CN109337288A - A kind of unleaded high CTI resin combination for copper-clad plate - Google Patents
A kind of unleaded high CTI resin combination for copper-clad plate Download PDFInfo
- Publication number
- CN109337288A CN109337288A CN201711482054.6A CN201711482054A CN109337288A CN 109337288 A CN109337288 A CN 109337288A CN 201711482054 A CN201711482054 A CN 201711482054A CN 109337288 A CN109337288 A CN 109337288A
- Authority
- CN
- China
- Prior art keywords
- copper
- clad plate
- epoxy resin
- resin combination
- high cti
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Classifications
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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
-
- 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
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
-
- 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
Abstract
The present invention discloses a kind of unleaded high CTI resin combination for copper-clad plate, includes following main component: 60~80PHR of mixture that brominated epoxy resin is mixed at least another epoxy resin；Curing agent 20-40PHR；0.01~1PHR of curing accelerator；30~70PHR of inorganic filler；0.01~1PHR of silane coupling agent；Appropriate solvent.The present invention has adjusted system aluminium hydroxide, boehmite ratio, while meeting UL-94V0 grades of flame-retardancy requirements, cooperates with high CTI epoxy resin effect with high creepage trace index, CTI >=600V.And high Tg curing agent is chosen instead of the use of dicyandiamide, its glass transition temperature is also improved while with high heat resistance and there is good machining property, is applicable to pb-free solder.The present invention can be made into the copper-clad laminate used suitable for white domestic appliances, inverter, outdoor charging pile etc..
Description
Technical field
The present invention relates to resin combination field technologies, refer in particular to a kind of unleaded high CTI resin group for copper-clad plate
Close object.
Background technique
The surface of insulating substrate used for printed circuit board is under the synergy of face electric field and PCB surface filth, because of part
Electric discharge forms conductive or partially electronically conductive channel, and material surface is made gradually to degrade, and tail end (road) occurs or electric property sharply drops
Low risk is increasing.It repeated flashover electric discharge between route and generate electric spark, and then form the trace of charing conducting channel,
Substrate surface insulation performance is destroyed, conductive channel is formed, creepage trace phenomenon occurs.
In order to improve the security reliability of electronic product, special printed circuit board makes under moist, environmental condition easy to pollute
Insulating reliability, the copper-clad plate with high creepage trace index (CTI) is also just come into being, and is widely applied.
Under the promotion of unleaded tide, original original part welding procedure is replaced by pb-free solder technique, welding temperature ratio
It was higher by 20 DEG C or more in the past；And a series of high speed development of circuit boards such as outdoor charging pile, inverter, therefore to high CTI copper-clad plate
The heat resistance and reliability of material are put forward higher requirements.For the FR-4 plate of conventional high CTI, resin uses amine
The defects of solidification, that there are heat resistances is low for plate, and Tg is low insufficient with chemical resistance, it is difficult to meet multi-layer board processing and pb-free solder
Needs.
Use low brominated epoxy as main body in 101654004 B of Chinese patent CN, DICY is as curing agent, though have
Have preferable phase ratio creepage tracking index (CTI), but its that there are heat resistances is poor, it is difficult to meet current industry leadless process need
It asks.
In 105419231 A of Chinese patent CN using cycloaliphatic epoxy resin, phosphorous epoxy resin, brominated epoxy resin,
Acid anhydrides, phosphorus-containing phenolic aldehyde, though having preferable phase ratio creepage tracking index and heat resistance, its glass transition temperature Tg is lower,
Limit the end PCB procedure for processing, it is difficult to meet electronic material under current trends higher and higher processing and use demand.
Therefore, developing one kind has high relative discharge tracking index (CTI), and has good heat resistance, higher glass
Change transition temperature, the composition epoxy resin for being able to satisfy PCB leadless process demand is current urgent problem to be solved.
Summary of the invention
In view of this, in view of the deficiencies of the prior art, the present invention aims to provide one kind to be used for copper-clad plate
Unleaded high CTI resin combination, with excellent proof tracking index.
To achieve the above object, the present invention is using following technical solution:
A kind of unleaded high CTI resin combination for copper-clad plate, include following main component: brominated epoxy resin with extremely
60~80PHR of mixture of few another kind epoxy resin mixing；Curing agent 20-40PHR；0.01~1PHR of curing accelerator；Nothing
30~70PHR of machine filler；0.01~1PHR of silane coupling agent；Appropriate solvent.
As a preferred embodiment, the brominated epoxy resin is the brominated epoxy resin of low bromine, structural formula are as follows:
As a preferred embodiment, at least another epoxy resin is one or more epoxy resin below,
Structural formula is respectively as follows:
As a preferred embodiment, the curing agent is one of acid anhydrides, DDS, TBBA, BPA, BPS or a variety of.
As a preferred embodiment, the acid anhydrides is one of phenylethylene-maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride
Or it is a variety of.
As a preferred embodiment, the inorganic filler is aluminium hydroxide, boehmite, silica, talcum powder, aluminosilicate
One or more of salt.
