CN104650543B - The preparation method of composition epoxy resin, and with the copper-clad plate prepared by it - Google Patents
The preparation method of composition epoxy resin, and with the copper-clad plate prepared by it Download PDFInfo
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- CN104650543B CN104650543B CN201510111166.5A CN201510111166A CN104650543B CN 104650543 B CN104650543 B CN 104650543B CN 201510111166 A CN201510111166 A CN 201510111166A CN 104650543 B CN104650543 B CN 104650543B
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Abstract
The present invention relates to the preparation method of composition epoxy resin, and with the copper-clad plate prepared by it.Described method comprises: 1). preparation UV functional reagent: UV is stopped white dyes mixes for subsequent use with the weight of UV functional resin in 1:20 ~ 1:120 ratio; 2). prepare composition epoxy resin: a). take each raw material by formula; B). drop in reaction unit by epoxy resin and tetrabromo-bisphenol, under catalyst action, be heated to 160 ~ 180 DEG C and carry out addition reaction, the insulation reaction time is 120 ~ 180 minutes at such a temperature; Be cooled to 120 ~ 150 DEG C, then add step 1) prepared by UV functional reagent reaction 30 ~ 60 minutes; C). reaction system is cooled to less than 60 DEG C, adds thinner, be uniformly mixed obtained described composition epoxy resin.Use special UV functional reagent, the UV barrier functionality making copper-clad plate is about as much as 6% tetrafunctional epoxy resin, thus greatly reduces production cost; Glass transition temp Tg after obtained composition epoxy resin and dicyandiamide cure can reach more than 135 DEG C, and CTI is up to 225V.
Description
Technical field
The present invention relates to a kind of preparation method of composition epoxy resin, more specifically, relate to a kind of there is the composition epoxy resin of UV barrier functionality preparation method and with the copper-clad plate prepared by it.
Background technology
Along with the development of printed circuit technique, printed wiring, constantly towards short and small type, high performance future development, is also had higher requirement to base material simultaneously, such as, is required higher glass transition temp Tg etc.In addition, due to the needs of environmental protection, global electronic industry has entered the pb-free solder epoch, and the temperature of pb-free solder exceeds more than 20 DEG C than before, this there has also been higher requirement to the thermotolerance of printed circuit copper-clad plate and thermostability, such as good resistance toheat etc.
On the other hand, printed circuit copper-clad plate in use, the surperficial prolongation along with duration of service of circuit of PCB, have the accumulation of dust, the condensation of moisture and be stained with negative ions pollutent etc., these factors can cause the destruction of copper-clad plate insulativity to a certain extent.Resistance to tracking is a key property of electrical security, usual employing relative discharge index (ComparativeTrackinglndex, CTI) this parameter evaluates electrical security and the reliability of copper-clad plate, CTI value is larger, its relative discharge index is higher, and insulating property are better.The relative discharge index (ComparativeTrackinglndex, CTI) of common FR4 plate is lower, is difficult to the high relative discharge index reaching more than 175V.
The brominated epoxy resin of common FR4 (the fire-retardant copper-clad plate of glass-fiber-fabric) copper-clad plate, 130 degrees Celsius are approximately with the glass transition temp after dicyandiamide cure, restriction (as lead-free process requires superior heat resistance and stronger UV barrier functionality etc.) is caused to some printed-wiring board (PWB) (PCB) application at present, by adding tetrafunctional epoxy resin to reach UV barrier functionality, but the cost adding tetrafunctional epoxy resin is higher.
Publication number is that CN103214796A Chinese invention patent application (publication date is 2013-07-24) is although provide a kind of composition epoxy resin and preparation method thereof, and copper-clad plate prepared by this composition epoxy resin, second-order transition temperature (Tg) after this epoxy resin composition can reach 140 ± 3 DEG C, and the CTI of made copper-clad plate is also improved, but it does not make a search in UV barrier functionality.
Therefore, how to prepare and a kind ofly not only there is stronger UV barrier functionality but also the composition epoxy resin that price is suitable is that prior art is badly in need of one of technical problem solved.
Summary of the invention
For the defect of prior art, the invention provides a kind of preparation method with the composition epoxy resin of strong UV barrier functionality, and the copper-clad plate that this composition epoxy resin is prepared from, the Tg after this composition epoxy resin and dicyandiamide cure can reach more than 135 degrees Celsius; Use special UV functional reagent, the UV barrier functionality making copper-clad plate is about as much as 6% tetrafunctional epoxy resin, and cost is lower.
