CN109082253A - A kind of halogen-free adhesive of polymolecularity and preparation method thereof - Google Patents
A kind of halogen-free adhesive of polymolecularity and preparation method thereof Download PDFInfo
- Publication number
- CN109082253A CN109082253A CN201810663197.5A CN201810663197A CN109082253A CN 109082253 A CN109082253 A CN 109082253A CN 201810663197 A CN201810663197 A CN 201810663197A CN 109082253 A CN109082253 A CN 109082253A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- slurry
- filler
- solvent
- halogen
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/04—Epoxynovolacs
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- 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
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to halogen-free adhesives of a kind of polymolecularity and preparation method thereof, are prepared using the raw material of following components and weight percent content: DOPO epoxy resin 5-50；Novolac epoxy resin 5-25；Phosphorus curing agent 1-40；Phenolic resin 1-30；Isocyanate modified epoxy resin 10-60；Inorganic filler slurry 20-60；Amine curing agent 0.5-5；Catalyst 0.002-0.2；Solvent 5-20.Compared with prior art, the present invention effectively improves secondary agglomeration of the glue when flowing in the duct after being detached from mechanical dispersion equipment, improves production reliability.
Description
Technical field
The present invention relates to copper-clad plate production technical fields, a kind of halogen-free adhesive more particularly, to polymolecularity and its
Preparation method.
Background technique
With the development of copper-clad plate technology, important means, electron level are had become using addition electron level filler in glue
Filler can be to improve a series of problems that copper-clad plate produces, but the dispersed situation of electron level filler and glue directly affects production
The reliability of product, especially more and more thinner in client thickness of dielectric layers, the design of line width line-spacing is more and more thinner, and drilling pitch of holes is more next
It is smaller, easily in process because the bad formation of powder lot dispersing powder agglomerated masses, occur reliability the problem of.
To improve glue dispersibility, mechanical dispersion equipment is added in each copper-clad plate producer successively, and dispersion effect has part
Promotion, but effect is not very significant, and can not evade secondary agglomeration during glue transhipment gluing, influences to glue section operation
Difficulty, such as filter effect, PP appearance.
Requirement with PCB client to HDI plate is higher and higher, causes processing procedure process not to be available more since dispersibility is bad
Thin strainer filtering causes short ratio in client higher, and Hi-Pot crash rate is relatively high, how to improve glue and is being detached from machinery
Secondary agglomeration when flowing in the duct after dispersing apparatus is at present technical problem urgently to be resolved.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of nothings of polymolecularity
Halogen adhesive.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of halogen-free adhesive of polymolecularity, is prepared into using the raw material of following components and weight percent content
It arrives:
DOPO epoxy resin 5-50；Novolac epoxy resin 5-25；Phosphorus curing agent 1-40；Phenolic resin 1-30；Isocyanic acid
Ester modified epoxy resin 10-60；Inorganic filler slurry 20-60；Amine curing agent 0.5-5；Catalyst 0.002-0.2；Solvent 5-
20。
The DOPO epoxy resin is selected from one kind of DOPO-HQ type epoxy resin or DOPO-NQ type epoxy resin；
The novolac epoxy resin is selected from bisphenol-A phenolic epoxy resin, o-cresol formaldehyde epoxy resin or BPA epoxy novolac tree
Rouge it is one or more；
The phosphorus curing agent is selected from bisphenol A-type phosphorus containing phenolic resin；
The phenolic resin is selected from common phenol and formaldehyde cross-linking resins, phenol formaldehyde resin, bisphenol A formaldehyde resin or adjacent first
One or more mixtures of fluosite；
The isocyanate modified epoxy resin be selected from the modified epoxy resin of aromatic series '-diphenylmethane diisocyanate or
One or two kinds of mixtures of the modified epoxy resin of toluene di-isocyanate(TDI).
The amine curing agent is selected from the one or more of dihydro-amine or diamine or diaminodiphenylsulfone；
The catalyst is selected from one of 2-methylimidazole, -4 methylimidazole of 2 ethyl, 2- phenylimidazole or boric acid or more
Kind mixture；
The solvent is a kind of or more in propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanone, cyclohexanone, toluene or dimethylbenzene
Kind mixture.
The inorganic filler slurry is prepared using the raw material of following components and weight percent content: inorganic filler
25-85；Coupling agent 0.2-3；Solvent 15-70；Filler affinity agent 0.02-2.
The inorganic filler is selected from talcum powder, silica flour, ceramic powder, aluminium hydroxide, silica, magnesium hydroxide, clay
Or the mixture of one or more of boron nitride, partial size are 1-3 μm；
The coupling agent is in silane coupling agent, titanate coupling agent, aluminate coupling agent or isocyanate coupler
One or more mixtures.