As a preferred embodiment, the curing accelerator be imidazoles curing accelerator, include 2- methylimidazole,
One of 2-ethyl-4-methylimidazole, 2- phenylimidazole, 2- undecyl imidazole are a variety of.
As a preferred embodiment, the solvent is acetone, butanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, hexamethylene
One of ketone is a variety of.
The present invention has obvious advantages and beneficial effects compared with the existing technology, specifically, by above-mentioned technical proposal
Known to:
The present invention has adjusted system aluminium hydroxide, boehmite ratio, while meeting UL-94V0 grades of flame-retardancy requirements, collaboration
High CTI epoxy resin effect is with high creepage trace index, CTI >=600V.And choose high Tg curing agent substitution
The use of dicyandiamide also improves its glass transition temperature and has good machinery while with high heat resistance
Processing performance is applicable to pb-free solder.The present invention can be made into be made suitable for white domestic appliances, inverter, outdoor charging pile etc.
Copper-clad laminate.
Specific embodiment
Present invention discloses a kind of unleaded high CTI resin combinations for copper-clad plate, it is characterised in that: includes following master
Want ingredient: 60~80PHR of mixture that brominated epoxy resin is mixed at least another epoxy resin；Curing agent 20-40PHR；
0.01~1PHR of curing accelerator；30~70PHR of inorganic filler；0.01~1PHR of silane coupling agent；Appropriate solvent.
The brominated epoxy resin is the brominated epoxy resin of low bromine, structural formula are as follows:
At least another epoxy resin is one or more epoxy resin below, and structural formula is respectively as follows:
The curing agent is one of acid anhydrides, DDS, TBBA, BPA, BPS or a variety of.The acid anhydrides is styrene-Malaysia
One of acid anhydrides, tetrahydrophthalic anhydride, hexahydrophthalic anhydride are a variety of.The inorganic filler be aluminium hydroxide, boehmite, silica,
One or more of talcum powder, alumino-silicate.The curing accelerator is imidazoles curing accelerator, includes 2- methyl miaow
One of azoles, 2-ethyl-4-methylimidazole, 2- phenylimidazole, 2- undecyl imidazole are a variety of.The solvent be acetone,
One of butanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, cyclohexanone are a variety of.
The present invention is described in further details below by the mode of list:
Ingredient code name:
The formula (one) (parts by weight) of 1 composition of table
| Code name | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| A1 | 30 | 20 | 30 | 30 | 25 | |
| A2 | 18 | 30 | 23 | 45 | 10 | 10 |
| A3 | 27 | 43 | 27 | 40 | 30 | |
| B1 | 3 | |||||
| B2 | 9 | 10 | 12 | 10 | ||
| B3 | 9 | 7 | 9 | |||
| B4 | 11 | 11 | 16 | 20 | ||
| B5 | 25 | |||||
| B6 | 5 | 5 | ||||
| C1 | 20 | 20 | 20 | 20 | 20 | 20 |
| C2 | 20 | 20 | 30 | 20 | 20 | |
| C3 | 20 | |||||
| E | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| D | 0.5 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
| F | 85 | 85 | 85 | 85 | 85 | 85 |
Above-mentioned resin is mixed according to the ratio in Table 1, is then coated on reinforcing material E-Glass, in 171 DEG C of ovens
Baking 3-5min obtains prepreg, and respectively covering a 10Z copper foil up and down with 8 prepregs is folded structure, is put into laminating machine and presses
Conjunction obtains laminate, carries out characteristic evaluation with this laminate.
2 characteristic evaluation of table:
(1), water imbibition: for ratio of the weight difference relative to example weight before PCT before and after PCT boiling 3h.
(2), PCT is the boiling 3h in 121 DEG C of 105KPa pressure cookers, is immersed in 288 DEG C of tin furnaces, when record plate bursting is layered
Between.
(3), it thermally stratified layer time T-288: is measured according to IPC-TM-650 2.4.24.1 method.
(4), glass transition temperature (Tg): according to differential scanning calorimetry (DSC), according to IPC-TM-6502.4.25
The DSC method of defined is measured.
(5), it flammability: is measured according to 94 vertical combustion of UL.
In conclusion high CTI composition epoxy resin of the invention has high creepage trace index CTI >=600V,
There is high glass-transition temperature, high heat resistance and good machining using copper-clad laminate made of the composition
Performance, anti-flammability reach the characteristics such as UL94V-0 grades, are suitable for pb-free solder.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore any subtle modifications, equivalent variations and modifications to the above embodiments according to the technical essence of the invention, still
Belong in the range of technical solution of the present invention.
Claims (8)
1. a kind of unleaded high CTI resin combination for copper-clad plate, it is characterised in that: include following main component: brominated ring
60~80PHR of mixture that oxygen resin is mixed at least another epoxy resin；Curing agent 20-40PHR；Curing accelerator 0.01
~1PHR；30~70PHR of inorganic filler；0.01~1PHR of silane coupling agent；Appropriate solvent.
