CN110283425A - A kind of epoxy resin prepreg and preparation method thereof - Google Patents
A kind of epoxy resin prepreg and preparation method thereof Download PDFInfo
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- CN110283425A CN110283425A CN201910559602.3A CN201910559602A CN110283425A CN 110283425 A CN110283425 A CN 110283425A CN 201910559602 A CN201910559602 A CN 201910559602A CN 110283425 A CN110283425 A CN 110283425A
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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
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of epoxy resin prepregs, according to parts by weight, including 10-20 containing brominated eopxy parts, 10-20 parts of high TG epoxy, 3-8 parts of tetrafunctional epoxy, 1-15 parts of brominated flame-retardant, 10-25 parts of acid anhydride type curing agent, 0-6 parts of amine curing agent, 10-25 parts of long-chain flexible resin, 0.02-0.3 parts of catalyst, 20-50 parts of solvent, 0-60 parts of filler.Epoxy resin prepreg of the present invention does not lose high bonding and infiltration fillibility while having extremely low mobility, with high Tg and high-fire resistance, dimensional stability with higher, it solves layering plate bursting caused by white point, Bai Si and dried flower, after copper wire falls off, deforms the problems such as copper wire displacement short circuit, improves product qualification rate and reliability.
Description
Technical field
The present invention relates to printed circuit board technologies more particularly to a kind of epoxy resin prepreg and preparation method thereof.
Background technique
With the development of science and technology with the raising of people's life requirement, " thin, light, short, small ", more function are proposed to electronic product
Energyization and personalized direction are developed, and need that the number of plies of PCB is more thinner, structure is more diversified, such as: wearing electronics, it can
Electronics, Rigid Flex are folded, just embedded part, thick copper filling perforation etc., the traditional semi-solid preparation made now inside board, PCB
Piece can not guarantee that the dimensional stability of product, and filling, caking property, resin system also can not meet because mobility is big
The repeatedly required heat resistance of pressing.Rigid Flex, just around board, multi-layer PCB board, after the pressing of traditional prepreg
Usually there are the fillings such as substrate white point, Bai Si and dried flower and contain empty quality problems, machining property is also poor, to easily divide
After layer plate bursting, copper wire fall off, deform the problems such as copper wire displacement short circuit.
Summary of the invention
Traditional prepreg makes Rigid Flex, the poor dimensional stability just occurred around board, multi-layer PCB board, with
And filling, adhesive property are poor, thus the white point, Bai Si and the dried flower that occur and cause to be layered copper wire after plate bursting, copper wire fall off, deform
Shift the various problems such as short circuit.In view of the above-mentioned problems, the present invention provides a kind of epoxy resin prepreg and preparation method thereof.
The technical scheme to solve the above technical problems is that a kind of epoxy resin prepreg, which is characterized in that
According to parts by weight, including following component: 10-20 containing brominated eopxy parts, 10-20 parts of high TG epoxy, 3-8 parts of tetrafunctional epoxy, contain
1-15 parts of bromine flame retardant, 10-25 parts of acid anhydride type curing agent, 0-6 parts of amine curing agent, 10-25 parts of long-chain flexible resin, catalyst
0.02-0.3 parts, 20-50 parts of solvent, 0-60 parts of filler.
Further, the bromine content containing brominated eopxy is 10wt%-70wt%, and epoxide number 300-600g/mol is double
Phenol A type, bisphenol-f type, polyphenol type diglycidyl ether type, aliphatic glycidyl ether type, glycidyl ester type, glycidyl amine
One of type, epoxidation of olefins or a variety of combinations；The epoxide number of the high TG epoxy is 180-300g/mol, bisphenol A-type
Epoxy novolac, bisphenol-f type epoxy novolac, isocyanate-modified epoxy, dicyclic pentylene modified epoxy, in naphthol type epoxy resin
One or more combinations.
Further, the epoxide number of the tetrafunctional epoxy is 180-300g/mol, structure are as follows:
Further, the brominated flame-retardant bromine content is 50wt%-90wt%, is tetrabromobisphenol A, tetrabromobisphenol F, three
(2,3- dibromopropyl) fulminuric acid ester, deca-BDE, hexabromocyclododecane, eight bromo ether, bis- (the tetrabromo-benzene neighbours two of ethyl-
Formamide) one of or a variety of combinations.
