CN102964777A - Phosphorus-containing and halogen-free flame retardant resin adhesive as well as preparation method and application thereof - Google Patents
Phosphorus-containing and halogen-free flame retardant resin adhesive as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a phosphorus-containing and halogen-free flame retardant resin adhesive as well as a preparation method and an application thereof. The phosphorus-containing and halogen-free flame retardant resin adhesive is composed of a solid matter and an organic solvent, wherein the content of the solid matter is 50-90wt%, the balance is the organic solvent, and the solid matter is composed of the following components in percentage by weight: 5-50% of phosphorus-containing epoxy resin, 10-60% of epoxy resin modified by isocyanic acid, 1-35% of phosphorus-containing curing agent, 1-30% of phenolic resin, 10-60% of inorganic filler and 0.002-0.015% of epoxy resin curing promoter. The phosphorus-containing and halogen-free flame retardant resin adhesive provided by the invention has the advantages of good heat resistance and flame retardancy and good toughness and peeling strength.
Description
Technical field
The present invention relates to the tackiness agent preparing technical field, relate in particular a kind of flame retardant resin tackiness agent of phosphor-containing halogen-free element, Preparation Method And The Use.
Background technology
To the concern of Global Environmental Problems, just further strict about the regulations of the formation of toxic substance in electronic and electronic product are processed along with recently.The conventional resin combination that is generally used for prepreg and veneer sheet uses the dual functional Resins, epoxy of bromination and polyfunctional Resins, epoxy as main ingredient, use amino curing agent and curing catalyst, wherein Resins, epoxy contains the bromine of 15～20wt%, to meet the flame-retardant standard of UL (Underwriters Laboratory Underwriters Laboratory).
Brominated halogenide has good flame retardant resistance, but produces malicious chlorine in its combustion processes.Because halogen-containing material can produce carcinogenic dioxin, its application is controlled extremely sternly.For this reason, industry requires to use the fire retardant type of non-halogen fire-retardant, namely require to use halogen-free flame-retardant printed electronic circuit base material, and detecting, PCB processing and application, appliance fire, waste treatment (comprises recovery, bury, burn) etc. in the process, such material can not produce the material harmful to human and environment, halogen-free flame-retardant printed electronic circuit base material comprises copper-clad laminate, prepreg, resin coated copper foils etc., halogen-free flame-retardant copper-clad laminate also claim " green type copper-clad laminate " (Green CCL), " environmentally friendly copper-clad laminate ", " environment-friendly type copper-clad laminate ".At present, industry has been developed the non-halogen fire retardant that is mixed in ordinary epoxy resin, such as the composition of nitrogenous compound, P contained compound, inorganics etc.But still have following point in these flame retardant resin compositions: epoxy cure is had detrimentally affect, reduced the thermotolerance of hardening composition or made the shortcomings such as hardening composition fragility is large, stripping strength is low.
Summary of the invention
The object of the invention is to overcome the shortcoming of the fire retardant tackiness agent that has halogen now, a kind of flame retardant resin tackiness agent of phosphor-containing halogen-free element is provided, this tackiness agent has good heat resistance and flame retardant resistance, and good toughness and the stripping strength of tool.
For realizing purpose of the present invention, technical scheme of the present invention is:
A kind of flame retardant resin tackiness agent of phosphor-containing halogen-free element, this tackiness agent is comprised of solid substance and organic solvent,
Wherein, the weight percentage of solid substance is 50-90%, and organic solvent is surplus,
Solid substance is comprised of the component of following weight percentage:
Phosphorous Resins, epoxy 5%-50%,
The Resins, epoxy 10%-60% of isocyanic acid modification,
Phosphorus curing agent 1%-35%,
Resol 1%-30%,
Mineral filler 10%-60%,
Epoxy resin cure promotor 0.002-0.015%.
In a preferred embodiment of the present invention, the weight percentage of solid substance is 55-75%, and organic solvent is surplus.
