CN104497486A - Anti-yellowing modified halogen-free white resin composition, laminated board and preparation method of composition - Google Patents
Anti-yellowing modified halogen-free white resin composition, laminated board and preparation method of composition Download PDFInfo
- Publication number
- CN104497486A CN104497486A CN201410782137.7A CN201410782137A CN104497486A CN 104497486 A CN104497486 A CN 104497486A CN 201410782137 A CN201410782137 A CN 201410782137A CN 104497486 A CN104497486 A CN 104497486A
- Authority
- CN
- China
- Prior art keywords
- resin
- mass
- bisphenol
- resin combination
- yellowing
- 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.)
- Pending
Links
Abstract
The invention discloses an anti-yellowing modified halogen-free white resin composition, a laminated board and a preparation method of the composition. The composition comprises 30-70 parts by mass of alicyclic epoxy resin, 30-70 parts by mass of universal epoxy resin, 10-50 parts by mass of cyanate ester resin, 5-30 parts by mass of glycidyl methacrylate, a curing agent of which the mole ratio is 0.8 to 1.2 based on an epoxy group, titanium dioxide powder of which the mass is 20% to 80% of the total mass of the resin, a fluorescent brightener of which the mass is 0.1% to 1.0% of the total mass of the resin and an anti-yellowing agent of which the mass is 0.1% to 1.0% of the total mass of the resin. The resin composition can reach the non-halogenation requirements of European Union RoSH commands, is applied to electronic products, and is environment-friendly and free of pollution; a pre-impregnated material prepared from the resin composition and a metal foil coated laminated board manufactured by overlapping one or a plurality of pre-impregnated materials with metal foils are excellent in yellowing resistance at high temperature for a long time and are lower in reflectivity attenuation.
Description
Technical field
The invention belongs to and relate to a kind of yellowing resistance white halogen-free resin combination, veneer sheet and preparation method thereof.The prepreg be made up through impregnation of this white resin composition, pressed sheet under the high temperature conditions excellent, the color of yellowing resistance maintains good level, and it is high to visible reflectance, and carrying field at LED has good utilization prospect.
Background technology
LED is little as a kind of volume, heating efficiency is high, power consumption is little, the light source of long service life, is widely used in the fields such as display screen, illumination, radiating light source.In recent years, along with the trend development of LED miniaturization, slimming, on printed circuit board, the packaged type of direct mounting related components is rapidly developed.
Along with the technical development of LED high brightness, LED becomes high brightness more, and LED element thermal value also increases simultaneously, in the past for carrying the substrate of LED element due to high calorie radiation, cause substrate color aging yellowing, the reflectivity of light is declined to some extent, reduce LED usefulness.Therefore, market has very vigorous demand for the LED bearing substrate of high whiteness, high heat-resisting not easily xanthochromia.
But the encapsulation base material market of this type of high whiteness yellowing resistance is captured by external product substantially at present, industry as prosperous in profit, Mitsubishi's gas etc., domesticly to come out without this product at present.
The prosperous industry of profit provides a white metal-clad laminate (CN101218285B), uses
the multifunctional cycloaliphatic epoxy resin of structure and solidifying agent react; add titanium dioxide filler, auxiliary agent preparation; its sheet material is good by thermal ageing discoloration-resistant, reflectivity is high, but this kind of structural epoxy resins at present only Japanese Daicel have production, expensive and by patent protection.
In addition, a kind of white metal-clad laminate prepared by Mitsubishi's gas (CN101005948B) polyimide, this kind of sheet material anti-yellowing property can also reach requirement, but polyimide is when boning with tinsel, there is the problem of stripping strength deficiency, the problem that circuit peels off easily occurs in subsequent installation component technology.And polyimide resin is difficult to accomplish complete water white transparency, when preparing this kind of ultrawhite sheet material, sheet material whiteness is still poor, and the reflectivity of sheet material to LED light line is lower.
Mitsubishi's resin thermoplastic resin has prepared a kind of white film, and a kind of white metal veneer sheet, its material therefor is the resistant to elevated temperatures thermoplastic resin such as polymeric amide, polyether-ether-ketone (CN101873929B), this invented technology complicated operation, need use the equipment such as ball milling masterbatch is made in compound grinding after melting curtain coating again or layer prolong preparation white film, and thermoplastic resin prepares its shrinking percentage of material comparatively greatly, is not suitable for the demand of high-accuracy circuit.