Further, the weight average molecular weight of the acid anhydride type curing agent is 2000-5000, is polystyrene maleic anhydride, double
One of cyclopentadiene maleic anhydride, the modified anhydride of type containing naphthalene nucleus, polyethylene maleic anhydride or polypropylene maleic anhydride are more
The combination of kind；The amine curing agent is one of dicyandiamide, two amido diphenyl sulphone (DPS)s or two amido diphenyl-methanes or a variety of
Combination.
Further, it is isocyanate-modified epoxy, benzene that the weight average molecular weight of the long-chain flexible resin, which is 30000-70000,
One of oxygen resin, organic siliconresin, polybutadiene or polyphenyl ether modified epoxy or a variety of combinations.
Further, the catalyst is 2 methylimidazoles, 4 methyl, 2 ethyl imidazol(e), hendecane imidazoles, 2 phenylimidazoles or boron
One of acid or a variety of combinations.
Further, the solvent is methanol, ethyl alcohol, acetone, cyclohexanone, butanone, propylene glycol monomethyl ether, ethylene glycol list first
One of ether, dimethylformamide or ethyl acetate or a variety of combinations.
Further, the granularity of the filler is 0.1-5 microns, is silicon powder, aluminium oxide, zirconium oxide, aluminium nitride or nitridation
One of zirconium or a variety of combinations.
The invention further relates to the preparation methods of above-mentioned epoxy resin prepreg, comprising the following steps:
1) prepare substrate: 0.14 mm of thickness glass-fiber-fabric below is cut into required size；
2) it prepares glue: weighing each component by weight, after ball milling mixing 30-60min, be coated on glass-fiber-fabric；
3) baking molding: the glass-fiber-fabric after step is coated toasts 1-3min at 170 DEG C -200 DEG C, and asphalt mixtures modified by epoxy resin is made
Rouge prepreg, qualified epoxy resin prepreg should meet: with a thickness of being lower than 0.3 millimeter, bubble in 10cm*10cm area
No more than 5.
The beneficial effects of the present invention are: epoxy resin prepreg of the present invention does not lose high glue while having extremely low mobility
Knot and infiltration fillibility, have high Tg and high-fire resistance, dimensional stability with higher solves white point, Bai Si and dried flower
After caused layering plate bursting, copper wire fall off, deform the problems such as copper wire displacement short circuit, product qualification rate and reliability are improved.
Specific embodiment
Below in conjunction with example, present invention is described, and the given examples are served only to explain the present invention, is not intended to limit this
The range of invention.
Embodiment 1
A kind of epoxy resin prepreg, according to parts by weight, including following component: 10 parts of bisphenol A type bromide epoxy, naphthalene
10 parts of phenolic epoxy, epoxide number are 15 parts of 3 parts of tetrafunctional epoxy, the tetrabromobisphenol A of 180g/mol, polystyrene maleic anhydride
10 parts, 10 parts of phenoxy resin, 0.02 part of 2 methylimidazole, 20 parts of acetone.
Each component is weighed by above-mentioned parts by weight, after ball mill disperses 30 minutes on 2116 cloth coated in 0.1mm, 170 DEG C
Lower baking sample 3min to get.
Embodiment 2
A kind of epoxy resin prepreg, according to parts by weight, including following component: 20 parts of bisphenol-f type brominated epoxy, double
20 parts of phenol A type epoxy novolac, epoxide number are 1 part of 8 parts of tetrafunctional epoxy, the decabromodiphenyl oxide of 300g/mol, dicyclopentadiene horse
Come 25 parts of acid anhydrides, 25 parts of organic siliconresin, 6 parts of dicyandiamide, 0.3 part of hendecane imidazoles, 50 parts of toluene, fusion silicon powder 60
Part.
Each component is weighed by above-mentioned parts by weight, ball mill dispersion is coated in after sixty minutes on 2116 cloth of 0.12mm, and 200 DEG C
Lower baking sample 1min to get.
