CN102093664A - Thermosetting glue solution for copper-clad substrate, preparation method thereof and forming process of halogen-free flame-retardant copper-clad substrate - Google Patents
Thermosetting glue solution for copper-clad substrate, preparation method thereof and forming process of halogen-free flame-retardant copper-clad substrate Download PDFInfo
- Publication number
- CN102093664A CN102093664A CN2009102497003A CN200910249700A CN102093664A CN 102093664 A CN102093664 A CN 102093664A CN 2009102497003 A CN2009102497003 A CN 2009102497003A CN 200910249700 A CN200910249700 A CN 200910249700A CN 102093664 A CN102093664 A CN 102093664A
- Authority
- CN
- China
- Prior art keywords
- copper clad
- foil substrate
- copper
- glue
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 C*CN**(C)C* Chemical compound C*CN**(C)C* 0.000 description 6
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a thermosetting glue solution for a lead-free process copper-clad substrate. The glue solution comprises the following components in percentage by weight: 30 to 60 percent of epoxy resin, 15 to 30 percent of curing agent, 0.01 to 1 percent of curing accelerator, 20 to 50 percent of solvent and 10 to 50 percent of filler. The invention also discloses a preparation method of the thermosetting glue solution for a copper-clad substrate, and discloses the application of the thermosetting glue solution to the copper-clad substrate and a manufacturing method of a high-heat-resistant copper-clad substrate. A prepreg prepared from the thermosetting glue solution has low water absorption rate. After being molded, the copper-clad substrate has high intensity and greatly improved heat resistance.
Description
Technical field
The present invention relates to a kind of thermoset glue, be specifically related to a kind of high-performance glue that is applicable to that the high heat-resisting copper clad foil substrate of leadless process uses.
Background technology
European Union instructed by RoHS in October, 2002, and in formal advertising on February 13rd, 2003, the declaration that its content is clear and definite will go into effect on July 1st, 2006, and electronic product is forbidden lead (Lead), cadmium (Cadmium), mercury (Mercury), sexavalent chrome (Hexavalent Chromium), bromide flame retardant 6 kinds of materials such as (Polybrominated Biphenyls, Polybrominated Diphenyl Ethers) comprehensively; After the formal announcement along with rules, the unleaded conversion time-histories of every electronic product also transfers to definite, and this pointer regulation has developed into global environmental requirement, also becomes information electronic industry basic fundamental threshold.
Along with the unleaded implementation of electron trade, the electronic component welding temperature greatly improves, thermotolerance, mechanical property to copper clad foil substrate have been made higher requirement, can possess this type of high performance copper clad foil substrate and then are referred to as " unleaded " change copper clad foil substrate by industry.For the copper clad foil substrate industry, it is better to develop thermotolerance, and " unleaded " change requirement that " unleaded " change copper clad foil substrate that other performance is also more excellent adapts to present industry is imperative.
Dyhard RU 100 (DICY) is a kind of latent curing agent, has outstanding comprehensive result of use.In FR-4 copper clad foil substrate is before produced, be widely adopted always.But blemish in an otherwise perfect thing is that this solidifying agent copper clad foil substrate resistance toheat of making is not good enough.Along with the arrival in pb-free solder epoch, need satisfy the requirement of high welding temperature, curing system originally is unable to do what one wishes.In order to improve the resistance toheat of copper clad foil substrate, industry generally can adopt other solidifying agent to replace traditional Dyhard RU 100, and for example Chinese patent CN200510101352.7 discloses, and adopts linear phenolic resin to replace Dyhard RU 100 as curing agent for epoxy resin.Yet, after the use linear phenolic resin replaces Dyhard RU 100, but there are some new problems, for example, the prepreg water-intake rate increases, and it is more crisp to solidify the back resin system, copper clad foil substrate stripping strength reduction or the like.
In view of this, the inventor studies this, be intended to develop a kind of thermoset glue that can be used for the leadless process copper clad foil substrate, this glue adopts novel curing agent of substituted curing agent dicyandiamide or linear phenolic aldehyde commonly used at present, can obtain lower excellent properties such as water-intake rate, so that can make the copper clad foil substrate that makes more be applicable to leadless process.
Summary of the invention
The object of the invention provides a kind of novel hot setting glue in order to overcome the deficiencies in the prior art, applicable to leadless process, provides the manufacture method of this thermoset glue with the copper clad foil substrate material of this glue preparation simultaneously.
Another object of the present invention provides the preparation method of halogen-free flameproof copper clad foil substrate substrate.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of thermoset glue that is used for copper clad foil substrate, component and weight ratio content thereof:
Resins, epoxy 30-60%;
Solidifying agent 15-30%;
Curing catalyst 0.01-1%;
Solvent 20-50%;
Filler 10-50%.
