CN109306149A - It is a kind of have halogen without antimony resin combination, using its prepreg, laminate and printed circuit board - Google Patents
It is a kind of have halogen without antimony resin combination, using its prepreg, laminate and printed circuit board Download PDFInfo
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- CN109306149A CN109306149A CN201811160775.XA CN201811160775A CN109306149A CN 109306149 A CN109306149 A CN 109306149A CN 201811160775 A CN201811160775 A CN 201811160775A CN 109306149 A CN109306149 A CN 109306149A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/12—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
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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
- 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
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/06—Layered products comprising a layer of paper or cardboard specially treated, e.g. surfaced, parchmentised
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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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
- B32B2260/028—Paper 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
- 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
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- 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
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provide it is a kind of have halogen without antimony resin combination, using its prepreg, laminate and printed circuit board, it is described to there is halogen to comprise the following components in parts by weight without antimony resin combination: the non-flame resistant type epoxy resin of 25~70 parts by weight fire-retardant epoxy resins, 10~40 parts by weight, 20~60 parts by weight curing agent, 0.05~1.0 parts by weight curing accelerator；The fire-retardant epoxy resin includes the composition of phosphorous epoxy resin, brominated epoxy resin and nitrogen-containing epoxy thermoset three.Cooperated using fire-retardant epoxy resin and non-flame resistant type epoxy resin, the cooperation of especially three kinds fire-retardant epoxy resins, make it possible to reach the bromo- phosphorus-nitrogen coordinated fire-retardant effect of phosphorus-, CEM-1 copper-clad laminate is assigned with good anti-flammability, broken tradition have in halogen CEM-1 copper-clad laminate halogen antimony cooperative flame retardant system can not substituted technical bottleneck, also have a comprehensive performance advantage outstanding such as high heat resistance, high wet-heat resisting.
Description
Technical field
The invention belongs to technical field of laminates, it is related to a kind of having halogen without antimony resin combination, the prepreg using it, layer
Pressing plate and printed circuit board.
Background technique
CEM-1 copper-clad laminate be using electronic-grade glass fiber cloth and bleached wood pulp paper as reinforcing material, be soaked respectively with
Fabric and core material is made in copper-clad laminate resin combination, and coated with copper foil, forms through hot pressing.Anti-flammability is that CEM-1 covers
The primary performance that copper-clad laminate must reach, but CEM-1 copper-clad laminate is the wood pulp paper using wood pulp paper bonding sheet as core material
Itself is flammable, to guarantee other performances of CEM-1 copper-clad laminate, the especially performances such as heat resistance, toughness, moisture resistance
Under the premise of, the anti-flammability for improving CEM-1 copper-clad laminate is difficult.Currently, there is the fire-retardant of halogen CEM-1 copper-clad laminate
Property relies primarily on halogen antimony composite flame retardant system and is achieved.
But according to the information of European Union ROHS, European Union's RHOS advisory organization on April 20th, 2018 refers to for ROHS in Pack15
It enables appendix II limitation substance evaluation revision initiate first time public consultation, seeks advice from 8 weeks by a definite date, cut on June 15th, 2018
Only, this consulting is related to seven substances and now related side is required to submit correlative within the consultation period wherein including antimony oxide
The technology evidence of matter includes the case where the use data and potential substitute of substance.
CN103804819A discloses one kind without antimony flame retardant composite material, while being related to a kind of gathering for not antimony containing compounds
Vinyl chloride resin composition, it is environmentally protective, and the balance for realizing anti-flammability, heat resistance, cold resistance and electrical insulating property is excellent
It is different.The flame retarding function of this scheme mainly passes through addition montmorillonite, hydrotalcite, magnalium flame retardant, silicone flame retardant, nitrogen phosphorus
Flame retardant, phosphate ester flame retardants are achieved, while being added to a large amount of nanon calcium carbonatefilled agent, and calcium carbonate acid and alkali-resistance
Property is poor, will affect the processability in plate later period in copper-clad laminate.In addition, the patent is primarily related to engineering thermoplastic
Cable in plastics cable material field, it is little with copper-clad laminate (thermosetting material) technical field correlation.
CN103764739A disclose by by the polyphenylene ether flame retardant of a kind of fluoropolymer resin, certain halogenations and
A kind of non-brominated phenoxy group oligomer or combination of polymers prepare the flame-retardant polymer of no antimony, this quasi polymer has excellent
Anti-flammability and excellent physical characteristic.But the patent is primarily related to thermoplastic technical field, with copper foil covered pressure
Plate (thermosetting material) technical field correlation is little.
