CN109627408A - A kind of preparation method of the Nitrogen-containing Phenolic Resins for high Tg halogen-free copper-clad plate - Google Patents
A kind of preparation method of the Nitrogen-containing Phenolic Resins for high Tg halogen-free copper-clad plate Download PDFInfo
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- CN109627408A CN109627408A CN201811524745.2A CN201811524745A CN109627408A CN 109627408 A CN109627408 A CN 109627408A CN 201811524745 A CN201811524745 A CN 201811524745A CN 109627408 A CN109627408 A CN 109627408A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
- C08G14/10—Melamines
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
- C08G14/08—Ureas; Thioureas
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- 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
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- 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
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention belongs to copper-clad plate preparation technical field more particularly to a kind of preparation methods of the Nitrogen-containing Phenolic Resins for high Tg halogen-free copper-clad plate.The method that the present invention carries out synthetic high polymer using first subsection synthesis oligomer, again, the resinamines of formation contain the phenolic resin block structure of high rigidity long-chain, reduce resin polarity;The molecular weight (Mw) of Nitrogen-containing Phenolic Resins obtained is in 700-1500, nitrogen content is in 8-20%, it is sufficiently dissolved using solvent, production for halogen-free copper-clad plate, it can be used as the curing agent of phosphorous epoxy resin, the performance of gained copper-clad plate is uniform, Tg180 or more, and heat resistance T288 is about 10min;The melamine modified phenolic resin that gained Nitrogen-containing Phenolic Resins of the invention produce in performance better than Japan, while reducing cost, it is thus also avoided that technology blockage.
Description
Technical field
The invention belongs to copper-clad plate preparation technical field more particularly to a kind of nitrogenous phenolic aldehyde for high Tg halogen-free copper-clad plate
The preparation method of resin.
Background technique
Copper-clad plate is the important materials of printed circuit board industry, and anti-flammability is the basic demand of safe handling, needs to reach
FV0Grade.The production of major part copper-clad plate at present is fire-retardant using halogen containing flame-retardant progress, but combustion process can generate dioxin etc.
Harmful carcinogen, pollutes the environment.As environmental requirement increasingly improves, the production of part copper-clad plate is by original halogen
Fire retardant is changed to phosphorous flame-retardant and nitrogen-phosphorus cooperative flame retardant.
Currently, 90% or more halogen-free copper-clad plate is to solidify phosphorous epoxy resin with phosphorus containing phenolic resin, reach FV0, this
Kind method is at high cost, and Tg150 or so, heat resistance T288 is about 5min;A small amount of halogen-free copper-clad plate is phosphorous with dicyandiamide cure
Based on epoxy resin, addition partial phosphate ester, phosphorous organic filler reach FV0, such method performance is minimum, and Tg is resistance to less than 140
Hot T288 is about 2min, can not meet PCB leadless process;A small amount of high-end halogen-free copper-clad plate is contained with a of Japanese DIC
Nitrogen phenolic resin curing phosphorous epoxy resin reaches FV0, Tg160 or so, heat resistance T288 are about 6min, existing for such method
Problem is that, first is that the synthetic technology of Nitrogen-containing Phenolic Resins is DIC patent, technical know-how, production is with being limited, second is that this tree
Rouge can only dissolve in methanol, DMF isopolarity solvent, and the solubility in ketones solvent is low, when being used in mixed way with epoxy resin
Dispersion effect it is poor, copper-clad plate performance is inhomogenous.
Summary of the invention
The present invention in view of the deficiency of the prior art, provides a kind of nitrogenous phenolic aldehyde for high Tg halogen-free copper-clad plate
The preparation method of resin.
The technical scheme to solve the above technical problems is that a kind of nitrogenous phenolic aldehyde for high Tg halogen-free copper-clad plate
The preparation method of resin, steps are as follows:
(1) low molecule linear phenolic resin is synthesized
By phenolic substances and aldehyde material according to molar ratio for weakly acidic aqueous solution is added in 1:(1-1.2) investment reaction kettle,
Adjustment pH value is 5-7;Heat temperature raising is warming up to 65-75 DEG C with the heating rate of 2-3 DEG C/min, after stopping heating, voluntarily reacts
Exotherm reacts 30-50min under the conditions of 95-100 DEG C to 90-95 DEG C;After reaction, it is cooled in 10-30min
40 DEG C hereinafter, spare;
(2) low molecule Nitrogen-containing Phenolic Resins are synthesized
Phenolic substances, aldehyde material and nitrogenous compound is anti-for (0.1-0.3): 6:(1-1.5) investment according to molar ratio
It answers in kettle;Weak base aqueous solution is added, adjustment pH value is 7-8;Heat temperature raising is warming up to 65-75 with the heating rate of 2-3 DEG C/min
DEG C, after stopping heating, voluntarily exothermic heat of reaction is warming up to 80-90 DEG C, reacts 20-30min under the conditions of 80-90 DEG C;Reaction terminates
Afterwards, 40 DEG C are cooled in 5-20min hereinafter, spare;
(3) high Tg halogen-free copper-clad plate Nitrogen-containing Phenolic Resins are synthesized
Take 30-50 parts of the low molecule linear phenolic resin of step (1), the low molecule Nitrogen-containing Phenolic Resins 30-50 of step (2)
Part and phenolic substances 0-5 parts of addition reaction kettle, add weakly acidic aqueous solution, and adjustment pH value is 5-7;Heat temperature raising, with 2-5 DEG C/
The heating rate of min is warming up to 95-100 DEG C, reacts 40-60min under the conditions of 95-100 DEG C;Reaction terminates, and negative-pressure vacuum is de-
The cooling dissolution of 20-50 part solvents is added when the water content of resin is less than 2wt% in water, obtained to be used to prepare high Tg Halogen and cover copper
The Nitrogen-containing Phenolic Resins of plate.