Wherein Resins, epoxy is brominated epoxy resin, or the mixture of brominated epoxy resin and halogen-free epoxy resin; Brominated epoxy resin is:
(1) brominated bisphenol A diglycidylether
N=1～10 wherein
(2) the linear phenolic aldehyde polyglycidyl ether of bromination
N=1～10 wherein
In any;
Halogen-free epoxy resin is:
(1) bisphenol A diglycidyl ether
N=1～10 wherein
(2) Bisphenol F diglycidylether
N=1～10 wherein
(3) bisphenol-S diglycidyl ether
N=1～10 wherein
(4) linear phenolic aldehyde polyglycidyl ether
(5) linear cresoform polyglycidyl ether
N=1～5 wherein
Or (6) glycidyl amine type epoxy resin
In any.
The solidifying agent general formula is:
N=2～9 wherein, m=0～5.
Curing catalyst is: glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-ethyl imidazol(e) or 2-phenylimidazole are wherein any.
Solvent is: the mixed solvent that toluene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, Propylene Glycol Dimethyl Ether, 1-Methoxy-2-propyl acetate, methylethylketone, pimelinketone or acetone are wherein any or several.
Filler is wherein one or more a mixture of silicon powder, talcum powder, kaolin, aluminium hydroxide, magnesium hydroxide.
The described manufacture method that is used for the thermoset glue of copper clad foil substrate of a kind of claim 1, feed composition and weight ratio content are Resins, epoxy 30-60%, solidifying agent 15-30%, curing catalyst 0.01-1%, solvent 20-50%, filler 10-50%, may further comprise the steps:
A, solidifying agent and curing catalyst are dissolved in solvent, be mixed with solution, stand-by;
B, with dimethyl formamide DMF, pimelinketone, butanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether amyl acetate etc. or its combination as solvent system, dilute as thinner with acetone, butanone or its combination, stand-by;
Under C, the room temperature, in proportion container, add solvent, curing agent solution respectively; Stir down, add the special composition in Resins, epoxy, fire retardant, curing catalyst and other prescription respectively, continue to stir 30 minutes.
D, the compound silica powder of adding mineral filler, restir 6 hours;
E, sampling, the test glue is controlled its gel time at the gel time of 170 ℃ of hot plates between 200～400 seconds by the addition of curing catalyst;
F, go out finished product.
Wherein among the step D for it is evenly distributed in the glue, need to mix, to avoid the adhesive aggregation effect between the particle through higher shear power.
A kind of moulding process of high heat-resisting copper clad foil substrate substrate comprises following flow process:
A, prepare the thermoset glue: Resins, epoxy 30-60%, solidifying agent 15-30% by following weight ratio; Curing catalyst 0.01-1%; Solvent 20-50%; Filler 10-50%;
B, will soak the thermoset glue adhesive plaster by vertical or horizontal type impregnation machine, by control wind-warm syndrome and furnace temperature, make prepreg;
C, prepreg is cut into certain size, its up and down with the Copper Foil combination after, put into the vacuum hotpressing machine, press down at certain temperature, pressure, time and vacuum condition and make copper clad foil substrate.
Owing to adopted said structure, water-intake rate was extremely low when thermoset glue of the present invention closed cured sheets in moulding, and copper clad foil substrate intensity height after the moulding improves the thermotolerance of copper clad foil substrate greatly.
Embodiment:
The present invention is further detailed explanation below in conjunction with embodiment.
1, specific embodiment prescription:
One of embodiment GEBR454A80 (brominated epoxy resin that grand prosperous electronics produces) 49.5%, solidifying agent para hydroxybenzene ethene and styrol copolymer 16.5%, propylene glycol monomethyl ether 22.0%, curing catalyst 2-ethyl-4-methylimidazole 0.3%, G2-C (gram company in Thebe produces compound silica powder) 11.7%.
Two (comparative example) GEBR454A80 of embodiment (brominated epoxy resin that grand prosperous electronics produces) 62.5%, curing agent dicyandiamide 3.5%, dimethyl formamide 22%, curing catalyst 2-ethyl-4-methylimidazole 0.3%, G2-C (gram company in Thebe produces compound silica powder) 11.7%.
Three (comparative example) GEBR454A80 of embodiment (brominated epoxy resin that grand prosperous electronics produces) 49.5%, solidifying agent 3363 (linear phenolic resin that Hexion produces) 16.5%, propylene glycol monomethyl ether 22.0%, 0.3% part of curing catalyst 2-ethyl-4-methylimidazole, G2-C (gram company in Thebe produces compound silica powder) 11.7%.