Technical purpose of the present invention is achieved by the following technical solution:
The preparation method with the composition epoxy resin of strong UV barrier functionality of the present invention, comprises the following steps:
1). preparation UV functional reagent: UV is stopped white dyes mixes for subsequent use with the weight of UV functional resin in 1:20 ~ 1:120 ratio;
2). prepare composition epoxy resin:
A). take each raw material by formula, described formula comprises each raw material of following weight percent:
B). above-mentioned epoxy resin and tetrabromo-bisphenol are dropped in reaction unit, under catalyst action, is heated to 160 ~ 180 DEG C and carries out addition reaction, at such a temperature 120 ~ 180 minutes insulation reaction time; Be cooled to 120 ~ 150 DEG C, then add step 1) prepared by UV functional reagent reaction 30 ~ 60 minutes;
C). reaction system is cooled to less than 60 DEG C, adds thinner, be uniformly mixed obtained described composition epoxy resin.
As another embodiment, the preparation method with the composition epoxy resin of strong UV barrier functionality of the present invention, comprises the following steps:
1). preparation UV functional reagent: UV is stopped white dyes mixes for subsequent use with the weight of UV functional resin in 1:20 ~ 1:120 ratio;
2). prepare composition epoxy resin:
A). take each raw material by formula, described formula comprises each raw material of following weight percent:
B). drop in reaction unit by above-mentioned epoxy resin and tetrabromo-bisphenol, under catalyst action, be heated to 160 ~ 180 DEG C and carry out addition reaction, the insulation reaction time is 120 ~ 180 minutes at such a temperature; Be cooled to 120 ~ 150 DEG C, then add step 1) prepared by UV functional reagent reaction 30 ~ 60 minutes;
C). reaction system is cooled to less than 60 DEG C, adds thinner, be uniformly mixed obtained described composition epoxy resin.
Further, described UV stops that white dyes is fluorescent whitening agent OB.
Further, described UV functional resin is four phenolic group ethane resol, and it is phenol and oxalic dialdehyde resultant, is preferably Devi and contains DH458, South Asia, Taiwan TPN2.Why select four phenolic group ethane resol, because containing conjugated double bond in its molecule, UV can be absorbed and production cost is lower.
Further, described epoxy resin is E-51 electronic-grade bisphenol A type epoxy resin, and its hydrolyzable chloride content is less than 300ppm, viscosity 9000 ~ 10500mPa.s, oxirane value 5.4 ~ 5.8eq/kg.
Preferably, the master of described tetrabromo-bisphenol is containing being greater than 98%, and bromine content is greater than 58%.
Preferably, described step 2) in addition reaction temperature be 165 ~ 175 DEG C, the reaction times controlled at 120 ~ 180 minutes.
Preferably, described catalyzer is imidazoles catalyzer, such as 2-phenylimidazole; Described thinner is acetone is premium grads, and its purity is greater than 99.5%, and moisture is less than 0.3%.
Another kind of technical scheme of the present invention for: adopt the copper-clad plate that obtained by above-mentioned preparation method, composition epoxy resin is made, it is prepared from as follows:
1). the ratio of the composition epoxy resin obtained by above-mentioned preparation method and Dyhard RU 100 and catalyzer 100:2.5-3.0:0.025-0.045 is by weight made into glue, through adhesive applicator, makes glue semicure on glass-fiber-fabric, become semicure PP sheet;
2). then PP sheet and Copper Foil are stacked on vacuum press, be pressed into copper-clad plate, the temperature of compacting is 170 ~ 190 DEG C, and pressure is 2 ~ 4MPa, and the press time is 60 ~ 120 minutes.
Technical scheme provided by the present invention has following beneficial effect:
1. use special UV functional reagent in the preparation process of composition epoxy resin of the present invention, the UV barrier functionality of the copper-clad plate of making is about as much as 6% tetrafunctional epoxy resin, makes cost lower like this.According to client's previous experiences: 6% tetrafunctional epoxy resin (tetraphenolethane epoxy resin, C
38o
8h
38) join in Natural color brominated epoxy resin, the UV transmittance of the copper-clad plate (thin plate, 0.2mm is thick) made from Dyhard RU 100 is less than 2%.
2. the invention provides a kind of composition epoxy resin, it adopts Special Ring epoxy resins, molecular-weight average is less than conventional epoxy resin, the molecular-weight average of this epoxy resin is how many 355 ~ 365, and the molecular-weight average of conventional epoxy resin is 370 ~ 390, viscosity is 9000 ~ 10500mPa.s, is conducive to improving its resistance toheat.Tg after the composition epoxy resin adopting formula of the present invention and preparation method to obtain and dicyandiamide cure can reach more than 135 degrees Celsius, and the second-order transition temperature of common FR4 epoxy resin is generally about 130 DEG C.