Further, the phenolic substances be phenol, bisphenol-A, naphthols, Bisphenol F, o-cresol, m-cresol, to toluene
Phenol, Resorcino mix one or more of biphenol;
The aldehyde material is formalin (formalin that concentration is 36.5-38%), metaformaldehyde, poly first
The mixing of one or more of aldehyde, acetaldehyde, propionic aldehyde, butyraldehyde or furfural;
The weakly acidic aqueous solution is the mixing of one or more of ethanedioic acid, acetic acid, benzene sulfonic acid or salicylic acid;
The nitrogenous compound is the mixing of one or more of melamine, guanamines or urea;
The weak base aqueous solution is one of ammonium hydroxide, triethylamine, diethylamine, barium hydroxide, pyridine or piperidines or two
Kind or more mixture;
The solvent is one or more of ketone, alcohols, benzene class, ethers or DMF mixing.
The features of the present invention and beneficial effect are:
The method that the present invention carries out synthetic high polymer using first subsection synthesis oligomer, again, the resinamines of formation contain
The phenolic resin block structure of high rigidity long-chain reduces resin polarity;The molecular weight (Mw) of Nitrogen-containing Phenolic Resins obtained exists
700-1500, nitrogen content are sufficiently dissolved in 8-20%, using solvent, for the production of halogen-free copper-clad plate, can be used as phosphorous ring
The performance of the curing agent of oxygen resin, gained copper-clad plate is uniform, Tg180 or more, and heat resistance T288 is about 10min;Gained of the invention
Nitrogen-containing Phenolic Resins, better than the melamine modified phenolic resin of Japan's production, while reducing cost, also avoid in performance
Technology blockage.
Specific embodiment
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
Embodiment 1
A kind of preparation method of the Nitrogen-containing Phenolic Resins for high Tg halogen-free copper-clad plate, steps are as follows:
(1) low molecule linear phenolic resin is synthesized
Phenol and formalin substance are put into reaction kettle according to molar ratio for 1:1.1, ethanedioic acid is added, adjusts pH value
For 5-7;Heat temperature raising is warming up to 70 DEG C with the heating rate of 2-3 DEG C/min, and after stopping heating, voluntarily exothermic heat of reaction is warming up to
90-95 DEG C, 40min is reacted under the conditions of 95-100 DEG C;After reaction, 40 DEG C are cooled in 10-30min hereinafter, spare;
(2) low molecule Nitrogen-containing Phenolic Resins are synthesized
Phenol, formalin and melamine are put into reaction kettle according to molar ratio for 0.2:6:1.3;Ammonium hydroxide is added,
Adjustment pH value is 7-8;Heat temperature raising is warming up to 72 DEG C with the heating rate of 2-3 DEG C/min, and after stopping heating, voluntarily reaction is put
Heat is warming up to 80-90 DEG C, reacts 26min under the conditions of 80-90 DEG C;After reaction, be cooled in 5-20min 40 DEG C with
Under, it is spare;
(3) high Tg halogen-free copper-clad plate Nitrogen-containing Phenolic Resins are synthesized
Take 40 parts of the low molecule linear phenolic resin of step (1), 40 parts of the low molecule Nitrogen-containing Phenolic Resins of step (2) and phenol
3 parts of addition reaction kettles of substance, add ethanedioic acid, and adjustment pH value is 5-7;Heat temperature raising, with the heating rate of 2-5 DEG C/min
95 DEG C are warming up to, reacts 40-60min under the conditions of 95 DEG C;Reaction terminates, negative-pressure vacuum dehydration, when the water content of resin is less than
When 2wt%, 20 parts of methanol cooling dissolutions are added, the Nitrogen-containing Phenolic Resins for being used to prepare high Tg halogen-free copper-clad plate are made.