Four XUS19074 of the embodiment (Resins, epoxy that Dow Chemical produces, possess 170 ℃ Tg after the curing) 49.5%, solidifying agent para hydroxybenzene ethene and styrol copolymer 16.5%, propylene glycol monomethyl ether 22.0%, curing catalyst 2-ethyl-4-methylimidazole 0.3%, G2-C (gram company in Thebe produces compound silica powder) 11.7%.
Five GEBR454A80 of embodiment (brominated epoxy resin that grand prosperous electronics produces) 39.5%, solidifying agent para hydroxybenzene ethene and styrol copolymer 26.5%, propylene glycol monomethyl ether 22.0%, curing catalyst 2-ethyl-4-methylimidazole 0.3%, G2-C (gram company in Thebe produces compound silica powder) 11.7%.
2, the preparation method of glue
A, solidifying agent and curing catalyst are dissolved in solvent, be mixed with solution, stand-by;
B, with dimethyl formamide DMF, pimelinketone, butanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether amyl acetate etc. or its combination as solvent system, dilute as thinner with acetone, butanone or its combination, stand-by;
Under C, the room temperature, in proportion container, add solvent, curing agent solution respectively; Stir down, add the special composition in Resins, epoxy, fire retardant, curing catalyst and other prescription respectively, continue to stir 30 minutes.
D, the compound silica powder of adding mineral filler, restir 6 hours;
E, sampling, the test glue is controlled its gel time at the gel time of 170 ℃ of hot plates between 200～400 seconds by the addition of curing catalyst;
F, go out thermoset glue finished product.
3, the moulding process of high heat-resisting copper clad foil substrate substrate
1), impregnation
The adhesive plaster that will soak the halogen-free flameproof glue by conditions such as control extruding wheel speed, linear speed, wind-warm syndrome and furnace temperature, makes prepreg by vertical or horizontal type impregnation machine.
With vertical impregnation machine is example:
The proportion of Varnish: 1.10～1.20;
Extruding wheel speed :-1.8～-2.5 ± 0.1M/min;
Main line speed: 5～14M/min;
Wind-warm syndrome: 130～160 ℃;
Furnace temperature: 140～180 ℃.
Make prepreg by above condition.
2), compacting
After the prepreg that cuts and Copper Foil combined, put into the vacuum hotpressing machine, obtaining substrate by following formula compacting.
Temperature formula: 130 ℃/30min+160 ℃/30min+180 ℃/20min+210 ℃/180min
Pressure formula: 20Kgf.cm
-2/ 30min+50Kgf.cm
-2/ 15min+95Kgf.cm
-2/ 150min+
20Kgf.cm
-2/65min
Vacuum is set: 30mmHg/130min+760mmHg/130min
4, following for the substrate performance of prescription:
Claims (9)
1. thermoset glue that is used for copper clad foil substrate, component and weight ratio content thereof:
Resins, epoxy 30-60%;
Solidifying agent 15-30%;
Curing catalyst 0.01-1%;
Solvent 20-50%;
Filler 10-50%.
2. the thermoset glue that is used for copper clad foil substrate according to claim 1, wherein Resins, epoxy is brominated epoxy resin, or the mixture of brominated epoxy resin and halogen-free epoxy resin;
Wherein brominated epoxy resin is:
(1) brominated bisphenol A diglycidylether
N=1～10 wherein
(2) the linear phenolic aldehyde polyglycidyl ether of bromination
N=1～10 wherein
In any;
Halogen-free epoxy resin is:
(1) bisphenol A diglycidyl ether
N=1～10 wherein
(2) Bisphenol F diglycidylether
N=1～10 wherein
(3) bisphenol-S diglycidyl ether
N=1～10 wherein
(4) linear phenolic aldehyde polyglycidyl ether
(5) linear cresoform polyglycidyl ether
N=1～5 wherein
Or (6) glycidyl amine type epoxy resin
In any.
3. the thermoset glue that is used for copper clad foil substrate according to claim 1, wherein the solidifying agent general formula is:
N=2～9 wherein, m=0～5.
4. the thermoset glue that is used for copper clad foil substrate according to claim 1, wherein curing catalyst is: glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-ethyl imidazol(e) or 2-phenylimidazole are wherein any.
5. the thermoset glue that is used for copper clad foil substrate according to claim 1, wherein solvent is: the mixed solvent that toluene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, Propylene Glycol Dimethyl Ether, 1-Methoxy-2-propyl acetate, methylethylketone, pimelinketone or acetone are wherein any or several.