There is halogen without antimony CEM-1 copper-clad laminate therefore, it is necessary to developing one kind and meets international newest environmental legislation pair
The environmental requirement of electronic product.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide one kind to have halogen without antimony resin combination, uses it
Prepreg, laminate and printed circuit board.
To achieve this purpose, the present invention adopts the following technical scheme:
On the one hand, the present invention, which provides one kind, has halogen without antimony resin combination, it is described have halogen without antimony resin combination include with
The component of lower parts by weight:
The non-flame resistant type epoxy resin of 25~70 parts by weight fire-retardant epoxy resins, 10~40 parts by weight, 20~60 parts by weight
Curing agent, 0.05~1.0 parts by weight curing accelerator；
The fire-retardant epoxy resin includes the group of phosphorous epoxy resin, brominated epoxy resin and nitrogen-containing epoxy thermoset three
Close object.
In the present invention, described to have halogen without in antimony resin combination, utilize fire-retardant epoxy resin and non-flame resistant type ring oxygen
Resin is cooperated, especially fire-retardant epoxy resin selection brominated epoxy resin, phosphorous epoxy resin and nitrogen-containing epoxy thermoset
Three's cooperation, makes it possible to reach the bromo- phosphorus-nitrogen coordinated fire-retardant effect of phosphorus-, can assign CEM-1 copper-clad laminate with good resistance
Combustion property, having broken tradition has in halogen CEM-1 copper-clad laminate that halogen antimony cooperative flame retardant system can not substituted technical bottleneck.
In the present invention, the fire-retardant epoxy resin refers in particular to the epoxy resin with anti-flammability containing phosphorus, bromine or nitrogen,
The non-flame resistant type epoxy resin refers in particular to the epoxy resin without containing phosphorus, bromine or nitrogen.
In the present invention have halogen without in antimony resin combination, the content of the fire-retardant epoxy resin can be 25 weight
Part, 28 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65
Parts by weight or 70 parts by weight.
Fire-retardant epoxy resin in the present invention, simultaneously contain reactive group and fire-retardant group, play cross-linking reaction and
Fire-retardant double action；If its dosage is insufficient, fire-retardant group is reduced, and will have a direct impact on anti-flammability；If its dosage is excessive, reactive group
Group and fire-retardant group increase, and anti-flammability improves, but fire-retardant epoxy resin reactivity itself is lower, and excessive response group cannot
Cross-linking reaction is participated in completely, thus will affect heat resistance, Gu its dosage must satisfy reaction completely and preferably fire-retardant two aspect.
Preferably, phosphorous epoxy resin in the fire-retardant epoxy resin, brominated epoxy resin and nitrogen-containing epoxy thermoset
Weight ratio be (1.3~1.5): (1.5~1.75): (1~1.2), such as 1.3:1.5:1,1.3:1.55:1,1.3:1.6:1.1,
1.3:1.75:1.2、1.35:1.5:1.2、1.4:1.6:1.1、1.4:1.75:1.2、1.5:1.5:1、1.5:1.6:1、1.5:
1.75:1.1,1.5:1.75:1.2,1.5:1.5:1.2,1.5:1.65:1.1 etc..
Fire-retardant epoxy resin with above range weight ratio can effectively improve the anti-flammability of solidfied material, resistance to immersed solder
Property, heat resistance, also available relatively low water absorption rate.
In the present invention, in the phosphorous epoxy resin phosphorus content be 2%~4%, such as 2%, 2.2%, 2.4%,
2.6%, 2.8%, 3%, 3.3%, 3.5%, 3.8% or 4%.
The phosphorus content of phosphorous epoxy resin is too low in the present invention will affect anti-flammability；Phosphorus content is too high, and resin reaction is living
Property reduce, will affect the crosslink density of solidfied material, and then influence the heat resistance of solidfied material.
In the present invention, in the brominated epoxy resin bromine content be 19%~50%, such as 19%, 20%, 22%,
25%, 28%, 30%, 33%, 35%, 38%, 40%, 43%, 45%, 48% or 50%, preferably 40%~50%.
The bromine content of brominated epoxy resin is too low in the present invention will affect anti-flammability；Bromine content is too high, and resin reaction is living
Property reduce, will affect the crosslink density of solidfied material, and then influence the heat resistance of solidfied material；Meanwhile bromine content is too high can be to resin
It is influenced with the bonding force of copper foil and reinforcing material.
In the present invention, in the nitrogen-containing epoxy thermoset nitrogen content be 5~14%, such as 5%, 6%, 7%, 8%, 9%,
10%, 11%, 12%, 13% or 14%.
The nitrogen content of nitrogen-containing epoxy thermoset is too low in the present invention will affect anti-flammability；Nitrogen content is too high, and resin reaction is living
Property reduce, will affect the crosslink density of solidfied material, and then influence the heat resistance of solidfied material.