The solvent is a kind of or more in propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanone, cyclohexanone, toluene or dimethylbenzene
Kind mixture
The filler affinity agent is selected from polyamide, polyimides, polyurethane, polyacrylic acid with filler affinity groups
One kind of ester, phosphonate ester, amine salt, sodium salt or sulfonate, the affinity groups end of the filler affinity agent and filler colloidal particle band are not
Same charge makes filler be in close contact cladding by affinity groups end, coats the filler surface band identical charges of affinity agent, makes filler
The cohesion of Van der Waals force is overcome between particle.
The inorganic filler slurry is prepared using following methods:
(1) solvent is pumped into pulp treatment tank, control flume temperature is affine by coupling agent and filler at 20-50 DEG C
Agent is poured into solvent, and stirring is opened, and 800~1500rpm of revolving speed is stirred decentralized processing to solution；
(2) inorganic filler is added in solvent, opens stirring, 800~1500rpm of revolving speed continues filler solution
It is dispersed with stirring processing；
(3) 1h is handled to slurry ultrasonic disperse in groove body using groove body outer ultrasonic wave dispersing apparatus；
(4) groove body bottom valve and circuit valve are opened, recycles slurry through piping, is opened on circulating line
Homogeneous emulsifying machine, revolving speed 7000-30000rpm carry out mechanical dispersion to slurry and handle to 25 μm of < of fineness test；
(5) inorganic filler slurry is prepared after the completion of homogenous disperse, keeps stirring at low speed, 800~1500rpm of revolving speed
For use.
Step (4) uses 1 μm of strainer and the Magnetic filtration device with the strong magnetic magnetic bar of 3-20 root in progress slurry dispersion process
Device is filtered.
A kind of preparation method of the halogen-free adhesive of polymolecularity, using following steps:
(1) it stocks up by formula；
(2) solvent is pumped into impregnation slot, opens stirring, 800~1000rpm of revolving speed, be gradually added amine curing agent until
Dissolution finishes；
(3) DOPO epoxy resin, novolac epoxy resin, phosphorus curing agent, phenolic resin, isocyanide are successively pumped into impregnation slot
Acid esters modified epoxy opens stirring, 800~1000rpm of revolving speed after being added；
(4) impregnation slot is added in the catalyst dissolved, persistently stirred 2 hours；
(5) scattered inorganic filler slurry is pumped into impregnation slot and is mixed with glue, open high shear in impregnation groove body
Blender, revolving speed 7000-30000rpm, emulsifying mixer, revolving speed 7000-30000rpm, while opening groove body bottom valve
Door and circuit valve, recycle glue through piping, open the homogeneous emulsifying machine on circulating line, revolving speed 7000-
30000rpm carries out mechanical dispersion to slurry and handles to 10 μm of < of fineness test；
(6) it keeps stirring at low speed after the completion of homogenous disperse, 800~1500rpm of revolving speed, gluing is supplied by pipeline and is used.
Compared with prior art, the present invention effectively improves glue and flows in the duct after being detached from mechanical dispersion equipment
When secondary agglomeration, improve production reliability, have the advantage that
1, inorganic filler slurry is prepared by adding a certain proportion of filler affinity agent, dispersion effect is good, the entirety of system
Viscosity reduces, and filler is dispersed in the relatively high resin of viscosity, and filler grain is coated by resin, the more difficult dispersion effect of dispersion
It is bad and uneven, it needs to cooperate prolonged high-speed stirred shearing and homogeneous grinding；Filler (1-2 μm of partial size) is detached from machinery and stirs
There is no under the action of filler affinity agent that reunion particle size analysis becomes larger after the reunion of filler after mixing, glue is in use, will cause filter
The frequent replacement and operation puzzlement of net, while the magnetic material in filler is coated by resin, is subtracted with the direct magnetic force attraction of magnetic bar
It is weak, cause magnetic force object absorption in glue insufficient.
Coupling agent and filler affinity agent are first added in the low dispersion phase solvent of viscosity by this slurry production method, add
The contact area of filler, filler and coupling agent and filler affinity agent increases, the affine base of filler colloidal particle and filler affinity agent
Group coats filler closely by the affinity groups of filler affinity agent, coats the filler surface band phase of affinity agent with different charges
Same charge makes the cohesion that Van der Waals force is overcome between filler grain, and prolonged slurry can also be maintained by being detached from mechanical dispersion equipment
Situation is unlikely to settle and reunite, and so that filler is saved single coating particles form and there is the strainer that can effectively pass through 10 μm
Impurity screening, while the magnetic bar in slurry directly attracts with magnetic impurity contact magnetic force, can effectively adsorb magnetic impurity,
Strainer filtering and the magnetic material absorption that 10 μm can be cycled through, make impurity and magnetic material ratio in slurry reduce by 70%.