6. the thermoset glue that is used for copper clad foil substrate according to claim 1, wherein filler is wherein one or more a mixture of silicon powder, talcum powder, kaolin, aluminium hydroxide, magnesium hydroxide.
7. described manufacture method that is used for the thermoset glue of copper clad foil substrate of claim 1, feed composition and weight ratio content are Resins, epoxy 30-60%, solidifying agent 15-30%, curing catalyst 0.01-1%, solvent 20-50%, filler 10-50%, may further comprise the steps:
A, solidifying agent and curing catalyst are dissolved in solvent, be mixed with solution, stand-by;
B, with dimethyl formamide DMF, pimelinketone, butanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether amyl acetate etc. or its combination as solvent system, dilute as thinner with acetone, butanone or its combination, stand-by;
Under C, the room temperature, in proportion container, add solvent, curing agent solution respectively; Stir down, add the special composition in Resins, epoxy, fire retardant, curing catalyst and other prescription respectively, continue to stir 30 minutes.
D, the compound silica powder of adding mineral filler, restir 6 hours;
E, sampling, the test glue is controlled its gel time at the gel time of 170 ℃ of hot plates between 200～400 seconds by the addition of curing catalyst;
F, go out finished product.
8. the manufacture method of thermoset glue according to claim 7, wherein among the step D for it is evenly distributed in the glue, need to mix, to avoid the adhesive aggregation effect between the particle through higher shear power.
9. the moulding process of a high heat-resisting copper clad foil substrate substrate comprises following flow process:
A, prepare the thermoset glue: Resins, epoxy 30-60%, solidifying agent 15-30% by following weight ratio; Curing catalyst 0.01-1%; Solvent 20-50%; Filler 10-50%;
B, will soak the thermoset glue adhesive plaster by vertical or horizontal type impregnation machine, by control wind-warm syndrome and furnace temperature, make prepreg;
C, prepreg is cut into certain size, its up and down with the Copper Foil combination after, put into the vacuum hotpressing machine, press down at certain temperature, pressure, time and vacuum condition and make copper clad foil substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910249700A CN102093664B (en) | 2009-12-14 | 2009-12-14 | Thermosetting glue solution for copper-clad substrate, preparation method thereof and forming process of halogen-free flame-retardant copper-clad substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910249700A CN102093664B (en) | 2009-12-14 | 2009-12-14 | Thermosetting glue solution for copper-clad substrate, preparation method thereof and forming process of halogen-free flame-retardant copper-clad substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102093664A true CN102093664A (en) | 2011-06-15 |
| CN102093664B CN102093664B (en) | 2012-09-26 |
Family
ID=44126943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910249700A Active CN102093664B (en) | 2009-12-14 | 2009-12-14 | Thermosetting glue solution for copper-clad substrate, preparation method thereof and forming process of halogen-free flame-retardant copper-clad substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102093664B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103057213A (en) * | 2012-12-31 | 2013-04-24 | 金安国纪科技股份有限公司 | Environment-friendly copper clad laminate for LED monochrome display, glue solution and preparation method |
| CN103057214A (en) * | 2012-12-31 | 2013-04-24 | 金安国纪科技股份有限公司 | Environment-friendly glue solution for LED full-color display, copper clad laminate and preparation method thereof |
| CN103194044A (en) * | 2013-04-14 | 2013-07-10 | 鲍联 | Halogen-free flame-retardant epoxy resin composition |
| CN103408903A (en) * | 2013-08-28 | 2013-11-27 | 四川迪弗电工科技有限公司 | High-strength insulating support beam and preparation method thereof |
| CN106519569A (en) * | 2016-10-26 | 2017-03-22 | 建滔(佛冈)积层板有限公司 | High-CTI-value halogen-free flame retardant glue solution and prepreg and copper-clad laminate prepared therefrom |
| CN110437585A (en) * | 2019-08-15 | 2019-11-12 | 重庆德凯实业股份有限公司 | One kind covering copper foil epoxy glass fiber fabric base laminate and its preparation process |
| CN113844039A (en) * | 2021-09-27 | 2021-12-28 | 山东金宝电子股份有限公司 | Preparation method of novel low-dielectric-constant copper-clad plate glue solution |
-
2009
- 2009-12-14 CN CN200910249700A patent/CN102093664B/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103057213A (en) * | 2012-12-31 | 2013-04-24 | 金安国纪科技股份有限公司 | Environment-friendly copper clad laminate for LED monochrome display, glue solution and preparation method |