In a preferred embodiment of the present invention, described phosphorous Resins, epoxy physical property requires as shown in the table 1:
Table 1
This phosphorous Resins, epoxy mainly provides the fire-retardant required phosphorus of material without element, and its chemical structure is as shown in the formula (1):
Wherein, n=1 ~ 3.
The structure of DOPO as shown in the formula:
In a preferred embodiment of the present invention, described phosphorous Resins, epoxy is preferably the PE-315 phosphorous epoxy resin of Shanxi, Taiwan one Chemical Manufacture, but is not limited only to this.
In a preferred embodiment of the present invention, described isocyanate-modified Resins, epoxy physical property requires as shown in the table 2:
Table 2
The mixture of one or both in the Resins, epoxy that this isocyanate-modified Resins, epoxy is the modification of aromatic series diphenylmethanediisocyanate, the Resins, epoxy of tolylene diisocyanate modification, it gives the needed basic machinery of tackiness agent of the present invention and thermal characteristics, and has good toughness and good copper-stripping intensity.
In a preferred embodiment of the present invention, the XZ-97103 Resins, epoxy that described isocyanate-modified Resins, epoxy is preferably produced with DOW Chemical, but be not limited only to this.
In a preferred embodiment of the present invention, described phosphorous solidifying agent is the bisphenol A-type phosphorus containing phenolic resin, and its physical property requires as shown in the table 3:
Table 3
This phosphorus curing agent is the bisphenol A-type phosphorus containing phenolic resin, and it is to be made by P contained compound and bisphenol A type epoxy resin reaction, can select the resin of DOW Chemical production, trade mark XZ-92741, but be not limited only to this.
In a preferred embodiment of the present invention, described resol is the resol of phenol and formaldehyde crosslinking, and described phenol is one or more the mixture in phenol, xylenol, ethylphenol, n-propyl phenol, isopropyl-phenol, normal-butyl phenol, isobutyl-phenol, tert.-butyl phenol or the dihydroxyphenyl propane.As the preferred described resol phenol resol that is phenol and formaldehyde crosslinking, or the bisphenol A phenolic resin of dihydroxyphenyl propane and formaldehyde crosslinking, or the mixture of phenol resol and bisphenol A phenolic resin.
Above resol can select Korea S can swell the KPH-L2003 resin of chemical production, but is not limited only to this.
In a preferred embodiment of the present invention, described mineral filler is one or more the mixture in talcum, silica powder, ceramics powder, aluminium hydroxide, silicon-dioxide, clay or the boron nitride, is preferably one or both the mixture in silicon-dioxide or the aluminium hydroxide.Mineral filler can improve chemical property and the electrical property of cured resin, as reducing thermal expansivity (CTE), increases modulus, accelerates the heat transmission and assists fire-retardant etc.
In a preferred embodiment of the present invention, described epoxy resin cure promotor is imidazolium compounds, is preferably the mixture of 2-ethyl 4-methylimidazole or 1 benzyl 2 methyl imidazole or 2-ethyl 4-methylimidazole and 1 benzyl 2 methyl imidazole.
In a preferred embodiment of the present invention, described organic solvent is one or more the mixture in acetone, methyl ethyl ketone, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether or the pimelinketone.
Another object of the present invention provides a kind of preparation method of flame retardant resin tackiness agent of phosphor-containing halogen-free element, it is characterized in that the method may further comprise the steps:
(1) press formula ratio and in steel basin, add the part organic solvent, turn on agitator, 500 ~ 1500 rev/mins of rotating speeds, the control flume temperature adds mineral filler again at 20 ~ 50 ℃ to keep continuing to stir also, adds complete rear lasting stirring 10 ~ 50 minutes;
(2) in steel basin, add successively phosphorous Resins, epoxy, the Resins, epoxy of isocyanic acid modification, phosphorus curing agent, resol by formula ratio, keep stirring with 1000 ~ 1500 rev/mins of rotating speeds in the reinforced process, add that complete rear unlatching is efficient shears and emulsification 0.5 ~ 4 hour, carry out simultaneously cooling water circulation with retentive control cell body temperature at 20 ~ 50 ℃;
(3) take by weighing epoxy resin cure promotor by formula ratio, it is joined in the remaining organic solvent, after the dissolving, this solution is added in the steel basin fully, and continue to keep 1000 ~ 1500 rev/mins of stirrings 3 ~ 15 hours, namely make tackiness agent.