Other compositions of thermosetting resin applied in LED glue as patent documentation CN101831143B, CN102676107A are applied to LED, general requirement is that light transmission is good, to require reflectivity to apply different from bearing substrate, simultaneously for component package, it is for the bonding stripping strength no requirement (NR) of tinsel.
Summary of the invention
In order to solve above-mentioned technical problem, an object of the present invention is to provide a kind of yellowing resistance halogen-free white resin combination, this resin combination can reach the non-halogen requirement of European Union RoSH command request, be applied to electronic product green non-pollution, the prepreg that manufactures of resin combination and superpose the metal-clad laminate that tinsel manufactures by individual or multiple prepregs thus, under its hot conditions, excellent, the reflectivity of long-time yellowing resistance is decayed less.
Two of object of the present invention is to provide a kind of metal-clad laminate and preparation method thereof, above-mentioned yellowing resistance halogen-free white resin combination is adopted to be prepared from, this metal-clad laminate, as LED element bearing substrate, has that yellowing resistance is good, substrate reflectivity is high, base material and an advantage such as tinsel stripping strength is high, cost is comparatively suitable.
To achieve the above object, present invention employs following technical scheme:
A kind of yellowing resistance halogen-free white resin combination, contains:
The cycloaliphatic epoxy resin of 30 ~ 70 mass parts;
The general purpose epoxy resin of 30 ~ 70 mass parts;
The cyanate ester resin of 10 ~ 50 mass parts;
The glycidyl methacrylate of 5 ~ 30 mass parts;
A kind of is the solidifying agent of 0.8 ~ 1.2 ratio in epoxide group mol ratio;
In the titanium dioxide of resin total mass 20 ~ 80% ratio;
In the white dyes of resin total mass 0.1 ~ 1.0% ratio;
In the anti-yellowing change agent of resin total mass 0.1 ~ 1.0% ratio.
(1) by the white resin composition of such scheme, cycloaliphatic epoxy resin contained by it can be alicyclic diglycidylether and modifier thereof, hexahydrophthalic acid 2-glycidyl ester, bisphenol-A epoxy resin, two (2, 3-epoxy group(ing) cyclopentyl) ether, 2, 3-epoxy group(ing) cyclopentyl cyclopentyl ether, vinyl cyclohexene diepoxide, diisoamyl diene diepoxide, hexanodioic acid two (3, 4-epoxy group(ing)-6-methylcyclohexyl methyl esters), Dicyclopentadiene (DCPD) diepoxide, 3, 4-epoxy group(ing)-6-methylcyclohexyl formic acid-3 ', 4 '-epoxy group(ing)-6 '-methylcyclohexyl methyl esters, 3, 4 expoxycyclohexyl formic acid-3 ', one or several in 4 '-expoxycyclohexyl methyl esters, preferably, the white prepreg of such scheme, cycloaliphatic epoxy resin contained by it is 3, 4 expoxycyclohexyl formic acid-3 ', 4 '-expoxycyclohexyl methyl esters, it accounts for 30 ~ 70% weight parts in composition resin component.
(2) by the white resin composition of such scheme, general purpose epoxy resin contained by it can be general bisphenol-type epoxy resin, General Linear novolac epoxy etc., preferably, the white prepreg of such scheme, universal resin contained by it is bisphenol A type epoxy resin, and its content shared by composition resin component is at 30 ~ 70% weight parts.
(3) by the white resin composition of such scheme, cyanate ester resin contained by it can be one or more in bisphenol A cyanate ester, dicyclopentadiene bisphenol type cyanate, tetramethyl-bisphenol-f type cyanate, bis-phenol M type cyanate, bisphenol-f type cyanate, bisphenol E-type cyanate and performed polymer thereof, preferably, the white prepreg of such scheme, cyanate ester resin contained by it is bisphenol-f type cyanate, and it accounts for 10 ~ 50% weight parts in composition resin component.
(4) by the white resin composition of such scheme, contained by it, glycidyl methacrylate polymkeric substance accounts for 5 ~ 30% weight parts in composition resin component.
(5) by the white resin composition of such scheme, its solidifying agent used can be one or several the mixture in phenolic, modified amine, Versamid, anhydrides, Dyhard RU 100, in order to the demand of sheet material color, Dyhard RU 100 and methylhexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride are preferably, and hardener dose and epoxide group equivalence ratio are preferably 0.8 ~ 1.2.
(6) by the white resin composition of such scheme, its curing catalyst used can be tertiary amines, imidazoles etc., and preferably, its consumption is total resin quality part 0.01 ~ 1.0%.