Embodiment 2
A kind of preparation method of the Nitrogen-containing Phenolic Resins for high Tg halogen-free copper-clad plate, steps are as follows:
(1) low molecule linear phenolic resin is synthesized
Bisphenol-A and furfural are put into reaction kettle according to molar ratio for 1:1.2, salicylic acid is added, adjustment pH value is 5-7;
Heat temperature raising is warming up to 75 DEG C with the heating rate of 2-3 DEG C/min, and after stopping heating, voluntarily exothermic heat of reaction is warming up to 90-95
DEG C, 50min is reacted under the conditions of 95-100 DEG C;After reaction, 40 DEG C are cooled in 10-30min hereinafter, spare;
(2) low molecule Nitrogen-containing Phenolic Resins are synthesized
Bisphenol-A, furfural and urea are put into reaction kettle according to molar ratio for 0.1:6:1;Weak pyridine is added, adjusts pH value
For 7-8;Heat temperature raising is warming up to 65-75 DEG C with the heating rate of 2-3 DEG C/min, and after stopping heating, voluntarily exothermic heat of reaction heats up
To 80-90 DEG C, 30min is reacted under the conditions of 80-90 DEG C;After reaction, 40 DEG C are cooled in 5-20min hereinafter, spare;
(3) high Tg halogen-free copper-clad plate Nitrogen-containing Phenolic Resins are synthesized
Take 50 parts of the low molecule linear phenolic resin of step (1), 50 parts of low molecule Nitrogen-containing Phenolic Resins additions of step (2)
Reaction kettle, adds salicylic acid, and adjustment pH value is 5-7;Heat temperature raising is warming up to 98 DEG C with the heating rate of 2-5 DEG C/min,
40-60min is reacted under the conditions of 98 DEG C;Reaction terminates, and negative-pressure vacuum dehydration is added 40 when the water content of resin is less than 2wt%
Part acetone cooling dissolution, is made the Nitrogen-containing Phenolic Resins for being used to prepare high Tg halogen-free copper-clad plate.
Application examples 1
A kind of high Tg halogen-free copper-clad plate, ingredient include: 100 parts of phosphorous epoxy resin, embodiment 1 in parts by weight
2 parts of 15 parts of 5 parts of 50 parts of Nitrogen-containing Phenolic Resins, tetrafunctional epoxy resin, bisphenol A type epoxy resin, the aluminium hydroxide of middle preparation, third
40 parts and 0.08 part of imidazoles of ketone.
Said components are taken, according to glass cloth base (FR-4) production method, the 1.0mm copper-clad plate of system.
The performance test of gained copper-clad plate is shown in Table 1.
Comparative example 1
A kind of copper-clad plate, ingredient include: 100 parts of phosphorous epoxy resin, 2.2 parts of dicyandiamide, four in parts by weight
5 parts of functional epoxy resins, 15 parts of bisphenol A type epoxy resin, 2 parts, DMF40 parts and 0.1 part of imidazoles of aluminium hydroxide.
Said components are taken, according to glass cloth base (FR-4) production method, the 1.0mm copper-clad plate of system.
The performance test of gained copper-clad plate is shown in Table 1.
Comparative example 2
A kind of copper-clad plate, ingredient include: 100 parts of phosphorous epoxy resin, Nitrogen-containing Phenolic Resins (day in parts by weight
This DIC705) 50 parts, 5 parts of tetrafunctional epoxy resin, 15 parts of bisphenol A type epoxy resin, 2 parts of aluminium hydroxide, propylene glycol monomethyl ether
40 parts and 0.1 part of imidazoles.
Said components are taken, according to glass cloth base (FR-4) production method, the 1.0mm copper-clad plate of system.
The performance test of gained copper-clad plate is shown in Table 1.