Below by the example of illustrating, the invention will be further elaborated, but the present invention is not limited to this specific examples.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail:
Embodiment 1
1. prepare UV functional reagent
Fluorescent whitening agent OB is mixed for subsequent use with the weight of South Asia, Taiwan TPN2 according to the ratio of 1:45; Wherein white dyes is also called the white dyes 184 of OB; 2.5-pair-(the 5-tertiary butyl-2-benzoxazolyl) thiophene; Two (5-tert-butyl-2-benzene azoles base) thiophene of 2,5-, its molecular formula is C
26h
26n
2o
2s, molecular weight is 430.56.In actually operating, also need to allocate the requirement Yellow environment-friendly dyestuff of product colour and fluorescent whitening agent OB according to client.This South Asia, Taiwan TPN2 is the resol with UV barrier functionality, is phenol and oxalic dialdehyde resultant, its hydroxyl equivalent 90-110g/eq, softening temperature 120-150 DEG C.
2. prepare composition epoxy resin
Take each component by following weight part: epoxy resin 52.1 parts, tetrabromo-bisphenol is 26.06 parts, 2-phenylimidazole 0.002 part, UV functional reagent 1.84 parts; 19.998 parts, acetone.
Epoxy resin and tetrabromo-bisphenol are dropped in reaction unit, under the effect of 2-phenylimidazole, is heated to 160 ~ 180 DEG C and carries out addition reaction, at such a temperature 120 ~ 180 minutes insulation reaction time; Be cooled to 120 ~ 150 DEG C, then add UV functional reagent reaction 30 ~ 60 minutes; After question response, reaction system is cooled to 50 ~ 60 DEG C, adds acetone, be uniformly mixed obtained described composition epoxy resin.
The epoxy resin of the present embodiment is E-51 type electronic-grade bisphenol A type epoxy resin, South Asia, Taiwan NPEL-127E, and its average molecular mass Mn is 363, and hydrolyzable chloride content is 150ppm, and viscosity is 10000mPa.s (25 DEG C), and oxirane value is 5.5eq/kg.The master of the tetrabromo-bisphenol used is containing being greater than 98%, and bromine content is greater than 58%, and the acetone used requires as premium grads, and its purity is greater than 99.5%, and moisture is less than 0.3%.
3. prepare copper-clad plate
The catalyzer glyoxal ethyline of 100 these composition epoxy resins of weight part with 2.6 weight parts and 0.035 weight part is mixed evenly, is made into glue, through adhesive applicator, makes glue semicure on glass-fiber-fabric, become semicure PP sheet; Then PP sheet and Copper Foil are stacked on vacuum press, press temperature keeps 170 ~ 190 DEG C, and pressure is 2 ~ 4MPa, is pressed into copper-clad plate through 60 ~ 120 minutes.Tg, CTI and UV barrier functionality of test sheet material, test result asks for an interview table 1.
Embodiment 2
1. prepare UV functional reagent
The weight of fluorescent whitening agent OB with South Asia, Taiwan TPN2 is mixed according to 1:20 ratio, evenly for subsequent use; In actually operating, also need to allocate the requirement Yellow environment-friendly dyestuff of product colour and fluorescent whitening agent OB according to client.
2. prepare composition epoxy resin
Take each component by following weight part: epoxy resin 52.49 parts, tetrabromo-bisphenol is 26.25 parts, 2-phenylimidazole 0.002 part, UV functional reagent 1.26 parts; 19.998 parts, acetone.
Drop in reaction unit by epoxy resin and tetrabromo-bisphenol, under the effect of 2-phenylimidazole, be heated to 165 ~ 175 DEG C and carry out addition reaction, the insulation reaction time is 150 ~ 180 minutes at such a temperature; Be cooled to 120 ~ 150 DEG C, then add UV functional reagent reaction 30 ~ 60 minutes; After question response, reaction system is cooled to 50 ~ 60 DEG C, adds acetone, be uniformly mixed obtained described composition epoxy resin.
The epoxy resin of the present embodiment is electronic-grade bisphenol A type epoxy resin, and average molecular mass Mn is 363, and hydrolyzable chloride content is 150ppm, and viscosity is 10000mPa.s (25 DEG C), and oxirane value is 5.5eq/kg.The master of the tetrabromo-bisphenol used is containing being greater than 98%, and bromine content is greater than 58%, and the acetone used requires as premium grads, and its purity is greater than 99.5%, and moisture is less than 0.3%.