(7) by the white resin composition of such scheme, consider from sheet material color and reflectivity, preferably, its filler used is titanium dioxide, and its consumption is 20 ~ 80% of total weight resin.
(8) by the white resin composition of such scheme, its white dyes used can be benzoxazoles derivative, naphthalimide derivative, diphenylethylene compounds, coumarin derivatives, pyrazoline derivative class one or several, its consumption is 0.1 ~ 1.0% of total weight resin.
(9) by the white resin composition of such scheme, its anti-yellowing change agent used can be one or several in the anti-yellowing change agent such as Hinered phenols, phosphorous acid esters, sulfo-lipid, and its consumption is 0.1 ~ 1.0% of total weight resin.
(10) by the white resin composition of such scheme, for improving the bonding force of filler and resin, improve the dispersiveness of filler, a certain amount of coupling agent need be added, its coupling agent used can be one or several of the coupling agent such as silane coupling agent, phthalate, and its consumption is 0.1 ~ 1.0% of filler weight.
(11) by the white prepreg in invention, by obtaining thickness prepreg among 0.05 ~ 0.5mms as the electronic grade glass cloths such as 106,1080,2116,7628 flood above white resin composition on vertical gluing machine at 180 ~ 200 DEG C of baking 2 ~ 8min by different model, gained prepreg, at 171 DEG C, 200Psi pressure 10min, control its degree of mobilization between 5 ~ 30%, preferably, its degree of mobilization controls 10 ~ 15%.
(12) by white metal-clad laminate of the present invention, the folded tinsel of joining of the prepreg one or more in available above-mentioned (11) is laminated into type obtained through heating and pressurizing, and sheet metal thickness is preferably at 0.075 ~ 3.0mm.
(13) by above-mentioned (12) described tinsel can be the tinsel of the different thickness such as 12um, 18um, 1OZ, 2OZ.
(14) by above-mentioned (12) described heating and pressurizing compacting laminated plate material, its condition of cure be between pressed sheet material material temperature 70 ~ 120 DEG C temperature rise rate at 1.0 ~ 1.5 DEG C/min, preferably, prepreg degree of mobilization is 10 ~ 15% time, and its temperature rise rate controls at 1.2 DEG C/min.Pressed sheet ties up warm section holding plate material temperature more than 180 DEG C more than 40min, to ensure sheet material completion of cure.
(15) by above-mentioned (12) described heating and pressurizing compacting laminated plate material, its pressure process divides three sections, 1/3 total head pressure is applied before resin melting, resin melting section applies 2/3 total head pressure, sheet material after fixing section applies total head, compacting total head pressure is preferably 25 ~ 35kgf/ ㎡, and 2/3 pressure suppresses point control between 90 ~ 110 DEG C.
A preparation method for veneer sheet, comprises the steps:
1) a kind of yellowing resistance halogen-free white resin combination as above: solids fraction wherein is first used dissolution with solvents, then adds other non-solid components, then add filler, be configured to resin combination;
2) on adhesive applicator, described step 1 is flooded by electronic grade glass cloth) resin combination that obtains, obtain prepreg;
3) by described step 2) prepreg that obtains one or more is folded joins tinsel through heating and pressurizing obtained metal-clad laminate laminated into type.
A kind of veneer sheet, preparation method described in employing obtains.
A preparation method for veneer sheet, comprises the steps:
1) a kind of yellowing resistance halogen-free white resin combination as above: solids fraction wherein is first used dissolution with solvents, then adds other non-solid components, then add filler, be configured to the resin combination that solid content is 60 ~ 75%;
2) on adhesive applicator, described step 1 is flooded by electronic grade glass cloth) resin combination that obtains, the prepreg of thickness within the scope of 0.05 ~ 0.5mm is obtained at 180 ~ 200 DEG C of baking 2 ~ 8min, gained prepreg, at 171 DEG C, 200Psi pressure 10min, control its degree of mobilization between 5 ~ 30%;
3) by described step 2) prepreg that obtains one or more is folded joins tinsel through heating and pressurizing obtained metal-clad laminate laminated into type, and sheet metal thickness is at 0.075 ~ 3.0mm; Its condition of cure be between pressed sheet material material temperature 70 ~ 120 DEG C temperature rise rate at 1.0 ~ 1.5 DEG C/min; Its pressure process divides three sections, and apply 1/3 total head pressure before resin melting, resin melting section applies 2/3 total head pressure, and sheet material after fixing section applies total head, and compacting total head pressure is preferably 25 ~ 35kgf/ ㎡, and 2/3 pressure suppresses point control between 90 ~ 110 DEG C.