2, by addition filler affinity agent, filler is dispersed in the relatively high resin of viscosity, and filler grain is coated by resin,
The more difficult dispersion effect of dispersion is bad and uneven, needs to cooperate prolonged high-speed stirred shearing and homogeneous grinding；Filler
Reunion particle size analysis becomes partial size after the reunion of filler under the action of not having filler affinity agent after 1-2 μm is detached from mechanical stirring
Greatly, glue is in use, will cause the frequent replacement and operation puzzlement of strainer.
The slurry of powder dicyandiamide solution production high degree of dispersion is first added in filler affinity agent by this adding method, is added by slurry
Enter into resin, then carry out mechanical dispersion, disperses dispersion effect twice and improve, glue can also be maintained in disengaging mechanical dispersion equipment
Prolonged dispersion situation is unlikely to settle and reunite, and makes powder in solvent dispersion process, and filler surface wraps up one layer of band phase
With the particle of charge, makes the filler of ultra-fine grain diameter be unlikely to generate secondary agglomeration under the situation for being detached from mechanical dispersion, glue glue
Water tune, which glues cyclic process, can effectively use 10 μm of strainer filtering 12h or more, and making to glue impurity ratio in PP reduces 80%
3, the substrate of glue production 1080 and following thin cloth can be tested by Hi-Pot (1KV), and crash rate is from early period
50% is reduced to 1%.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
The preparation method and related data of inorganic filler slurry
Inorganic filler: talcum powder, silica flour, ceramic powder, aluminium hydroxide, silica, magnesium hydroxide, clay, nitrogen are selected from
Change in boron
One or more kinds of mixtures, the partial size D50 of inorganic filler is at 1-3 μm.
Coupling agent is selected from one of silane coupling agent, titanate coupling agent, aluminate coupling agent, isocyanate coupler
Or a variety of mixture.
Solvent: propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanone, cyclohexanone, toluene, one or more mixed in dimethylbenzene is selected
Close object
Filler affinity agent is selected from polyamide (polyimides) type, polyurethane, polyacrylate with filler affinity groups
Type, phosphonic acids ester type, amine salt type, one kind of sodium-salt type, sulfonate type.
Data are as follows:
| Classification | Comparative example 1 | Embodiment 1 | Embodiment 2 |
| Inorganic filler (g) | 60 | 60 | 60 |
| Coupling agent (g) | 0.5 | 0.5 | 0.5 |
| Solvent (g) | 40 | 40 | 40 |
| Filler affinity agent (g) | 0 | 0.5 | 1.3 |
(1) solvent is pumped into pulp treatment tank, control flume temperature is affine by coupling agent and filler at 20-50 DEG C
Agent is poured into solvent, is opened normal agitation (800~1500RPM of revolving speed) and is stirred decentralized processing 1h to solution；
(2) inorganic filler is added in solvent, open normal agitation (800~1500RPM of revolving speed) to filler solution into
Row is persistently dispersed with stirring processing；
(3) 1h is handled to slurry ultrasonic disperse in groove body using groove body outer ultrasonic wave dispersing apparatus；
Groove body bottom valve and circuit valve are opened, recycles glue through piping, is opened equal on circulating line
Matter mulser (7000-30000RPM) carries out mechanical dispersion processing 0.5h~4h to slurry until 25 μm of < of fineness test (is used
Hegman grind gage test)；
(4) inorganic filler slurry dispersion process uses 1 μm of strainer and the magnetic filter with the strong magnetic magnetic bar of 3-20 root
It is filtered, obtains slurry of the solid content 65%.
(5) keep stirring at low speed (800~1500RPM of revolving speed) after the completion of homogenous disperse for use.
The comparison of inorganic filler slurry situation
| Classification | Comparative example 1 | Embodiment 1 | Embodiment 2 |
| Viscosity (sec) | > 60 | 18 | 13 |
| Fineness (μm) | 150 | 9 | 7 |
| 10 μm tail over ratio (%) | 100% | 10% | 8% |
The halogen-free adhesive (wt%) of polymolecularity is done according to following components and content stock:
DOPO epoxy resin: one kind selected from DOPO-HQ type epoxy resin or DOPO-NQ type epoxy resin.
Novolac epoxy resin: selected from bisphenol-A phenolic epoxy resin, o-cresol formaldehyde epoxy resin, BPA novolac epoxy resin
It is one or more.
Phosphorus curing agent: it is selected from bisphenol A-type phosphorus containing phenolic resin.
Phenolic resin: common phenol and formaldehyde cross-linking resins, phenol formaldehyde resin, bisphenol A formaldehyde resin, o-cresol first are selected from
One or more mixtures of urea formaldehyde.
Isocyanate modified epoxy resin: selected from the modified epoxy resin of aromatic series '-diphenylmethane diisocyanate, toluene
One or two kinds of mixtures of the ester modified epoxy resin of diisocyanate.