A further object of the present invention provides the purposes of flame retardant resin tackiness agent in preparation copper-clad plate (copper-clad laminate) of phosphor-containing halogen-free element.
Copper-clad laminate with the preparation of the flame retardant resin tackiness agent of phosphor-containing halogen-free element of the present invention has 〉=150 ℃ second-order transition temperature, good heat resistance and flame retardant resistance, and the toughness that tool is good and stripping strength, can make the good halogen-free environmental printed-wiring board (PWB) of various characteristics, be applicable to the demand that PCB leadless process and multi-ply wood are produced fully.
Embodiment
Further specify the present invention below by embodiment and Comparative Examples.
The characteristic of the copper-clad laminate of embodiment 1-4 and comparative example 1-2 is measured by following methods (with reference to IPC-TM-650).
(1) second-order transition temperature (Tg)
Second-order transition temperature refer to sheet material in the situation of being heated by glassy transition be the corresponding temperature of elastomeric state (rubbery state) (℃).
Detection method: adopt differential scanning calorimetry (DSC).
(2) the thermally stratified layer time (T-288)
The T-288 thermally stratified layer time refers to sheet material under 288 ℃ design temperature, because duration before this demixing phenomenon appears, in the effect of heat.
Detection method: adopt thermo-mechanical analysis method (TMA).
(3) scolding tin thermotolerance
The scolding tin thermotolerance refers in the melting scolding tin of 288 ℃ of sheet material immersions, without layering occurring and bubbling duration.
Detection method: the substrate after the etching is cut into 5.0cm * 5.0cm size, and edges of boards are used 120 orders and 800 order sand paperings successively, pressure-cook certain hour, put into 288 ℃ of tin melting furnaces, observe phenomenons such as having or not layering.
(4) stripping strength
Test according to the IPC-TM-650-2.4.8C method.
(5) flame retardant resistance
Surperficial Copper Foil is removed in etching, carries out preparation of samples and test according to the flammability test of UL94 veneer sheet.
Describe the present invention in detail below in conjunction with specific embodiment, unless following examples have special explanation, the phosphorous Resins, epoxy of mentioning is the PE-315 phosphorous epoxy resin of Shanxi, Taiwan and Hongkong one Chemical Manufacture, the Resins, epoxy of isocyanic acid modification is the XZ-97103 Resins, epoxy that DOW Chemical is produced, phosphorus curing agent is the trade mark XZ-92741 resin that DOW Chemical is produced, and resol is that the KPH-L2003 resin of chemical production can be swelled in Korea S.Glasscloth can be selected the E level, and specification can be selected from 101,104,106,1078,1080,1086,2113,2313,2116,1506 or 7628.Used Copper Foil can be selected 1/3oz, Hoz, 1oz, 2oz, 3oz, 4oz or 5oz.Bisphenol A epoxide resin is the BNE200 resin of Changchun, Taiwan chemical industry.
Embodiment 1
1. the quality percentage composition of the solid substance in the tackiness agent is 65.2%, and all the other are organic solvent (for example propylene glycol monomethyl ether),
Wherein, the prescription of solid substance sees Table 4(by weight)
Table 4
2. the preparation method of tackiness agent:
(1) in steel basin, add organic solvent propylene glycol monomethyl ether 106 grams by above weight, turn on agitator, 600 rev/mins of rotating speeds add aluminium hydroxide and silicon-dioxide again, add complete rear lasting stirring 20 minutes;
(2) in steel basin, add successively phosphorous Resins, epoxy, the Resins, epoxy of isocyanic acid modification, phosphorus curing agent, resol by formula ratio, keep stirring with 1000 rev/mins of rotating speeds in the reinforced process;
(3) take by weighing 2E4MZ by formula ratio, after it is dissolved fully with the ratio of weight ratio 1:10 and organic solvent propylene glycol monomethyl ether, this solution is added in steel basin, and continue to keep 1200 rev/mins and stirred 2 hours, make resin glue.