The present invention is owing to have employed above technical scheme, this resin combination can reach the non-halogen requirement of European Union RoSH command request, be applied to electronic product green non-pollution, the prepreg that manufactures of resin combination and superpose the metal-clad laminate that tinsel manufactures by individual or multiple prepregs thus, under its hot conditions, excellent, the reflectivity of long-time yellowing resistance is decayed less.This metal-clad laminate, as LED element bearing substrate, has that yellowing resistance is good, substrate reflectivity is high, base material and an advantage such as tinsel stripping strength is high, cost is comparatively suitable.
Embodiment
The following specific embodiments of the present invention is to make a detailed explanation.
Embodiment 1
By 30g bisphenol-f type cyanate ester monomer, 20g cycloaliphatic epoxy resin, the general bisphenol A type epoxy resin of 40g, 10g glycidyl methacrylate, 65g methylhexahydrophthalic anhydride adds in beaker, add 60g butanone and dissolve stirring, another beaker adds 0.06g undecyl imidazole, 0.5g white dyes, 0.5g anti-yellowing change agent 20g butanone adds in above-mentioned resin components after dissolving, stir and add 115g titanium dioxide after one hour, 0.5gKH560, high speed dispersor obtains white resin composition after disperseing 1 lab scale, 3 minutes obtained prepregs are toasted at 170 DEG C with after electronic grade glass cloth dipping, an electrolytic copper foil is superposed with 5 above-mentioned prepregs, a release film makes singlesided copperclad laminate, its curing process is as follows: 120 DEG C of solidification 40min, 160 DEG C of solidification 30min, 200 DEG C of solidification 90min, pressure presses 10kg 20min, 20kg 30min, 30kg110min.
Embodiment 2
By 25g bisphenol-f type cyanate ester monomer, 25g cycloaliphatic epoxy resin, the universal bisphenol A type epoxy resin of 40g, 10g glycidyl methacrylate adds in beaker, add 30g butanone and dissolve stirring, another beaker adds 2.28g Dyhard RU 100, 0.05g diethyl tetramethyl-imidazoles, 0.5g white dyes, 0.5g anti-yellowing change agent 30gDMF adds in above-mentioned resin components after dissolving, stir and add 80g titanium dioxide after one hour, 0.4gKH560, high speed dispersor obtains white resin composition after disperseing one hour, singlesided copperclad laminate is prepared by the method in above-described embodiment 1.
Embodiment 3
By 20g bisphenol-f type cyanate ester monomer, 40g bisphenol-A epoxy resin, the general bisphenol A type epoxy resin of 30g, 10g glycidyl methacrylate, 35g Tetra Hydro Phthalic Anhydride adds in beaker, add 50g butanone and dissolve stirring, another beaker adds 0.06g methylimidazole, 0.5g white dyes, 0.5g anti-yellowing change agent 20g butanone adds in above-mentioned resin components after dissolving, stir and add 88g titanium dioxide after one hour, 0.4gKH560, high speed dispersor obtains white resin composition after disperseing one hour, singlesided copperclad laminate is prepared by the method in above-described embodiment 1.
Embodiment 4
By 30g bisphenol-f type cyanate ester monomer, 30g cycloaliphatic epoxy resin, the general bisphenol A type epoxy resin of 30g, 10g glycidyl methacrylate, 33g methylhexahydrophthalic anhydride adds in beaker, add 60g butanone and dissolve stirring, another beaker adds 1.2g Dyhard RU 100, 0.06g undecyl imidazole, 0.5g white dyes, 0.5g anti-yellowing change agent 30gDMF adds in above-mentioned resin components after dissolving, stir and add 95g titanium dioxide after one hour, 0.5gKH560, high speed dispersor obtains white resin composition after disperseing 1 lab scale, singlesided copperclad laminate is prepared by the method in above-described embodiment 1.
Comparative example 1
2.4g Dyhard RU 100,0.06g methylimidazole are dissolved in 60g DMF, add the general bisphenol A type epoxy resin of 100g, stir and add 70g titanium dioxide, 0.35g KH560 after one hour, high speed dispersion, after one hour, prepares singlesided copperclad laminate by the method in above-described embodiment 1.
Comparative example 2
0.06g methylimidazole, 3.9g Dyhard RU 100 are dissolved in 60g N, in dinethylformamide, add 50g bisphenol A type epoxy resin, 50g bisphenol A-type novolac epoxy, stir and add 70g titanium dioxide, 0.35Gkh560 after one hour, high speed dispersion, after one hour, prepares singlesided copperclad laminate by the method in above-described embodiment 1.