Inorganic filler slurry: the solid content 50-90% high degree of dispersion that filler is surface-treated according to 2.2 ratio requirements
The slurry of property.
Amine curing agent: selected from dihydro-amine or diamine, diaminodiphenylsulfone it is one or more.
Catalyst: one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, boric acid or a variety of are selected from
Mixture.
Solvent: propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanone, cyclohexanone, toluene, one or more mixed in dimethylbenzene is selected
Close object.
| Classification | Comparative example 2 | Embodiment 3 | Embodiment 4 |
| DOPO epoxy resin (g) | 35 | 35 | 35 |
| Novolac epoxy resin (g) | 15 | 15 | 15 |
| Phosphorus curing agent (g) | 20 | 20 | 20 |
| Phenolic resin (g) | 20 | 20 | 20 |
| Isocyanate modified epoxy resin (g) | 15 | 15 | 15 |
| Inorganic filler slurry (g) | - | 35 | 50 |
| Inorganic filler (g) | 25 | - | - |
| Amine curing agent (g) | 2.0 | 2.0 | 2.0 |
| Catalyst (g) | 0.01 | 0.01 | 0.01 |
| Coupling agent (g) | - | - | - |
| Solvent (g) | 45 | 10 | 10 |
(1) solvent is pumped by the amount of formula and enters impregnation slot, open normal agitation (800~1000RPM of revolving speed), be gradually added
Amine curing agent is until dissolution finishes.
(2) DOPO epoxy resin, novolac epoxy resin, phosphorus curing agent, phenolic resin, isocyanide are successively pumped into impregnation slot
Acid esters modified epoxy opens normal agitation (800~1000RPM of revolving speed) after being added
(3) impregnation slot is added in the catalyst dissolved, continues normal agitation 2 hours；
(4) scattered inorganic filler slurry is pumped into impregnation slot and is mixed with glue, open high shear in impregnation groove body
Blender (7000-30000RPM)；Emulsifying mixer (7000-30000RPM), while opening groove body bottom valve and return valve
Door, recycles glue through piping, and the homogeneous emulsifying machine (7000-30000RPM) opened on circulating line carries out slurry
Mechanical dispersion handles 0.5h~2h until 10 μm of < of fineness test (being tested using Hegman grind gage)
(5) it keeps after the completion of homogenous disperse stirring at low speed (800~1500RPM of revolving speed) and passes through pipeline supply gluing use.
The dispersibility and gluing behaviour in service of glue are as follows:
The prepreg and substrate reliability performance (by taking 8*7628 1.5mm1/1 as an example) of glue production are as follows:
Embodiment 5
A kind of halogen-free adhesive of polymolecularity, is prepared into using the raw material of following components and weight percent content
It arrives:
DOPO epoxy resin 5；Novolac epoxy resin 5；Phosphorus curing agent 1；Phenolic resin 1；Isocyanate-modified asphalt mixtures modified by epoxy resin
Rouge 10；Inorganic filler slurry 20；Amine curing agent 0.5；Catalyst 0.002；Solvent 5.
The DOPO epoxy resin used is DOPO-HQ type epoxy resin, and novolac epoxy resin is bisphenol-A phenolic asphalt mixtures modified by epoxy resin
Rouge, phosphorus curing agent are bisphenol A-type phosphorus containing phenolic resin, and phenolic resin is common phenol and formaldehyde cross-linking resins, and isocyanates changes
Property epoxy resin be the modified epoxy resin of aromatic series '-diphenylmethane diisocyanate, amine curing agent is dihydro-amine or binary
Amine, catalyst are 2-methylimidazole, and solvent is propylene glycol monomethyl ether.
Inorganic filler slurry is prepared using the raw material of following components and weight percent content: inorganic filler 25；It is even
Join agent 0.2；Solvent 15；Filler affinity agent 0.02.Inorganic filler is the talcum powder that partial size is 1-3 μm, and coupling agent is silane coupled
Agent, solvent are propylene glycol monomethyl ether, and filler affinity agent is the polyamide with filler affinity groups.Inorganic filler slurry is using following
Method is prepared:
(1) solvent is pumped into pulp treatment tank, control flume temperature falls coupling agent and filler affinity agent at 20 DEG C
Enter in solvent, open stirring, revolving speed 800rpm is stirred decentralized processing to solution；
(2) inorganic filler is added in solvent, opens stirring, revolving speed 800rpm carries out filler solution to continue stirring point
Dissipate processing；
(3) 1h is handled to slurry ultrasonic disperse in groove body using groove body outer ultrasonic wave dispersing apparatus；
(4) groove body bottom valve and circuit valve are opened, recycles slurry through piping, is opened on circulating line
Homogeneous emulsifying machine, revolving speed 7000rpm carry out mechanical dispersion to slurry and handle to 25 μm of < of fineness test, dispersed carrying out slurry
Magnetic filter of the journey using 1 μm of strainer and with the strong magnetic magnetic bar of 3-20 root is filtered；
(5) inorganic filler slurry is prepared after the completion of homogenous disperse, keeps stirring at low speed, revolving speed 800rpm is stand-by.