Table 1
Test item | Application examples 1 | Comparative example 1 | Comparative example 2 |
Glass transition temperature Tg (DSC)/DEG C | 170 | 140 | 160 |
Thermally stratified layer T300/min | 30 | 5 | 16 |
Td thermal decomposition temperature/DEG C | 385 | 330 | 360 |
288 DEG C/min of soldering resistance | 30 | 2 | 20 |
Flammability | FV-0 | FV-0 | FV-0 |
Peel strength (18 μm) N/mm | 1.63 | 1.4 | 1.43 |
Water absorption rate % | 0.08 | 0.12 | 0.1 |
Surface resistivity/M Ω | 5×105 | 4×105 | 4.5×105 |
Dielectric constant (1GHz) | 4.05 | 4.2 | 4.1 |
Seen from table 1, compared to comparative example 1 and comparative example 2, preparation is participated in by Nitrogen-containing Phenolic Resins prepared by the present invention
Copper-clad plate, in addition to water absorption rate, dielectric constant are close, other properties, which have, significantly to be promoted.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (2)
1. a kind of preparation method of the Nitrogen-containing Phenolic Resins for high Tg halogen-free copper-clad plate, which is characterized in that steps are as follows:
(1) low molecule linear phenolic resin is synthesized
In 1:(1-1.2) investment reaction kettle, weakly acidic aqueous solution, adjustment is added according to molar ratio in phenolic substances and aldehyde material
PH value is 5-7;Heat temperature raising is warming up to 65-75 DEG C with the heating rate of 2-3 DEG C/min, stops after heating, voluntarily exothermic heat of reaction
It is warming up to 90-95 DEG C, reacts 30-50min under the conditions of 95-100 DEG C;After reaction, 40 DEG C are cooled in 10-30min
Hereinafter, spare;
(2) low molecule Nitrogen-containing Phenolic Resins are synthesized
Phenolic substances, aldehyde material and nitrogenous compound are put into reaction kettle according to molar ratio for (0.1-0.3): 6:(1-1.5)
In;Weak base aqueous solution is added, adjustment pH value is 7-8;Heat temperature raising is warming up to 65-75 DEG C with the heating rate of 2-3 DEG C/min,
After stopping heating, voluntarily exothermic heat of reaction is warming up to 80-90 DEG C, reacts 20-30min under the conditions of 80-90 DEG C;After reaction,
40 DEG C are cooled in 5-20min hereinafter, spare;
(3) high Tg halogen-free copper-clad plate Nitrogen-containing Phenolic Resins are synthesized
Take 30-50 parts of the low molecule linear phenolic resin of step (1), step (2) 30-50 parts of low molecule Nitrogen-containing Phenolic Resins and
0-5 parts of addition reaction kettles of phenolic substances, add weakly acidic aqueous solution, and adjustment pH value is 5-7;Heat temperature raising, with 2-5 DEG C/min's
Heating rate is warming up to 95-100 DEG C, reacts 40-60min under the conditions of 95-100 DEG C;Reaction terminates, negative-pressure vacuum dehydration, when
When the water content of resin is less than 2wt%, 20-50 parts of solvent cooling dissolutions are added, is made and is used to prepare high Tg halogen-free copper-clad plate
Nitrogen-containing Phenolic Resins.
2. preparation method according to claim 1, which is characterized in that the phenolic substances be phenol, bisphenol-A, naphthols,
Bisphenol F, o-cresol, m-cresol, p-cresol, Resorcino mix one or more of biphenol;
The aldehyde material be formalin (formalin that concentration is 36.5-38%), metaformaldehyde, paraformaldehyde,
The mixing of one or more of acetaldehyde, propionic aldehyde, butyraldehyde or furfural;
The weakly acidic aqueous solution is the mixing of one or more of ethanedioic acid, acetic acid, benzene sulfonic acid or salicylic acid;
The nitrogenous compound is the mixing of one or more of melamine, guanamines or urea;
The weak base aqueous solution be one or both of ammonium hydroxide, triethylamine, diethylamine, barium hydroxide, pyridine or piperidines with
Upper mixture;
The solvent is one or more of ketone, alcohols, benzene class, ethers or DMF mixing.
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CN113088032A (en) * | 2021-03-25 | 2021-07-09 | 建滔(佛冈)积层纸板有限公司 | Linear phenolic resin and method for manufacturing high-performance halogen-free environment-friendly paper-based copper-clad plate by using same |
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JPH04209647A (en) * | 1990-12-03 | 1992-07-31 | Toshiba Chem Corp | Phenolic resin composition and copper-clad laminate |
JP2000239335A (en) * | 1999-02-25 | 2000-09-05 | Sumitomo Durez Co Ltd | High-density cured spherical phenolic resin |
JP2000290490A (en) * | 1999-04-01 | 2000-10-17 | Asahi Chem Ind Co Ltd | Flame retardant curable resin composition |
JP2002363259A (en) * | 2001-06-04 | 2002-12-18 | Mitsubishi Gas Chem Co Inc | Flame-retardant resin composition |
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CN104085155A (en) * | 2014-07-16 | 2014-10-08 | 山东金宝电子股份有限公司 | Preparation method of Fv0-grade flame-retardant paper-base copper clad plate |
CN106739372A (en) * | 2016-11-26 | 2017-05-31 | 山东金宝科创股份有限公司 | A kind of Halogen, without phosphorus, environment friendly flame-retardant composite-based copper clad plate preparation method |
Cited By (1)
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CN113088032A (en) * | 2021-03-25 | 2021-07-09 | 建滔(佛冈)积层纸板有限公司 | Linear phenolic resin and method for manufacturing high-performance halogen-free environment-friendly paper-based copper-clad plate by using same |
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