3. preparation copper-clad laminate
The resin glue continuously coating or the impregnated glass fiber cloth that make in order to the top method, drying obtains prepreg under 170 ℃ of baking conditions, 8 prepregs are superimposed, its upper and lower high temperature extension Copper Foil of respectively placing 1 35um, heating under 195 ℃, the pressure of 25Kg/cm2, pressurization 140 minutes obtain the copper-clad laminate of 1.6mm.
4. it is as shown in table 5 that present embodiment prepares the performance perameter of copper-clad laminate of gained:
Table 5
Embodiment 2:
1. preparation tackiness agent
The quality percentage composition of the solid substance in the adhesive therefor is 66%, and all the other are organic solvent (such as propylene glycol monomethyl ether), and wherein, the prescription of solid substance sees Table 6(by weight)
Table 6
| Raw material | Solid weight (gram) |
| Phosphorous Resins, epoxy | 45 |
| The Resins, epoxy of isocyanic acid modification | 55 |
| Phosphorus curing agent | 18 |
| Resol | 10 |
| Aluminium hydroxide | 39 |
| Silicon-dioxide | 24 |
| 2E4MZ | 0.03 |
2. the preparation method of tackiness agent:
(1) in steel basin, add organic solvent propylene glycol monomethyl ether 98 grams by above weight, turn on agitator, 600 rev/mins of rotating speeds add aluminium hydroxide and silicon-dioxide again, add complete rear lasting stirring 20 minutes;
(2) in steel basin, add successively phosphorous Resins, epoxy, the Resins, epoxy of isocyanic acid modification, phosphorus curing agent, resol by formula ratio, keep stirring with 1000 rev/mins of rotating speeds in the reinforced process;
(3) take by weighing 2E4MZ by formula ratio, after it is dissolved fully with the ratio of weight ratio 1:10 and organic solvent propylene glycol monomethyl ether, this solution is added in steel basin, and continue to keep 1200 rev/mins and stirred 2 hours, make resin glue.
3. preparation copper-clad laminate
The resin glue continuously coating or the impregnated glass fiber cloth that make in order to the top method, drying obtains prepreg under 170 ℃ of baking conditions, 8 prepregs are superimposed, its upper and lower high temperature extension Copper Foil of respectively placing 1 35um, heating under 195 ℃, the pressure of 25Kg/cm2, pressurization 140 minutes obtain the copper-clad laminate of 1.6mm.
4. it is as shown in table 7 that present embodiment prepares the performance perameter of copper-clad laminate of gained:
Table 7
| Project | Test result |
| Second-order transition temperature (DSC), ℃ | 159 |
| Peel strength of copper foil (1oz), lb/in | 9.7 |
| T288(TMA),min | >60 |
| Scolding tin thermotolerance (PCT/3h, 288 ℃ of wickings) | >10min |
| Flame retardant resistance (UL-94, rating) | V-0 |
Embodiment 3:
1. preparation tackiness agent
(1) the quality percentage composition of the solid substance in the adhesive therefor is 66%, and all the other are organic solvent (such as propylene glycol monomethyl ether), and wherein, the prescription of solid substance sees Table 8(by weight)
Table 8
| Raw material | Solid weight (gram) |
| Phosphorous Resins, epoxy | 30 |
| The Resins, epoxy of isocyanic acid modification | 70 |
| Phosphorus curing agent | 18 |
| Resol | 12 |
| Aluminium hydroxide | 53 |
| Silicon-dioxide | 10 |
| 2E4MZ | 0.03 |
2. the preparation method of tackiness agent:
(1) in steel basin, add organic solvent propylene glycol monomethyl ether 99 grams by above weight, turn on agitator, 600 rev/mins of rotating speeds add aluminium hydroxide and silicon-dioxide again, add complete rear lasting stirring 20 minutes;
(2) in steel basin, add successively phosphorous Resins, epoxy, the Resins, epoxy of isocyanic acid modification, phosphorus curing agent, resol by formula ratio, keep stirring with 1000 rev/mins of rotating speeds in the reinforced process;
(3) take by weighing 2E4MZ by formula ratio, after it is dissolved fully with the ratio of weight ratio 1:10 and organic solvent propylene glycol monomethyl ether, this solution is added in steel basin, and continue to keep 1200 rev/mins and stirred 2 hours, make resin glue.