The preparation method of the halogen-free adhesive of polymolecularity, using following steps:
(1) it stocks up by formula；
(2) solvent is pumped into impregnation slot, opens stirring, revolving speed 800rpm is gradually added amine curing agent until having dissolved
Finish；
(3) DOPO epoxy resin, novolac epoxy resin, phosphorus curing agent, phenolic resin, isocyanide are successively pumped into impregnation slot
Acid esters modified epoxy opens stirring, revolving speed 800rpm after being added；
(4) impregnation slot is added in the catalyst dissolved, persistently stirred 2 hours；
(5) scattered inorganic filler slurry is pumped into impregnation slot and is mixed with glue, open high shear in impregnation groove body
Blender, revolving speed 7000rpm, emulsifying mixer, revolving speed 7000rpm, while groove body bottom valve and circuit valve are opened,
It recycles glue through piping, opens the homogeneous emulsifying machine on circulating line, revolving speed 7000rpm carries out machine to slurry
Tool decentralized processing to fineness tests 10 μm of <；
(6) it keeps stirring at low speed after the completion of homogenous disperse, revolving speed 800rpm, gluing is supplied by pipeline and is used.
Embodiment 6
A kind of halogen-free adhesive of polymolecularity, is prepared into using the raw material of following components and weight percent content
It arrives: DOPO epoxy resin 50；Novolac epoxy resin 25；Phosphorus curing agent 40；Phenolic resin 30；Isocyanate modified epoxy resin
60；Inorganic filler slurry 60；Amine curing agent 5；Catalyst 0.2；Solvent 20.
The DOPO epoxy resin used is DOPO-NQ type epoxy resin；Novolac epoxy resin is o-cresol formaldehyde epoxy resin
With the mixture of BPA novolac epoxy resin；Phosphorus curing agent is bisphenol A-type phosphorus containing phenolic resin；Phenolic resin is phenol formaldehyde (PF)
Resin；Isocyanate modified epoxy resin is selected from the modified epoxy resin of aromatic series '-diphenylmethane diisocyanate and toluene two is different
One or two kinds of mixtures of cyanate modified epoxy resin.Amine curing agent is diaminodiphenylsulfone；Catalyst is 2-
Phenylimidazole；Solvent is the mixture of butanone, cyclohexanone.
Inorganic filler slurry is prepared using the raw material of following components and weight percent content: inorganic filler 85；It is even
Join agent 3；Solvent 70；Filler affinity agent 2.Inorganic filler is the mixture of silica flour, ceramic powder, and partial size is 1-3 μm；Coupling agent is
Titanate coupling agent, solvent are the mixture of butanone, cyclohexanone, and it is sub- that filler affinity agent is selected from the polyamides with filler affinity groups
Amine.
Inorganic filler slurry is prepared using following methods:
(1) solvent is pumped into pulp treatment tank, control flume temperature falls coupling agent and filler affinity agent at 50 DEG C
Enter in solvent, open stirring, revolving speed 1500rpm is stirred decentralized processing to solution；
(2) inorganic filler is added in solvent, opens stirring, revolving speed 1500rpm carries out filler solution to continue stirring
Decentralized processing；
(3) 1h is handled to slurry ultrasonic disperse in groove body using groove body outer ultrasonic wave dispersing apparatus；
(4) groove body bottom valve and circuit valve are opened, recycles slurry through piping, is opened on circulating line
Homogeneous emulsifying machine, revolving speed 30000rpm carry out mechanical dispersion to slurry and handle to 25 μm of < of fineness test, are carrying out slurry dispersion
Magnetic filter of the process using 1 μm of strainer and with the strong magnetic magnetic bar of 3-20 root is filtered；
(5) inorganic filler slurry is prepared after the completion of homogenous disperse, keeps stirring at low speed, revolving speed 1500rpm is stand-by.