Comparative example
A kind of prepreg, according to parts by weight, including following component: 100 parts of bisphenol A type bromide epoxy, phenol novolac
20 parts, 2 parts of tetrafunctional epoxy, 1 part of dicyandiamide, 0.067 part of 2 methylimidazole, 50 parts of acetone, 30 parts of silicon powder.
Glue is prepared by above-mentioned formula, stirs 30 minutes, with the 2116 cloth impregnations of thickness 0.1mm, is dried under 170 degrees Celsius
Sample 3min to get.
By with a thickness of 0.25mm, standard of the bubble no more than 5 chooses embodiment 1,2 and comparison in 10cm*10cm area
Example gained prepreg, carries out performance comparison, as shown in table 1.As can be seen from the table, Examples 1 and 2 epoxy resin half
Cured sheets glass transition temperature is higher than comparative example, i.e., it can still be able to maintain the higher glass of intensity at higher temperatures
The temperature range of state, adaptation is wider.Caking property is higher after Multi-layer force fit, and without the white silk of white point after pressing, dimensional stability is more excellent.More
Important, heat resistance is promoted significant than comparative example after the pressing of Examples 1 and 2 epoxy resin prepreg, is promoted from 188 degrees Celsius
To 600 degrees Celsius or more.
1. embodiment 1,2 of table and comparative example prepreg performance comparison
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of epoxy resin prepreg, which is characterized in that according to parts by weight, including following component: 10-20 containing brominated eopxy
Part, 10-20 parts of high TG epoxy, 3-8 parts of tetrafunctional epoxy, 1-15 parts of brominated flame-retardant, 10-25 parts of acid anhydride type curing agent, amine
0-6 parts of curing agent, 10-25 parts of long-chain flexible resin, 0.02-0.3 parts of catalyst, 20-50 parts of solvent, 0-60 parts of filler.
2. epoxy resin prepreg according to claim 1, which is characterized in that the bromine content containing brominated eopxy is
10wt%-70wt%, epoxide number 300-600g/mol are bisphenol A-type, bisphenol-f type, polyphenol type diglycidyl ether type, fat
One of race's diglycidyl ether type, glycidyl ester type, glycidic amine type, epoxidation of olefins or a variety of combinations；It is described
The epoxide number of high TG epoxy is 180-300g/mol, bisphenol A-type epoxy novolac, bisphenol-f type epoxy novolac, isocyanate-modified ring
One of oxygen, dicyclic pentylene modified epoxy, naphthol type epoxy resin or a variety of combinations.
3. epoxy resin prepreg according to claim 1, which is characterized in that the epoxide number of the tetrafunctional epoxy is
180-300g/mol, structure are as follows:
4. epoxy resin prepreg according to claim 1, which is characterized in that the brominated flame-retardant bromine content is
50wt%-90wt%, be tetrabromobisphenol A, tetrabromobisphenol F, three (2,3- dibromopropyl) fulminuric acid esters, deca-BDE,
One of hexabromocyclododecane, eight bromo ether, ethyl-bis- (tetrabromo-benzene neighbour diformamides) or a variety of combinations.
5. epoxy resin prepreg according to claim 1 again, which is characterized in that the acid anhydride type curing agent is divided equally
Son amount is 2000-5000, is polystyrene maleic anhydride, dicyclopentadiene maleic anhydride, the modified anhydride of type containing naphthalene nucleus, polyethylene
One of maleic anhydride or polypropylene maleic anhydride or a variety of combinations；The amine curing agent is dicyandiamide, two amidos two
One of benzene sulfone or two amido diphenyl-methanes or a variety of combinations.
6. epoxy resin prepreg according to claim 1 again, which is characterized in that the long-chain flexible resin is divided equally
It is isocyanate-modified epoxy, phenoxy resin, organic siliconresin, polybutadiene or polyphenyl ether modified that son amount, which is 30000-70000,
One of epoxy or a variety of combinations.
7. epoxy resin prepreg according to claim 1, which is characterized in that the catalyst is 2 methylimidazoles, 4
One of 2 ethyl imidazol(e) of methyl, hendecane imidazoles, 2 phenylimidazoles or boric acid or a variety of combinations.