3. prepare copper-clad plate
The method preparing copper-clad plate of embodiment 1 is adopted to prepare.Tg, CTI and UV barrier functionality of test sheet material, test result asks for an interview table 1.
Embodiment 3
1. prepare UV functional reagent
The weight of fluorescent whitening agent OB with South Asia, Taiwan TPN2 is mixed according to the ratio of 1:120, evenly for subsequent use; In actually operating, also need to allocate the requirement Yellow environment-friendly dyestuff of product colour and fluorescent whitening agent OB according to client.
2. prepare composition epoxy resin
Take each component by following weight part: epoxy resin 51.72 parts, tetrabromo-bisphenol is 25.86 parts, 2-phenylimidazole 0.002 part, UV functional reagent 2.42 parts; 19.998 parts, acetone.
Drop in reaction unit by epoxy resin and tetrabromo-bisphenol, under the effect of 2-phenylimidazole, be heated to 160 ~ 170 DEG C and carry out addition reaction, the insulation reaction time is 150 ~ 180 minutes at such a temperature; Be cooled to 120 ~ 150 DEG C, then add UV functional reagent reaction 30 ~ 60 minutes; After question response, reaction system is cooled to 50 ~ 60 DEG C, adds acetone, be uniformly mixed obtained described composition epoxy resin.
The epoxy resin of the present embodiment is electronic-grade bisphenol A type epoxy resin, and average molecular mass Mn is 363, and hydrolyzable chloride content is 150ppm, and viscosity is 10000mPa.s (25 DEG C), and oxirane value is 5.5eq/kg.The master of the tetrabromo-bisphenol used is containing being greater than 98%, and bromine content is greater than 58%, and the acetone used requires as premium grads, and its purity is greater than 99.5%, and moisture is less than 0.3%.
3. prepare copper-clad plate
The method preparing copper-clad plate of embodiment 1 is adopted to prepare.Tg, CTI and UV barrier functionality of test sheet material, test result asks for an interview table 1.
Comparative example 1
After the common FR4 of 100 weight part (the fire-retardant copper-clad plate of glass-fiber-fabric) epoxy resin and 2.6 weight part Dyhard RU 100s and 0.035 weight part glyoxal ethyline solidify, make copper-clad plate, and test Tg and CTI of sheet material and UV and stop, test result asks for an interview table 1.
The common FR4 epoxy resin of the preparation copper-clad plate adopted is Poly28000A80 etc., and its oxirane value is generally 2.2 ~ 2.4eq/kg, chlorine is generally less than 300ppm, viscosity is generally 800 ~ 2000mPa.s in hydrolysis.
Comparative example 2
(weight percent shared by tetrafunctional epoxy resin is 6% to get the tetrafunctional epoxy resin solution of 100 weight parts and FR4 ordinary epoxy resin mixture, and FR4 ordinary epoxy resin accounts for 94%), prepare copper-clad plate by method in embodiment 1 and test Tg, CTI and UV barrier functionality of sheet material.
Table 1
| Tg (degree Celsius) | UV transmittance (%) | CTI(V) | Cost ($/kg) | |
| X Customer Standard | ≥135 | ≤2 | ≥175 | |
| Embodiment 1 | 137.0 | 1.6 | 225 | 17.09 |
| Embodiment 2 | 136.8 | 1.5 | 225 | 17.12 |
| Embodiment 3 | 137.2 | 1.7 | 225 | 17.05 |
| Comparative example 1 | 132.6 | - | 150 | 16.73 |
| Comparative example 2 | 134.8 | 1.5 | 150 | 17.80 |
Data as can be seen from table 1: the product that the present invention obtains has good UV barrier functionality and cost is lower, and adopt FR4 ordinary epoxy resin in comparative example 1 and not there is UV barrier functionality, although and meet UV barrier functionality requirement cost increase in comparative example 2 a lot.In addition, the product glass transition temp Tg value that the present invention obtains reaches more than 135 DEG C, and the Tg of common FR4 epoxy resin (being 130 ~ 135 DEG C) is significantly increased, and CTI is also significantly increased, and is brought up to the level of 225V by the 150V of common FR4 copper-clad plate.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, all comprise protection scope of the present invention.
Claims (8)
1. a preparation method for composition epoxy resin, is characterized in that, comprises the following steps:
1). preparation UV functional reagent: UV is stopped white dyes mixes for subsequent use with the weight of UV functional resin in 1:20 ~ 1:120 ratio;
2). prepare composition epoxy resin:
A). take each raw material by formula, described formula comprises each raw material of following weight percent:
B). drop in reaction unit by above-mentioned epoxy resin and tetrabromo-bisphenol, under catalyst action, be heated to 160 ~ 180 DEG C and carry out addition reaction, the insulation reaction time is 120 ~ 180 minutes at such a temperature; Be cooled to 120 ~ 150 DEG C, then add step 1) prepared by UV functional reagent reaction 30 ~ 60 minutes;
C). reaction system is cooled to less than 60 DEG C, adds thinner, be uniformly mixed obtained described composition epoxy resin; Wherein:
Described UV stops that white dyes is fluorescent whitening agent OB;
Described UV functional resin is four phenolic group ethane resol.