The preparation method of the halogen-free adhesive of polymolecularity, using following steps:
(1) it stocks up by formula；
(2) solvent is pumped into impregnation slot, opens stirring, revolving speed 1000rpm is gradually added amine curing agent until having dissolved
Finish；
(3) DOPO epoxy resin, novolac epoxy resin, phosphorus curing agent, phenolic resin, isocyanide are successively pumped into impregnation slot
Acid esters modified epoxy opens stirring, revolving speed 1000rpm after being added；
(4) impregnation slot is added in the catalyst dissolved, persistently stirred 2 hours；
(5) scattered inorganic filler slurry is pumped into impregnation slot and is mixed with glue, open high shear in impregnation groove body
Blender, revolving speed 30000rpm, emulsifying mixer, revolving speed 30000rpm, while opening groove body bottom valve and return valve
Door, recycle glue through piping, open circulating line on homogeneous emulsifying machine, revolving speed 30000rpm, to slurry into
Row mechanical dispersion handles to fineness and tests 10 μm of <；
(6) it keeps stirring at low speed after the completion of homogenous disperse, revolving speed 1500rpm, gluing is supplied by pipeline and is used.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (9)
1. a kind of halogen-free adhesive of polymolecularity, which is characterized in that the adhesive uses following components and weight percent
The raw material of content is prepared:
DOPO epoxy resin 5-50；Novolac epoxy resin 5-25；Phosphorus curing agent 1-40；Phenolic resin 1-30；Isocyanates changes
Property epoxy resin 10-60；Inorganic filler slurry 20-60；Amine curing agent 0.5-5；Catalyst 0.002-0.2；Solvent 5-20.
2. a kind of halogen-free adhesive of polymolecularity according to claim 1, which is characterized in that
The DOPO epoxy resin is selected from one kind of DOPO-HQ type epoxy resin or DOPO-NQ type epoxy resin；
The novolac epoxy resin is selected from bisphenol-A phenolic epoxy resin, o-cresol formaldehyde epoxy resin or BPA novolac epoxy resin
It is one or more；
The phosphorus curing agent is selected from bisphenol A-type phosphorus containing phenolic resin；
The phenolic resin is selected from common phenol and formaldehyde cross-linking resins, phenol formaldehyde resin, bisphenol A formaldehyde resin or o-cresol first
One or more mixtures of urea formaldehyde；
The isocyanate modified epoxy resin is selected from the modified epoxy resin or toluene of aromatic series '-diphenylmethane diisocyanate
One or two kinds of mixtures of the ester modified epoxy resin of diisocyanate.
3. a kind of halogen-free adhesive of polymolecularity according to claim 1, which is characterized in that
The amine curing agent is selected from the one or more of dihydro-amine or diamine or diaminodiphenylsulfone；
The catalyst is selected from one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole or boric acid or a variety of
Mixture；
The solvent is one or more mixed in propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanone, cyclohexanone, toluene or dimethylbenzene
Close object.
4. a kind of halogen-free adhesive of polymolecularity according to claim 1, which is characterized in that the inorganic filler slurry
Material is prepared using the raw material of following components and weight percent content: inorganic filler 25-85；Coupling agent 0.2-3；Solvent
15-70；Filler affinity agent 0.02-2.
5. a kind of halogen-free adhesive of polymolecularity according to claim 4, which is characterized in that
The inorganic filler is selected from talcum powder, silica flour, ceramic powder, aluminium hydroxide, silica, magnesium hydroxide, clay or nitrogen
Change the mixture of one or more of boron, partial size is 1-3 μm；
The coupling agent in silane coupling agent, titanate coupling agent, aluminate coupling agent or isocyanate coupler one
Kind or a variety of mixtures.
The solvent is one or more mixed in propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanone, cyclohexanone, toluene or dimethylbenzene
Close object
The filler affinity agent is selected from polyamide, polyimides, polyurethane, polyacrylate, phosphine with filler affinity groups
One kind of acid esters, amine salt, sodium salt or sulfonate.
6. a kind of halogen-free adhesive of polymolecularity according to claim 4 or 5, which is characterized in that described inorganic to fill out
Slurry material is prepared using following methods:
(1) solvent is pumped into pulp treatment tank, control flume temperature falls coupling agent and filler affinity agent at 20-50 DEG C
Enter in solvent, opens stirring and decentralized processing is stirred to solution；
(2) inorganic filler is added in solvent, opens stirring and processing is persistently dispersed with stirring to filler solution；
(3) 1h is handled to slurry ultrasonic disperse in groove body using groove body outer ultrasonic wave dispersing apparatus；
(4) groove body bottom valve and circuit valve are opened, recycles slurry through piping, opens the homogeneous on circulating line
Mulser carries out mechanical dispersion to slurry and handles to 25 μm of < of fineness test；
(5) inorganic filler slurry is prepared after the completion of homogenous disperse, holding stirs at low speed stand-by.
7. a kind of halogen-free adhesive of polymolecularity according to claim 6, which is characterized in that step (4) is carrying out
Magnetic filter of the slurry dispersion process using 1 μm of strainer and with the strong magnetic magnetic bar of 3-20 root is filtered.