| CN103057214A (en) * | 2012-12-31 | 2013-04-24 | 金安国纪科技股份有限公司 | Environment-friendly glue solution for LED full-color display, copper clad laminate and preparation method thereof |
| CN103057214B (en) * | 2012-12-31 | 2015-03-11 | 金安国纪科技股份有限公司 | Environment-friendly glue solution for LED full-color display, copper clad laminate and preparation method thereof |
| CN103057213B (en) * | 2012-12-31 | 2015-10-07 | 金安国纪科技股份有限公司 | The copper-clad plate of environment-friendly type LED single color display screen, glue and preparation method |
| CN103194044A (en) * | 2013-04-14 | 2013-07-10 | 鲍联 | Halogen-free flame-retardant epoxy resin composition |
| CN103408903A (en) * | 2013-08-28 | 2013-11-27 | 四川迪弗电工科技有限公司 | High-strength insulating support beam and preparation method thereof |
| CN103408903B (en) * | 2013-08-28 | 2015-12-02 | 四川迪弗电工科技有限公司 | A kind of high-strength insulating supporting beam and preparation method thereof |
| CN106519569A (en) * | 2016-10-26 | 2017-03-22 | 建滔(佛冈)积层板有限公司 | High-CTI-value halogen-free flame retardant glue solution and prepreg and copper-clad laminate prepared therefrom |
| CN110437585A (en) * | 2019-08-15 | 2019-11-12 | 重庆德凯实业股份有限公司 | One kind covering copper foil epoxy glass fiber fabric base laminate and its preparation process |
| CN113844039A (en) * | 2021-09-27 | 2021-12-28 | 山东金宝电子股份有限公司 | Preparation method of novel low-dielectric-constant copper-clad plate glue solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102093664B (en) | 2012-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102093664B (en) | Thermosetting glue solution for copper-clad substrate, preparation method thereof and forming process of halogen-free flame-retardant copper-clad substrate | |
| AU2013201482B2 (en) | Epoxy Resin Composition, and Prepreg and Copper Clad Laminate Made Therefrom | |
| CN100519179C (en) | Preparation method of glass transition temperature halogenless fire retardant glass cloth laminated board | |
| KR101799717B1 (en) | Thermosetting resin composition and use thereof | |
| TWI638001B (en) | Thermosetting resin composition and use thereof | |
| CN106671548B (en) | A kind of preparation method of CEM-1 copper-clad plates | |
| CN102585440B (en) | High-CTI (comparative tracking index) halogen-free flame retardant resin composition for copper-clad laminate | |
| CN101921458B (en) | Unleaded epoxy resin composite for printed circuit copper clad laminate | |
| EP2706091B1 (en) | Epoxy resin composition, and prepreg and copper clad laminate made therefrom | |
| TWI588202B (en) | Low dielectric resin composition and copper foil substrate and printed circuit board using the same | |
| CN101104727B (en) | Halogen-free resin composition and resin-coated copper foil of the same for high-density interconnection | |
| CN101547558B (en) | Copper clad base plate and preparation method thereof | |
| CN104927353A (en) | Inflaming-retarding halogen-free and phosphorus-free resin composition and use thereof and preparation method applying to half-curing piece, laminated board and copper-clad plate | |
| KR101730283B1 (en) | Thermosetting resin composition and use thereof | |
| WO2015149449A1 (en) | Halogen-free resin composition and use thereof | |
| TW201425448A (en) | Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same | |
| CN101165076A (en) | Anti-flaming phosphorus-containing epoxy resin, preparation method thereof and composition containing the same | |
| JPH073053A (en) | Production of modified polyphenylene oxide resin system for electrical laminate board with improved soldability and solvent resistance | |
| CN111793327A (en) | Epoxy resin composition for high-speed high-frequency copper-clad plate and preparation method thereof | |
| JP4915549B2 (en) | Resin composition for printed wiring board, prepreg and laminate using the same | |
| EP0537005A1 (en) | Process for making thermoset polyphenylene oxide/epoxy laminates | |
| JPH0819213B2 (en) | Epoxy resin composition and copper clad laminate | |
| CN111500015B (en) | Halogen-free resin composition | |
| TWI388622B (en) | And a thermosetting resin composition having an acid anhydride hardening | |
| CN101580630A (en) | Halogen-free flame retarding epoxy resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200708 Address after: 214028 No.26, Xiqin Road, Xinwu District, Wuxi City, Jiangsu Province Patentee after: WUXI GRACE ELECTRONIC MATERIAL TECHNOLOGY Co.,Ltd. Address before: 510530, No. 1, Po pan Road, Guangzhou, Guangdong, Luogang District Patentee before: GUANGZHOU GRACE ELECTRONIC INDUSTRY Co.,Ltd. |
|
| TR01 | Transfer of patent right |