3. preparation copper-clad laminate
The resin glue continuously coating or the impregnated glass fiber cloth that make in order to the top method, drying obtains prepreg under 170 ℃ of baking conditions, 8 prepregs are superimposed, its upper and lower high temperature extension Copper Foil of respectively placing 1 35um, heating under 195 ℃, the pressure of 25Kg/cm2, pressurization 140 minutes obtain the copper-clad laminate of 1.6mm.
4. it is as shown in table 9 that present embodiment prepares the performance perameter of copper-clad laminate of gained:
Table 9
| Project | Test result |
| Second-order transition temperature (DSC), ℃ | 156 |
| Peel strength of copper foil (1oz), lb/in | 9.5 |
| T288(TMA),min | >60 |
| Scolding tin thermotolerance (PCT/3h, 288 ℃ of wickings) | >10min |
| Flame retardant resistance (UL-94, rating) | V-0 |
Embodiment 4:
1. preparation tackiness agent
(1) the quality percentage composition of the solid substance in the adhesive therefor is 65%, and all the other are organic solvent (such as propylene glycol monomethyl ether), and wherein, the prescription of solid substance sees Table 10(by weight)
Table 10
| Raw material | Solid weight (gram) |
| Phosphorous Resins, epoxy | 40 |
| The Resins, epoxy of isocyanic acid modification | 60 |
| Phosphorus curing agent | 14 |
| Resol | 10 |
| Aluminium hydroxide | 45 |
| Silicon-dioxide | 18 |
| 2E4MZ | 0.01 |
2. the preparation method of tackiness agent:
(1) in steel basin, add organic solvent propylene glycol monomethyl ether 102 grams by above weight, turn on agitator, 600 rev/mins of rotating speeds add aluminium hydroxide and silicon-dioxide again, add complete rear lasting stirring 20 minutes;
(2) in steel basin, add successively phosphorous Resins, epoxy, the Resins, epoxy of isocyanic acid modification, phosphorus curing agent, resol by formula ratio, keep stirring with 1000 rev/mins of rotating speeds in the reinforced process;
(3) take by weighing 2E4MZ by formula ratio, after it is dissolved fully with the ratio of weight ratio 1:10 and organic solvent propylene glycol monomethyl ether, this solution is added in steel basin, and continue to keep 1200 rev/mins and stirred 2 hours, make resin glue.
3. preparation copper-clad laminate
The resin glue continuously coating or the impregnated glass fiber cloth that make in order to the top method, drying obtains prepreg under 170 ℃ of baking conditions, 8 prepregs are superimposed, its upper and lower high temperature extension Copper Foil of respectively placing 1 35um, heating under 195 ℃, the pressure of 25Kg/cm2, pressurization 140 minutes obtain the copper-clad laminate of 1.6mm.