8. a kind of preparation method of the halogen-free adhesive of polymolecularity as described in claim 1, which is characterized in that this method
Using following steps:
(1) it stocks up by formula；
(2) solvent is pumped into impregnation slot, opens stirring, be gradually added amine curing agent until dissolution finishes；
(3) DOPO epoxy resin, novolac epoxy resin, phosphorus curing agent, phenolic resin, isocyanates are successively pumped into impregnation slot
Modified epoxy opens stirring after being added；
(4) impregnation slot is added in the catalyst dissolved, persistently stirred 2 hours；
(5) scattered inorganic filler slurry is pumped into impregnation slot and is mixed with glue, open high shear stirring in impregnation groove body
Machine and emulsifying mixer, while groove body bottom valve and circuit valve are opened, it recycles glue through piping, opens circulation
Homogeneous emulsifying machine on pipeline carries out mechanical dispersion to slurry and handles to 10 μm of < of fineness test；
(6) it keeps stirring at low speed after the completion of homogenous disperse and gluing use is supplied by pipeline.
9. a kind of preparation method of the halogen-free adhesive of polymolecularity according to claim 8, which is characterized in that step
(5) revolving speed of high-shear impeller is 7000-30000rpm in, and the revolving speed of emulsifying mixer is 7000-30000rpm, homogenized milk
The revolving speed of change machine is 7000-30000rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810663197.5A CN109082253A (en) | 2018-06-25 | 2018-06-25 | A kind of halogen-free adhesive of polymolecularity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810663197.5A CN109082253A (en) | 2018-06-25 | 2018-06-25 | A kind of halogen-free adhesive of polymolecularity and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109082253A true CN109082253A (en) | 2018-12-25 |
Family
ID=64840149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810663197.5A Pending CN109082253A (en) | 2018-06-25 | 2018-06-25 | A kind of halogen-free adhesive of polymolecularity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109082253A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880546A (en) * | 2019-03-14 | 2019-06-14 | 南亚新材料科技股份有限公司 | Barium sulfate filler slurry of polymolecularity applied to copper-clad plate and preparation method thereof |
| CN109912932A (en) * | 2019-03-14 | 2019-06-21 | 南亚新材料科技股份有限公司 | A kind of halogen-free adhesive of high CTI value and its preparation method and application |
| CN112760071A (en) * | 2021-01-22 | 2021-05-07 | 东莞市派乐玛新材料技术开发有限公司 | Sealant and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59193936A (en) * | 1983-04-19 | 1984-11-02 | Sumitomo Alum Smelt Co Ltd | Filler for resin |
| CN1334281A (en) * | 2001-06-15 | 2002-02-06 | 华中科技大学 | Process for preparing inorganic filler reinforced polymer composite material |
| CN1570010A (en) * | 2004-04-23 | 2005-01-26 | 阚小勇 | Making method of epoxy resin adhesive for building |
| US20110086956A1 (en) * | 2006-11-27 | 2011-04-14 | Naturalnano, Inc. | Nanocomposite master batch composition and method of manufacture |
| CN102079957A (en) * | 2010-12-09 | 2011-06-01 | 深圳市库泰克电子材料技术有限公司 | Low-temperature rapidly-curable surface mounting adhesive |
| CN102964777A (en) * | 2012-11-27 | 2013-03-13 | 上海南亚覆铜箔板有限公司 | Phosphorus-containing and halogen-free flame retardant resin adhesive as well as preparation method and application thereof |
| CN103788576A (en) * | 2013-12-02 | 2014-05-14 | 上海南亚覆铜箔板有限公司 | Epoxy resin composition and preparation method thereof |
| CN105176484A (en) * | 2015-09-02 | 2015-12-23 | 中国科学院电工研究所 | Potting adhesive for power electronic devices, and preparation method thereof |
| CN106084277A (en) * | 2016-06-17 | 2016-11-09 | 江苏科技大学 | A kind of porous material of split-phase synthesis and preparation method thereof |
| WO2018100798A1 (en) * | 2016-11-30 | 2018-06-07 | 東洋ゴム工業株式会社 | Sensor for detecting deformation of sealed secondary cell, sealed secondary cell, and method for detecting deformation of sealed secondary cell |
-
2018
- 2018-06-25 CN CN201810663197.5A patent/CN109082253A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59193936A (en) * | 1983-04-19 | 1984-11-02 | Sumitomo Alum Smelt Co Ltd | Filler for resin |
| CN1334281A (en) * | 2001-06-15 | 2002-02-06 | 华中科技大学 | Process for preparing inorganic filler reinforced polymer composite material |
| CN1570010A (en) * | 2004-04-23 | 2005-01-26 | 阚小勇 | Making method of epoxy resin adhesive for building |
| US20110086956A1 (en) * | 2006-11-27 | 2011-04-14 | Naturalnano, Inc. | Nanocomposite master batch composition and method of manufacture |