2. the preparation method of composition epoxy resin according to claim 1, is characterized in that, comprises the following steps:
1). preparation UV functional reagent: UV is stopped white dyes mixes for subsequent use with the weight of UV functional resin in 1:20 ~ 1:120 ratio;
2). prepare composition epoxy resin:
A). take each raw material by formula, described formula comprises each raw material of following weight percent:
B). drop in reaction unit by above-mentioned epoxy resin and tetrabromo-bisphenol, under catalyst action, be heated to 160 ~ 180 DEG C and carry out addition reaction, the insulation reaction time is 120 ~ 180 minutes at such a temperature; Be cooled to 120 ~ 150 DEG C, then add step 1) prepared by UV functional reagent reaction 30 ~ 60 minutes;
C). reaction system is cooled to less than 60 DEG C, adds thinner, be uniformly mixed obtained described composition epoxy resin.
3. the preparation method of composition epoxy resin according to claim 1 and 2, it is characterized in that, described epoxy resin is electronic-grade bisphenol A type epoxy resin, and its hydrolyzable chloride content is less than 300ppm, viscosity 9000 ~ 10500mPa.s, oxirane value 5.4 ~ 5.8eq/kg.
4. the preparation method of composition epoxy resin according to claim 1 and 2, is characterized in that, the master of described tetrabromo-bisphenol is containing being greater than 98%, and bromine content is greater than 58%.
5. the preparation method of composition epoxy resin according to claim 1 and 2, is characterized in that, described step 2) in addition reaction temperature be 165 ~ 175 DEG C, the insulation reaction time is 120 ~ 180 minutes.
6. the preparation method of composition epoxy resin according to claim 1 and 2, is characterized in that, described catalyzer is imidazoles catalyzer; Described thinner is acetone.
7. the preparation method of composition epoxy resin according to claim 6, is characterized in that, described catalyzer is 2-phenylimidazole.
8. a copper-clad plate used for printed circuit, is characterized in that, it is prepared from as follows:
1). by the composition epoxy resin such as obtained by claim 1 or 2 preparation method and Dyhard RU 100 and catalyzer by weight 100:2.5-3.0:0.025-0.045 mix, be made into glue, through adhesive applicator, make glue semicure on glass-fiber-fabric, become semicure PP sheet;
2). then PP sheet and Copper Foil are stacked on vacuum press, be pressed into copper-clad plate, the temperature of compacting is 170 ~ 190 DEG C, and pressure is 2 ~ 4MPa, and the press time is 60 ~ 120 minutes.
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| CN106280261B (en) * | 2016-08-25 | 2019-04-16 | 纽宝力精化(广州)有限公司 | Composition epoxy resin and preparation method thereof with high tg values |
| CN107344993B (en) * | 2017-06-14 | 2018-09-11 | 建滔(番禺南沙)石化有限公司 | A kind of preparation method of antiultraviolet epoxy resin and the product of acquisition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1286701A (en) * | 1998-09-22 | 2001-03-07 | 博登化学公司 | Phenol-novolacs with improved optical properties |
| CN101210168A (en) * | 2006-12-30 | 2008-07-02 | 财团法人工业技术研究院 | Packaging material composition |
| CN103214796A (en) * | 2013-04-28 | 2013-07-24 | 纽宝力精化(广州)有限公司 | Epoxy resin composition, preparation method of epoxy resin composition, and copper-clad plate prepared by epoxy resin composition |
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|---|---|---|---|---|
| JP2611711B2 (en) * | 1991-10-18 | 1997-05-21 | 新神戸電機株式会社 | Resin composition for laminate and method for producing laminate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1286701A (en) * | 1998-09-22 | 2001-03-07 | 博登化学公司 | Phenol-novolacs with improved optical properties |
| CN101210168A (en) * | 2006-12-30 | 2008-07-02 | 财团法人工业技术研究院 | Packaging material composition |
| CN103214796A (en) * | 2013-04-28 | 2013-07-24 | 纽宝力精化(广州)有限公司 | Epoxy resin composition, preparation method of epoxy resin composition, and copper-clad plate prepared by epoxy resin composition |
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