4. it is as shown in table 11 that present embodiment prepares the performance perameter of copper-clad laminate of gained:
Table 11
| Project | Test result |
| Second-order transition temperature (DSC), ℃ | 157 |
| Peel strength of copper foil (1oz), lb/in | 9.9 |
| T288(TMA),min | >60 |
| Scolding tin thermotolerance (PCT/3h, 288 ℃ of wickings) | >10min |
| Flame retardant resistance (UL-94, rating) | V-0 |
Comparative example 1:
1. preparation tackiness agent
The quality percentage composition of the solid substance in the adhesive therefor is 65%, and all the other are organic solvent (dimethyl formamide), and wherein, the prescription of solid substance sees Table 12(by weight)
Table 12
| Raw material | Solid weight (gram) |
| Phosphorous Resins, epoxy | 70 |
| Bisphenol-A phenolic Resins, epoxy | 30 |
| Dicy-curing agent | 2.5 |
| Aluminium hydroxide | 23 |
| Silicon-dioxide | 7 |
| 2MI | 0.01 |
2. the preparation method of tackiness agent:
(1) in steel basin, add organic solvent dimethyl formamide 68 grams, dicy-curing agent 2.5 grams by above weight, turn on agitator, 600 rev/mins of rotating speeds add aluminium hydroxide and silicon-dioxide again, add complete rear lasting stirring 20 minutes;
(2) in steel basin, add successively phosphorous Resins, epoxy, bisphenol-A phenolic Resins, epoxy by formula ratio, keep stirring with 1000 rev/mins of rotating speeds in the reinforced process;
(3) take by weighing 2MI by formula ratio, after it is dissolved fully with the ratio of weight ratio 1:10 and organic solvent dimethyl formamide, this solution is added in steel basin, and continue to keep 1200 rev/mins and stirred 2 hours, make resin glue.
3. preparation copper-clad laminate
The resin glue continuously coating or the impregnated glass fiber cloth that make in order to the top method, drying obtains prepreg under 170 ℃ of baking conditions, 8 prepregs are superimposed, its upper and lower high temperature extension Copper Foil of respectively placing 1 35um, heating under 195 ℃, the pressure of 25Kg/cm2, pressurization 140 minutes obtain the copper-clad laminate of 1.6mm.
4. it is as shown in table 13 below that this comparative example prepares the performance perameter of copper-clad laminate of gained:
Table 13
| Project | Test result |
| Second-order transition temperature (DSC), ℃ | 147 |
| Peel strength of copper foil (1oz), lb/in | 9.4 |
| T288(TMA),min | 3 |
| Scolding tin thermotolerance (PCT/3h, 288 ℃ of wickings) | 1min |
| Flame retardant resistance (UL-94, rating) | V-0 |
Comparative example 2:
1. preparation tackiness agent
The quality percentage composition of the solid substance in the adhesive therefor is 65%, and all the other are organic solvent (dimethyl formamide), and wherein, the prescription of solid substance sees Table 14(by weight)
Table 14
| Raw material | Solid weight (gram) |
| Phosphorous Resins, epoxy | 85 |
| Bisphenol-A phenolic Resins, epoxy | 15 |
| Dicy-curing agent | 3.2 |
| Aluminium hydroxide | 20 |
| Silicon-dioxide | 10 |
| 2MI | 0.02 |
2. the preparation method of tackiness agent:
(1) in steel basin, add organic solvent dimethyl formamide 70 grams, dicy-curing agent 3.2 grams by above weight, turn on agitator, 600 rev/mins of rotating speeds add aluminium hydroxide and silicon-dioxide again, add complete rear lasting stirring 20 minutes;
(2) in steel basin, add successively phosphorous Resins, epoxy, bisphenol-A phenolic Resins, epoxy by formula ratio, keep stirring with 1000 rev/mins of rotating speeds in the reinforced process;
(3) take by weighing 2MI by formula ratio, after it is dissolved fully with the ratio of weight ratio 1:10 and organic solvent dimethyl formamide, this solution is added in steel basin, and continue to keep 1200 rev/mins and stirred 2 hours, make resin glue.
3. preparation copper-clad laminate
The resin glue continuously coating or the impregnated glass fiber cloth that make in order to the top method, drying obtains prepreg under 170 ℃ of baking conditions, 8 prepregs are superimposed, its upper and lower high temperature extension Copper Foil of respectively placing 1 35um, heating under 195 ℃, the pressure of 25Kg/cm2, pressurization 140 minutes obtain the copper-clad laminate of 1.6mm.