Comparative example 3
Organic-silicon-modified for 100g cycloaliphatic epoxy resin, 78g methylhexahydrophthalic anhydride are dissolved in 50g butanone, 0.1g triphenylphosphine, 0.5g white dyes, 0.5g antioxidant are dissolved in 30g butanone by another beaker, mix two kinds of solution stirring and to add after 125g titanium dioxide, 0.7Gkh560 high speed dispersion after one hour one hour, prepare singlesided copperclad laminate according to the method in above-described embodiment 1.
Comparative example 4
The universal bisphenol A type epoxy resin of 50g Daicel cycloaliphatic epoxy resin EHPE3150,40g, 10g glycidyl methacrylate are dissolved in 50g butanone, 3g Dyhard RU 100,0.1gC11Z-CN (1-cyanoethyl-2-undecyl imidazole), 0.3g white dyes are dissolved in 30g DMF by another beaker, stir one hour after mixing two kinds of solution mixing, add 73g titanium dioxide high speed dispersion after one hour, prepare singlesided copperclad laminate by the method in above-described embodiment 1.
Comparative example 5
Comparative example 5 directly adopts Mitsubishi gas HL820 product to compare, and this product adopts polyimide preparation.
By above embodiment and its Tg of comparative example evaluation test, peel strength of copper foil, reflectivity, whiteness and 180 DEG C of bakings 4 reflectivity, whiteness performance as a child, evaluation result sees the following form:
As seen from the above table, the white laminated plate that white resin composition of the present invention is made, it is strong to visible reflectance, under high temperature, radiation condition, the decay of its reflectivity is little, colour-change is little, Copper Foil and base material bonding force good, with the prosperous industry of profit, Mitsubishi's gas product, there is close performance and there is good cost advantage (prepreg cost reduces about 30 ~ 50%), have great benefit to the luminescence of installation LED element, in LED element carrying, expection has good application.
It is emphasized that: be only preferred embodiment of the present invention above, not any pro forma restriction is done to the present invention, every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (10)
1. a yellowing resistance halogen-free white resin combination, is characterized in that, contains:
The cycloaliphatic epoxy resin of 30 ~ 70 mass parts;
The general purpose epoxy resin of 30 ~ 70 mass parts;
The cyanate ester resin of 10 ~ 50 mass parts;
The glycidyl methacrylate of 5 ~ 30 mass parts;
A kind of is the solidifying agent of 0.8 ~ 1.2 ratio in epoxide group mol ratio;
In the titanium dioxide of resin total mass 20 ~ 80% ratio;
In the white dyes of resin total mass 0.1 ~ 1.0% ratio;
In the anti-yellowing change agent of resin total mass 0.1 ~ 1.0% ratio.
2. a kind of yellowing resistance halogen-free white resin combination according to claim 1, is characterized in that, this yellowing resistance halogen-free white resin combination is also added with: in the curing catalyst of resin total mass 0.01 ~ 1.0% ratio; And, in the coupling agent of packing quality 0.1 ~ 1.0% ratio.
3. a kind of yellowing resistance halogen-free white resin combination according to claim 1, it is characterized in that, described cycloaliphatic epoxy resin can be alicyclic diglycidylether and modifier thereof, hexahydrophthalic acid 2-glycidyl ester, bisphenol-A epoxy resin, two (2, 3-epoxy group(ing) cyclopentyl) ether, 2, 3-epoxy group(ing) cyclopentyl cyclopentyl ether, vinyl cyclohexene diepoxide, diisoamyl diene diepoxide, hexanodioic acid two (3, 4-epoxy group(ing)-6-methylcyclohexyl methyl esters), Dicyclopentadiene (DCPD) diepoxide, 3, 4-epoxy group(ing)-6-methylcyclohexyl formic acid-3 ', 4 '-epoxy group(ing)-6 '-methylcyclohexyl methyl esters, 3, 4 expoxycyclohexyl formic acid-3 ', one or several in 4 '-expoxycyclohexyl methyl esters, preferably, described cycloaliphatic epoxy resin be 3,4 expoxycyclohexyl formic acid-3 ', 4 '-expoxycyclohexyl methyl esters.
4. a kind of yellowing resistance halogen-free white resin combination according to claim 1, it is characterized in that, described general purpose epoxy resin can be general bisphenol-type epoxy resin, General Linear novolac epoxy etc.; Preferably, described universal resin is bisphenol A type epoxy resin.
