 | 2024-02-02 | 江苏耀鸿电子有限公司 | Ageing-resistant flame-retardant epoxy resin-based copper-clad plate and preparation method thereof |
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| WO2016101497A1 (en) | 2016-06-30 |
| CN105778412B (en) | 2018-05-29 |
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