2. a kind of unleaded high CTI resin combination for copper-clad plate according to claim 1, it is characterised in that: described
Brominated epoxy resin is the brominated epoxy resin of low bromine, structural formula are as follows:
3. a kind of unleaded high CTI resin combination for copper-clad plate according to claim 1, it is characterised in that: described
At least another epoxy resin is one or more epoxy resin below, and structural formula is respectively as follows:
4. a kind of unleaded high CTI resin combination for copper-clad plate according to claim 1, it is characterised in that: described
Curing agent is one of acid anhydrides, DDS, TBBA, BPA, BPS or a variety of.
5. a kind of unleaded high CTI resin combination for copper-clad plate according to claim 4, it is characterised in that: described
Acid anhydrides is one of phenylethylene-maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or a variety of.
6. a kind of unleaded high CTI resin combination for copper-clad plate according to claim 1, it is characterised in that: described
Inorganic filler is one or more of aluminium hydroxide, boehmite, silica, talcum powder, alumino-silicate.
7. a kind of unleaded high CTI resin combination for copper-clad plate according to claim 1, it is characterised in that: described
Curing accelerator is imidazoles curing accelerator, includes 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, 2-
One of undecyl imidazole is a variety of.
8. a kind of unleaded high CTI resin combination for copper-clad plate according to claim 1, it is characterised in that: described
Solvent is one of acetone, butanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, cyclohexanone or a variety of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711482054.6A CN109337288A (en) | 2017-12-29 | 2017-12-29 | A kind of unleaded high CTI resin combination for copper-clad plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711482054.6A CN109337288A (en) | 2017-12-29 | 2017-12-29 | A kind of unleaded high CTI resin combination for copper-clad plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109337288A true CN109337288A (en) | 2019-02-15 |
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| CN201711482054.6A Pending CN109337288A (en) | 2017-12-29 | 2017-12-29 | A kind of unleaded high CTI resin combination for copper-clad plate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872430A (en) * | 2019-11-29 | 2020-03-10 | 陕西生益科技有限公司 | High CTI resin composition, prepreg, laminated board and metal foil-clad laminated board |
| CN111849124A (en) * | 2020-07-24 | 2020-10-30 | 重庆德凯实业股份有限公司 | Copper-clad plate and preparation method thereof |
| CN112175354A (en) * | 2020-10-21 | 2021-01-05 | 广德龙泰电子科技有限公司 | Heat-resistant epoxy resin composition, lead-free high-Tg copper-clad plate and preparation method thereof |
| CN112250997A (en) * | 2020-10-21 | 2021-01-22 | 广德龙泰电子科技有限公司 | Heat-resistant epoxy resin composition, lead-free middle-Tg copper-clad plate and preparation method thereof |
| CN112625632A (en) * | 2020-11-27 | 2021-04-09 | 江西省宏瑞兴科技股份有限公司 | Epoxy resin adhesive with high phase ratio electric leakage tracking index and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175994A (en) * | 2015-08-03 | 2015-12-23 | 广东生益科技股份有限公司 | Epoxy resin composition for copper-clad plate and application thereof |
| JP2016003335A (en) * | 2014-06-12 | 2016-01-12 | 廣東生益科技股▲ふん▼有限公司Ｓｈｅｎｇｙｉ Ｔｅｃｈｎｏｌｏｇｙｃｏ．，Ｌｔｄ． | Thermosetting epoxy resin composition, prepreg and laminate |
| CN105273362A (en) * | 2015-11-12 | 2016-01-27 | 广东生益科技股份有限公司 | Epoxy resin composition and application thereof |
-
2017
- 2017-12-29 CN CN201711482054.6A patent/CN109337288A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016003335A (en) * | 2014-06-12 | 2016-01-12 | 廣東生益科技股▲ふん▼有限公司Ｓｈｅｎｇｙｉ Ｔｅｃｈｎｏｌｏｇｙｃｏ．，Ｌｔｄ． | Thermosetting epoxy resin composition, prepreg and laminate |
| CN105175994A (en) * | 2015-08-03 | 2015-12-23 | 广东生益科技股份有限公司 | Epoxy resin composition for copper-clad plate and application thereof |
| CN105273362A (en) * | 2015-11-12 | 2016-01-27 | 广东生益科技股份有限公司 | Epoxy resin composition and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872430A (en) * | 2019-11-29 | 2020-03-10 | 陕西生益科技有限公司 | High CTI resin composition, prepreg, laminated board and metal foil-clad laminated board |
| CN111849124A (en) * | 2020-07-24 | 2020-10-30 | 重庆德凯实业股份有限公司 | Copper-clad plate and preparation method thereof |
| CN112175354A (en) * | 2020-10-21 | 2021-01-05 | 广德龙泰电子科技有限公司 | Heat-resistant epoxy resin composition, lead-free high-Tg copper-clad plate and preparation method thereof |
| CN112250997A (en) * | 2020-10-21 | 2021-01-22 | 广德龙泰电子科技有限公司 | Heat-resistant epoxy resin composition, lead-free middle-Tg copper-clad plate and preparation method thereof |
| CN112625632A (en) * | 2020-11-27 | 2021-04-09 | 江西省宏瑞兴科技股份有限公司 | Epoxy resin adhesive with high phase ratio electric leakage tracking index and preparation method thereof |
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