5. a kind of yellowing resistance halogen-free white resin combination according to claim 1, it is characterized in that, described cyanate ester resin can be one or more in bisphenol A cyanate ester, dicyclopentadiene bisphenol type cyanate, tetramethyl-bisphenol-f type cyanate, bis-phenol M type cyanate, bisphenol-f type cyanate, bisphenol E-type cyanate and performed polymer thereof; Preferably, described cyanate ester resin is bisphenol-f type cyanate.
6. a kind of yellowing resistance halogen-free white resin combination according to claim 1, is characterized in that, described solidifying agent can be one or several the mixture in phenolic, modified amine, Versamid, anhydrides, Dyhard RU 100; Preferably, described solidifying agent is one or several the mixture in Dyhard RU 100, methylhexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride.
7. a kind of yellowing resistance halogen-free white resin combination according to claim 1, it is characterized in that, described white dyes can be benzoxazoles derivative, naphthalimide derivative, diphenylethylene compounds, coumarin derivatives, pyrazoline derivative class one or several; Described anti-yellowing change agent can be one or several in the anti-yellowing change agent such as Hinered phenols, phosphorous acid esters, sulfo-lipid.
8. a preparation method for veneer sheet, is characterized in that, comprises the steps:
1) a kind of yellowing resistance halogen-free white resin combination according to any one of claim 1 to 7: solids fraction wherein is first used dissolution with solvents, then adds other non-solid components, then add filler, be configured to resin combination;
2) on adhesive applicator, described step 1 is flooded by electronic grade glass cloth) resin combination that obtains, obtain prepreg;
3) by described step 2) prepreg that obtains one or more is folded joins tinsel through heating and pressurizing obtained metal-clad laminate laminated into type.
9. a veneer sheet, adopts preparation method according to claim 8 to obtain.
10. a preparation method for veneer sheet, is characterized in that, comprises the steps:
1) a kind of yellowing resistance halogen-free white resin combination according to any one of claim 1 to 7: solids fraction wherein is first used dissolution with solvents, add other non-solid components again, then add filler, be configured to the resin combination that solid content is 60 ~ 75%;
2) on adhesive applicator, described step 1 is flooded by electronic grade glass cloth) resin combination that obtains, the prepreg of thickness within the scope of 0.05 ~ 0.5mm is obtained at 180 ~ 200 DEG C of baking 2 ~ 8min, gained prepreg, at 171 DEG C, 200Psi pressure 10min, control its degree of mobilization between 5 ~ 30%;
3) by described step 2) prepreg that obtains one or more is folded joins tinsel through heating and pressurizing obtained metal-clad laminate laminated into type, and sheet metal thickness is at 0.075 ~ 3.0mm; Its condition of cure be between pressed sheet material material temperature 70 ~ 120 DEG C temperature rise rate at 1.0 ~ 1.5 DEG C/min; Its pressure process divides three sections, and apply 1/3 total head pressure before resin melting, resin melting section applies 2/3 total head pressure, and sheet material after fixing section applies total head, and compacting total head pressure is preferably 25 ~ 35kgf/ ㎡, and 2/3 pressure suppresses point control between 90 ~ 110 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410782137.7A CN104497486A (en) | 2014-12-16 | 2014-12-16 | Anti-yellowing modified halogen-free white resin composition, laminated board and preparation method of composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410782137.7A CN104497486A (en) | 2014-12-16 | 2014-12-16 | Anti-yellowing modified halogen-free white resin composition, laminated board and preparation method of composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104497486A true CN104497486A (en) | 2015-04-08 |
Family
ID=52938949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410782137.7A Pending CN104497486A (en) | 2014-12-16 | 2014-12-16 | Anti-yellowing modified halogen-free white resin composition, laminated board and preparation method of composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104497486A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273347A (en) * | 2015-11-11 | 2016-01-27 | 吴江市莘塔前进五金厂 | Electronic heat-resisting composite material |