4. it is as shown in table 15 below that this Comparative Examples prepares the performance perameter of copper-clad laminate of gained:
Table 15
| Project | Test result |
| Second-order transition temperature (DSC), ℃ | 151 |
| Peel strength of copper foil (1oz), lb/in | 9.2 |
| T288(TMA),min | 4 |
| Scolding tin thermotolerance (PCT/3h, 288 ℃ of wickings) | 2min |
| Flame retardant resistance (UL-94, rating) | V-0 |
In sum, the copper-clad plate for preparing gained with not halogen-containing phosphor-containing flame-proof tackiness agent of the present invention, have good heat resistance and Zu Ran ﹐ and have good toughness and stripping strength, this copper-clad plate can be made the good halogen-free environmental printed-wiring board (PWB) of various characteristics.
Claims (18)
1. the flame retardant resin tackiness agent of a phosphor-containing halogen-free element is characterized in that, this tackiness agent is comprised of solid substance and organic solvent,
Wherein, the weight percentage of solid substance is 50-90%, and organic solvent is surplus,
Solid substance is comprised of the component of following weight percentage:
Phosphorous Resins, epoxy 5%-50%,
The Resins, epoxy 10%-60% of isocyanic acid modification,
Phosphorus curing agent 1%-35%,
Resol 1%-30%,
Mineral filler 10%-60%,
Epoxy resin cure promotor 0.002-0.015%.
2. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1 is characterized in that, the weight percentage of solid substance is 55-75%, and organic solvent is surplus.
3. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1 is characterized in that, the chemical structure of described phosphorous Resins, epoxy is as shown in the formula (1):
Wherein, n=1 ~ 3.
The structure of DOPO is as shown in the formula (2):
4. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1 is characterized in that, described phosphorous Resins, epoxy is the PE-315 phosphorous epoxy resin of Shanxi, Taiwan one Chemical Manufacture.
5. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1, it is characterized in that the mixture of one or both in the Resins, epoxy that described isocyanate-modified Resins, epoxy is the modification of aromatic series diphenylmethanediisocyanate, the Resins, epoxy of tolylene diisocyanate modification.
6. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1 is characterized in that, described isocyanate-modified Resins, epoxy is the XZ-97103 Resins, epoxy that DOW Chemical is produced.
7. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1 is characterized in that, described phosphorus curing agent is the bisphenol A-type phosphorus containing phenolic resin.
8. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1 is characterized in that, described phosphorus curing agent is that DOW Chemical is produced trade mark XZ-92741 resin.
9. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1, it is characterized in that, described resol is the resol of phenol and formaldehyde crosslinking, and described phenol is one or more the mixture in phenol, xylenol, ethylphenol, n-propyl phenol, isopropyl-phenol, normal-butyl phenol, isobutyl-phenol, tert.-butyl phenol or the dihydroxyphenyl propane.
10. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 9 is characterized in that, described phenol is one or both the mixture in phenol or the dihydroxyphenyl propane.
11. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1 is characterized in that, described resol is that the KPH-L2003 resin of chemical production can be swelled in Korea S.
12. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1 is characterized in that, described mineral filler is one or more the mixture in talcum, silica powder, ceramics powder, aluminium hydroxide, silicon-dioxide, clay or the boron nitride.
13. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 12 is characterized in that, described mineral filler is one or both the mixture in silicon-dioxide or the aluminium hydroxide.
14. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1 is characterized in that, described epoxy resin cure promotor is imidazolium compounds.
15. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 14 is characterized in that, described imidazolium compounds is one or both the mixture in 2-ethyl-4-methylimidazole or the 1 benzyl 2 methyl imidazole.
16. the flame retardant resin tackiness agent of phosphor-containing halogen-free element according to claim 1, it is characterized in that described organic solvent is one or more the mixture in acetone, methyl ethyl ketone, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether or the pimelinketone.