8. epoxy resin prepreg according to claim 1, which is characterized in that the solvent is methanol, ethyl alcohol, third
One of ketone, cyclohexanone, butanone, propylene glycol monomethyl ether, glycol monoethyl ether, dimethylformamide or ethyl acetate are a variety of
Combination.
9. epoxy resin prepreg according to claim 1, which is characterized in that the granularity of the filler is that 0.1-5 is micro-
Rice is one of silicon powder, aluminium oxide, zirconium oxide, aluminium nitride or zirconium nitride or a variety of combinations.
10. a kind of preparation method of such as described in any item epoxy resin prepregs of claim 1-9, which is characterized in that packet
Include following steps:
1) prepare substrate: 0.14 mm of thickness glass-fiber-fabric below is cut into required size；
2) it prepares glue: weighing each component by weight, after ball milling mixing 30-60min, be coated on glass-fiber-fabric；
3) baking molding: the glass-fiber-fabric after step is coated toasts 1-3min at 170 DEG C -200 DEG C, and epoxy resin half is made
Cured sheets, qualified epoxy resin prepreg should meet: with a thickness of being lower than 0.3 millimeter, bubble does not surpass in 10cm*10cm area
Cross 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910559602.3A CN110283425A (en) | 2019-06-26 | 2019-06-26 | A kind of epoxy resin prepreg and preparation method thereof |
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| CN201910559602.3A CN110283425A (en) | 2019-06-26 | 2019-06-26 | A kind of epoxy resin prepreg and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637289A (en) * | 2021-06-17 | 2021-11-12 | 上海道宜半导体材料有限公司 | Epoxy resin composition and preparation method and application thereof |
| EP4180477A1 (en) | 2021-11-15 | 2023-05-17 | Evonik Operations GmbH | Epoxy resin compositions for the preparation of storage-stable composites |
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| JPS6445418A (en) * | 1987-08-13 | 1989-02-17 | Showa Denko Kk | Polymer composition for laminated board for electrical use |
| CN101240109A (en) * | 2007-09-30 | 2008-08-13 | 广东生益科技股份有限公司 | Resin composition and semi-solidifying sheet for printed board prepared from the same |
| CN107286583A (en) * | 2017-06-20 | 2017-10-24 | 苏州生益科技有限公司 | A kind of resin combination and the low flow prepreg made using it |
| CN109094166A (en) * | 2018-08-24 | 2018-12-28 | 山东金宝电子股份有限公司 | A kind of preparation method of High Tg CCL |
| CN109535390A (en) * | 2018-11-21 | 2019-03-29 | 常熟生益科技有限公司 | The prepreg and laminate of its preparation of phosphorous epoxy resin composition and application |
-
2019
- 2019-06-26 CN CN201910559602.3A patent/CN110283425A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6445418A (en) * | 1987-08-13 | 1989-02-17 | Showa Denko Kk | Polymer composition for laminated board for electrical use |
| CN101240109A (en) * | 2007-09-30 | 2008-08-13 | 广东生益科技股份有限公司 | Resin composition and semi-solidifying sheet for printed board prepared from the same |
| CN107286583A (en) * | 2017-06-20 | 2017-10-24 | 苏州生益科技有限公司 | A kind of resin combination and the low flow prepreg made using it |
| CN109094166A (en) * | 2018-08-24 | 2018-12-28 | 山东金宝电子股份有限公司 | A kind of preparation method of High Tg CCL |
| CN109535390A (en) * | 2018-11-21 | 2019-03-29 | 常熟生益科技有限公司 | The prepreg and laminate of its preparation of phosphorous epoxy resin composition and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637289A (en) * | 2021-06-17 | 2021-11-12 | 上海道宜半导体材料有限公司 | Epoxy resin composition and preparation method and application thereof |
| EP4180477A1 (en) | 2021-11-15 | 2023-05-17 | Evonik Operations GmbH | Epoxy resin compositions for the preparation of storage-stable composites |
| WO2023083782A1 (en) | 2021-11-15 | 2023-05-19 | Evonik Operations Gmbh | Epoxy resin compositions for producing storage-stable composites |
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