| CN105461902A (en) * | 2015-11-11 | 2016-04-06 | 吴江市莘塔前进五金厂 | Ultrathin film material for electronic product and preparation method thereof |
| CN107214808A (en) * | 2017-06-15 | 2017-09-29 | 浙江润格木业科技有限公司 | Composite wood and its manufacture method |
| CN107406681A (en) * | 2015-03-31 | 2017-11-28 | 太阳油墨制造株式会社 | Hardening resin composition, dry film, solidfied material and printed circuit board (PCB) |
| CN108276557A (en) * | 2018-01-10 | 2018-07-13 | 苏州益可泰电子材料有限公司 | Heat resistant resin material and preparation method thereof |
| CN111907158A (en) * | 2020-08-26 | 2020-11-10 | 三鑫笑为电子材料(苏州)有限公司 | White epoxy glass fiber cloth laminated board with two-dimensional code laser-printed and press-fitting process |
| CN111923562A (en) * | 2020-08-10 | 2020-11-13 | 三鑫笑为电子材料(苏州)有限公司 | Laminating process of white epoxy glass fiber cloth laminated board |
| CN114231229A (en) * | 2021-12-14 | 2022-03-25 | 南亚新材料科技(江西)有限公司 | Halogen-free high-Tg yellowing-resistant copper-clad plate adhesive applicable to LED packaging field and preparation method and application thereof |
| CN114736487A (en) * | 2022-03-21 | 2022-07-12 | 深圳市鑫裕达塑胶模具有限公司 | Spraying-free material with metal texture and preparation method thereof |
| CN116082793A (en) * | 2022-12-28 | 2023-05-09 | 东莞联茂电子科技有限公司 | Epoxy resin composition for yellowing-resistant white copper-clad plate, prepreg and substrate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457013A (en) * | 2009-01-14 | 2009-06-17 | 长沙蓝星化工新材料有限公司 | Light scattering type epoxy resin composition and preparation method thereof |
| CN101555313A (en) * | 2009-04-30 | 2009-10-14 | 苏州大学 | Ethylene rhodanate/epoxide resin microballoon and preparation method thereof |
| WO2013008667A1 (en) * | 2011-07-11 | 2013-01-17 | 三菱瓦斯化学株式会社 | Curable resin composition and process for producing cured products using same |
| CN102985458A (en) * | 2010-10-06 | 2013-03-20 | 株式会社大赛璐 | Method for producing cured product and cured product |
| CN103265810A (en) * | 2013-05-29 | 2013-08-28 | 苏州生益科技有限公司 | Resin composition for high-frequency high-speed substrate as well as prepreg and laminated board made of resin composition |
| CN103492482A (en) * | 2011-06-27 | 2014-01-01 | 株式会社大赛璐 | Curable resin composition for reflection of light, and optical semiconductor device |
| CN103635532A (en) * | 2011-07-14 | 2014-03-12 | 积水化学工业株式会社 | White curable composition for optical semiconductor device, molded object for optical semiconductor device, and optical semiconductor device |
-
2014
- 2014-12-16 CN CN201410782137.7A patent/CN104497486A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457013A (en) * | 2009-01-14 | 2009-06-17 | 长沙蓝星化工新材料有限公司 | Light scattering type epoxy resin composition and preparation method thereof |
| CN101555313A (en) * | 2009-04-30 | 2009-10-14 | 苏州大学 | Ethylene rhodanate/epoxide resin microballoon and preparation method thereof |
| CN102985458A (en) * | 2010-10-06 | 2013-03-20 | 株式会社大赛璐 | Method for producing cured product and cured product |
| CN103492482A (en) * | 2011-06-27 | 2014-01-01 | 株式会社大赛璐 | Curable resin composition for reflection of light, and optical semiconductor device |
| WO2013008667A1 (en) * | 2011-07-11 | 2013-01-17 | 三菱瓦斯化学株式会社 | Curable resin composition and process for producing cured products using same |
| CN103635532A (en) * | 2011-07-14 | 2014-03-12 | 积水化学工业株式会社 | White curable composition for optical semiconductor device, molded object for optical semiconductor device, and optical semiconductor device |
| CN103265810A (en) * | 2013-05-29 | 2013-08-28 | 苏州生益科技有限公司 | Resin composition for high-frequency high-speed substrate as well as prepreg and laminated board made of resin composition |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107406681B (en) * | 2015-03-31 | 2020-02-07 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, and printed wiring board |
| CN107406681A (en) * | 2015-03-31 | 2017-11-28 | 太阳油墨制造株式会社 | Hardening resin composition, dry film, solidfied material and printed circuit board (PCB) |
| CN105273347A (en) * | 2015-11-11 | 2016-01-27 | 吴江市莘塔前进五金厂 | Electronic heat-resisting composite material |
| CN105461902A (en) * | 2015-11-11 | 2016-04-06 | 吴江市莘塔前进五金厂 | Ultrathin film material for electronic product and preparation method thereof |