17. the preparation method of the flame retardant resin tackiness agent of each described phosphor-containing halogen-free element of claim 1-16 is characterized in that the method may further comprise the steps:
(1) press formula ratio and in steel basin, add the part organic solvent, turn on agitator, 500 ~ 1500 rev/mins of rotating speeds, the control flume temperature adds mineral filler again at 20 ~ 50 ℃ to keep continuing to stir also, adds complete rear lasting stirring 10 ~ 50 minutes;
(2) in steel basin, add successively phosphorous Resins, epoxy, the Resins, epoxy of isocyanic acid modification, phosphorus curing agent, resol by formula ratio, keep stirring with 1000 ~ 1500 rev/mins of rotating speeds in the reinforced process, add that complete rear unlatching is efficient shears and emulsification 0.5 ~ 4 hour, carry out simultaneously cooling water circulation with retentive control cell body temperature at 20 ~ 50 ℃;
(3) take by weighing epoxy resin cure promotor by formula ratio, it is joined in the remaining organic solvent, after the dissolving, this solution is added in the steel basin fully, and continue to keep 1000 ~ 1500 rev/mins of stirrings 3 ~ 15 hours, namely make tackiness agent.
18. the application of the flame retardant resin tackiness agent of each described phosphor-containing halogen-free element of claim 1-12 in the preparation copper-clad plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210491704.4A CN102964777B (en) | 2012-11-27 | 2012-11-27 | Phosphorus-containing and halogen-free flame retardant resin adhesive as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210491704.4A CN102964777B (en) | 2012-11-27 | 2012-11-27 | Phosphorus-containing and halogen-free flame retardant resin adhesive as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN102964777A true CN102964777A (en) | 2013-03-13 |
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| CN104628996A (en) * | 2015-02-10 | 2015-05-20 | 广东广山新材料有限公司 | Flame retardant with bisphenol F group, flame-retardant epoxy resin and flame-retardant composition |
| CN106009532A (en) * | 2016-06-29 | 2016-10-12 | 上海南亚覆铜箔板有限公司 | Halogen-free thermosetting resin composition as well as preparation method and application thereof |
| CN106166874A (en) * | 2016-06-29 | 2016-11-30 | 上海南亚覆铜箔板有限公司 | Halogen-free copper-clad plate and preparation method thereof |
| CN108841196A (en) * | 2018-06-12 | 2018-11-20 | 杨杰 | A kind of Halogen-free low-smoke flame-retardant TPE cable material and preparation method |
| CN109082253A (en) * | 2018-06-25 | 2018-12-25 | 南亚新材料科技股份有限公司 | A kind of halogen-free adhesive of polymolecularity and preparation method thereof |
| CN109181225A (en) * | 2018-08-09 | 2019-01-11 | 陕西生益科技有限公司 | A kind of heat conductive flame-retarding resin combination and its application |
| CN109265920A (en) * | 2018-08-09 | 2019-01-25 | 陕西生益科技有限公司 | A kind of highly thermal-conductive resin composition and its application |
| CN109851991A (en) * | 2018-12-04 | 2019-06-07 | 吉安市宏瑞兴科技有限公司 | A kind of halogen-free epoxy resin composition and preparation method thereof and application thereof |
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| CN106166874B (en) * | 2016-06-29 | 2018-07-20 | 南亚新材料科技股份有限公司 | halogen-free copper-clad plate and preparation method thereof |
| CN108841196A (en) * | 2018-06-12 | 2018-11-20 | 杨杰 | A kind of Halogen-free low-smoke flame-retardant TPE cable material and preparation method |
| CN109082253A (en) * | 2018-06-25 | 2018-12-25 | 南亚新材料科技股份有限公司 | A kind of halogen-free adhesive of polymolecularity and preparation method thereof |
| CN109181225A (en) * | 2018-08-09 | 2019-01-11 | 陕西生益科技有限公司 | A kind of heat conductive flame-retarding resin combination and its application |
| CN109265920A (en) * | 2018-08-09 | 2019-01-25 | 陕西生益科技有限公司 | A kind of highly thermal-conductive resin composition and its application |
| CN109851991A (en) * | 2018-12-04 | 2019-06-07 | 吉安市宏瑞兴科技有限公司 | A kind of halogen-free epoxy resin composition and preparation method thereof and application thereof |
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Address after: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Patentee after: South Asia new materials Polytron Technologies Inc Address before: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Patentee before: Shanghai Nanya Copper Clad Laminate Co., Ltd. |