| CN102079957A (en) * | 2010-12-09 | 2011-06-01 | 深圳市库泰克电子材料技术有限公司 | Low-temperature rapidly-curable surface mounting adhesive |
| CN102964777A (en) * | 2012-11-27 | 2013-03-13 | 上海南亚覆铜箔板有限公司 | Phosphorus-containing and halogen-free flame retardant resin adhesive as well as preparation method and application thereof |
| CN103788576A (en) * | 2013-12-02 | 2014-05-14 | 上海南亚覆铜箔板有限公司 | Epoxy resin composition and preparation method thereof |
| CN105176484A (en) * | 2015-09-02 | 2015-12-23 | 中国科学院电工研究所 | Potting adhesive for power electronic devices, and preparation method thereof |
| CN106084277A (en) * | 2016-06-17 | 2016-11-09 | 江苏科技大学 | A kind of porous material of split-phase synthesis and preparation method thereof |
| WO2018100798A1 (en) * | 2016-11-30 | 2018-06-07 | 東洋ゴム工業株式会社 | Sensor for detecting deformation of sealed secondary cell, sealed secondary cell, and method for detecting deformation of sealed secondary cell |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880546A (en) * | 2019-03-14 | 2019-06-14 | 南亚新材料科技股份有限公司 | Barium sulfate filler slurry of polymolecularity applied to copper-clad plate and preparation method thereof |
| CN109912932A (en) * | 2019-03-14 | 2019-06-21 | 南亚新材料科技股份有限公司 | A kind of halogen-free adhesive of high CTI value and its preparation method and application |
| CN112760071A (en) * | 2021-01-22 | 2021-05-07 | 东莞市派乐玛新材料技术开发有限公司 | Sealant and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109082253A (en) | A kind of halogen-free adhesive of polymolecularity and preparation method thereof | |
| KR100961417B1 (en) | High-stability microencapsulated hardener for epoxy resin and epoxy resin composition | |
| KR100976303B1 (en) | Microcapsule type hardener for epoxy resin, masterbatch type hardener composition for epoxy resin, one-pack type epoxy resin composition, and processed article | |
| TWI531610B (en) | Thermal curable resin composition, fabricating method of resin composition varnish, perpreg and laminated board | |
| JP5763527B2 (en) | Imidazole compound-containing microencapsulated composition, curable composition using the same, and masterbatch type curing agent | |
| JP6484446B2 (en) | Curing agent for epoxy resin, epoxy resin composition and material containing the same | |
| JP5558118B2 (en) | Microcapsule type epoxy resin curing agent and masterbatch type epoxy resin curing agent composition containing the same | |
| CN108431133B (en) | Resin combination, prepreg, clad with metal foil plywood, resin sheet and printed circuit board | |
| KR20130141449A (en) | Resin composition, prepreg, and laminate | |
| CN102732096A (en) | Halogen-free flame-retardant solvent-free double-curing ink composition and preparation method thereof | |
| KR20140007819A (en) | Resin composition, prepreg and laminate | |
| WO2021192680A1 (en) | Resin composition, prepreg, resin sheet, laminate board, metal foil-clad laminate board, and printed wiring board | |
| US20220363539A1 (en) | Method for producing hexagonal boron nitride powder, and hexagonal boron nitride powder | |
| KR102393446B1 (en) | Zinc ammonium molybdate hydrate for electronic materials, resin compositions for electronic materials, prepregs, resin sheets, laminates, metal foil-clad laminates, and printed wiring boards | |
| CN101842407B (en) | Method for producing latent curing agent for powder epoxy resin, latent curing agent for powder epoxy resin obtained by the method, and curable epoxy resin composition using the same | |
| CN104628996A (en) | Flame retardant with bisphenol F group, flame-retardant epoxy resin and flame-retardant composition | |
| CN100369964C (en) | Resin composition, prepreg and laminate using the composition | |
| CN109912932A (en) | A kind of halogen-free adhesive of high CTI value and its preparation method and application | |
| WO2019208476A1 (en) | Resin composition, resin film, metal foil with resin, prepreg, metal-clad laminate and printed wiring board | |
| CN109880546A (en) | Barium sulfate filler slurry of polymolecularity applied to copper-clad plate and preparation method thereof | |
| CN104628997A (en) | Flame-retardant substance with bisphenol S group, flame-retardant epoxy resin and flame-retardant composition | |
| JP4301044B2 (en) | Prepreg and laminate manufacturing method | |
| EP3597688B1 (en) | Thermosetting resin composition | |
| KR101696484B1 (en) | Sizing Agent for Carbon Fiber, Aqueous Dispersion Thereof, Carbon Fiber Treated by Sizing and Sheet-Form Object Comprising the Carbon Fiber | |
| JP5176968B2 (en) | Manufacturing method of substrate with resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for 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: 20181225 |