| CN105461902B (en) * | 2015-11-11 | 2017-06-30 | 吴江市莘塔前进五金厂 | A kind of use for electronic products thin-film material and preparation method thereof |
| CN107214808B (en) * | 2017-06-15 | 2019-06-07 | 浙江润格木业科技有限公司 | Composite wood and its manufacturing method |
| CN107214808A (en) * | 2017-06-15 | 2017-09-29 | 浙江润格木业科技有限公司 | Composite wood and its manufacture method |
| CN108276557A (en) * | 2018-01-10 | 2018-07-13 | 苏州益可泰电子材料有限公司 | Heat resistant resin material and preparation method thereof |
| CN111923562A (en) * | 2020-08-10 | 2020-11-13 | 三鑫笑为电子材料(苏州)有限公司 | Laminating process of white epoxy glass fiber cloth laminated board |
| CN111907158A (en) * | 2020-08-26 | 2020-11-10 | 三鑫笑为电子材料(苏州)有限公司 | White epoxy glass fiber cloth laminated board with two-dimensional code laser-printed and press-fitting process |
| CN114231229A (en) * | 2021-12-14 | 2022-03-25 | 南亚新材料科技(江西)有限公司 | Halogen-free high-Tg yellowing-resistant copper-clad plate adhesive applicable to LED packaging field and preparation method and application thereof |
| CN114231229B (en) * | 2021-12-14 | 2023-08-04 | 南亚新材料科技(江西)有限公司 | Halogen-free high-Tg yellowing-resistant adhesive for copper-clad plate in field of LED packaging, and preparation method and application thereof |
| CN114736487A (en) * | 2022-03-21 | 2022-07-12 | 深圳市鑫裕达塑胶模具有限公司 | Spraying-free material with metal texture and preparation method thereof |
| CN116082793A (en) * | 2022-12-28 | 2023-05-09 | 东莞联茂电子科技有限公司 | Epoxy resin composition for yellowing-resistant white copper-clad plate, prepreg and substrate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104497486A (en) | Anti-yellowing modified halogen-free white resin composition, laminated board and preparation method of composition | |
| CN101684191B (en) | Halogen-less high frequency resin composition, and prepreg and laminate manufacturing by using same | |
| CN102504532B (en) | Halogen-free low dielectric resin composition and prepreg and copper clad laminate made of same | |
| CN100519179C (en) | Preparation method of glass transition temperature halogenless fire retardant glass cloth laminated board | |
| CN106147132B (en) | Resin combination and the glue containing it, prepreg and copper-clad plate and preparation method | |
| CN103897346B (en) | A kind of compositions of thermosetting resin | |
| JP5072822B2 (en) | Biomass-derived epoxy compound and method for producing the same | |
| CN101747854A (en) | Adhesive combination, covering film and flexible circuit board | |
| JP2016094603A (en) | Low dielectric phosphorus-containing polyester compound and preparation method therefor | |
| CN102344772A (en) | High thermal conducting insulating epoxy resin adhesive and its application in flexible aluminum based copper-clad plate for LED | |
| CN109135193A (en) | Compositions of thermosetting resin, prepreg, laminate and printed circuit board | |
| CN109795188A (en) | A kind of copper-clad plate and preparation method thereof with good heat resistance | |
| CN114231229B (en) | Halogen-free high-Tg yellowing-resistant adhesive for copper-clad plate in field of LED packaging, and preparation method and application thereof | |
| KR102316144B1 (en) | Epoxy resin composition, resin sheet, and prepreg, and metal-clad laminate board, printed circuit board, and semiconductor device | |
| JP2009263549A (en) | Epoxy resin composition of vegetable origin, and various instruments using the same | |
| CN104804687B (en) | Conductive die bond bonding glue, conductive die bond Gumming glue film, preparation method and application | |
| CN103540103A (en) | Epoxy resin composition and method for preparing adhesive by using same | |
| CN110328914A (en) | A kind of copper-clad plate and preparation method thereof suitable for PCB processing procedure with good flame-retardance | |
| CN103435812A (en) | Benzoxazine intermediate product and preparation method thereof | |
| CN105482753A (en) | High-CTI resin composition and application thereof | |
| CN105199619B (en) | Aluminum-based copper-clad plate high-heat-conductivity glue membrane preparation method | |
| CN104002524A (en) | Making method for high thermal conductive, high heat resistant and high CTI FR-4 copper-clad plate | |
| CN113462128B (en) | Resin composition, functional membrane and application thereof | |
| JP2009292884A (en) | Lignophenol-based epoxy resin composition | |
| JP6430787B2 (en) | Optical semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150408 |