Preferably, the phosphorous epoxy resin is DOPO base epoxy, ODOPB base epoxy, three phosphonitrile basic ring of ring
In oxygen resin or diphenyl phosphate oxidation epoxy resin any one or at least two combination.
Preferably, the brominated epoxy resin is BPA (bis-phenol base propane) epoxy resin, BPF epoxy resin (bisphenol-f type
Epoxy resin) or novolac epoxy resin in any one or at least two combination.
Preferably, the nitrogen-containing epoxy thermoset is glycidyl amine epoxy resin, para-aminophenol epoxy resin, diamino
Diphenyl-methane epoxy resin, poly-isocyanurate-oxazole alkanoic acid epoxy resin, cyanic acid ester epoxy resin, cyanuric acid three shrink
Glyceramine epoxy resin, the cyanuric acid three-glycidyl amine epoxy resin or nitrogenous novolac epoxy resin that triazine ring is nuclear skeleton
In any one or at least two combination.
Preferably, the epoxide equivalent of the fire-retardant epoxy resin is 100g/eq~800g/eq.Such as 100g/eq,
130g/eq、150g/eq、180g/eq、200g/eq、230g/eq、250g/eq、280g/eq、300g/eq、350g/eq、400g/
Eq, 450g/eq, 500g/eq, 550g/eq, 600g/eq, 650g/eq, 700g/eq, 750g/eq or 800g/eq, preferably 100g/
Eq~500g/eq.
In the present invention, fire-retardant epoxy resin plays cross-linking reaction and fire-retardant double action, due to fire-retardant group
In the presence of the reactivity of resin itself is slightly lower, so preferred 100g/eq~500g/eq is advisable when selecting equivalent.
There is halogen without in antimony resin combination in of the invention, the content of the non-flame resistant type epoxy resin can be 10 weight
Part, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 33
Parts by weight, 35 parts by weight, 38 parts by weight or 40 parts by weight.
Non-flame resistant type epoxy resin in the present invention is the higher polyfunctional epoxy resin of reactivity, in resin combination
Main function in object is to improve solidfied material molecular backbone rigidity and crosslink density, the final heat resistance for improving solidfied material.If its
Dosage is very few, can not just effectively improve the heat resistance of solidfied material；If its dosage is excessive, it will lead to the increase of solidfied material brittleness, glue
Conjunction property reduces.
Preferably, the non-flame resistant type epoxy resin is two functional epoxy resins, trifunctional epoxy resin or tetrafunctional ring
In oxygen resin any one or at least two combination.
Preferably, the non-flame resistant type epoxy resin is bisphenol A type epoxy resin (such as bisphenol A-type epoxy novolac tree
Rouge), bisphenol f type epoxy resin, biphenyl type epoxy resin, alkyl phenol epoxy resin, DCPD-containing epoxy resin, triphenol type ring
In oxygen resin, o-cresol type novolac epoxy resin or phenol type novolac epoxy resin any one or at least two combination.
Preferably, the epoxide equivalent of the non-flame resistant type epoxy resin be 100g/eq~800g/eq, such as 100g/eq,
130g/eq、150g/eq、180g/eq、200g/eq、230g/eq、250g/eq、280g/eq、300g/eq、350g/eq、400g/
Eq, 450g/eq, 500g/eq, 550g/eq, 600g/eq, 650g/eq, 700g/eq, 750g/eq or 800g/eq, preferably 100g/
Eq~300g/eq.
In the present invention, non-flame resistant type epoxy resin is the higher polyfunctional epoxy resin of reactivity, and main function is
Solidfied material molecular backbone rigidity and crosslink density are improved, so cannot be too big when selecting equivalent, preferably 100g/eq~300g/
Eq is advisable.
There is halogen without in antimony resin combination in of the invention, the content of the curing agent can be 20 parts by weight, 23 weight
Part, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 45 parts by weight, 48 parts by weight, 50
Parts by weight, 55 parts by weight, 58 parts by weight or 60 parts by weight.
Preferably, the curing agent is linear phenolic resin class curing agent.
Preferably, the linear phenolic resin class curing agent is phenol type phenolic resin, bisphenol A type phenolic resin, adjacent first
In phenolic phenolic resin, triphenol phenolic resin, naphthalene type phenolic resin, biphenyl type phenolic resin or dicyclopentadiene phenolic resin
Any one or at least two combination.
Preferably, the phenolic hydroxyl equivalent of the linear phenolic resin class curing agent is 100~700g/eq, such as 100g/
eq、120g/eq、150g/eq、180g/eq、200g/eq、230g/eq、250g/eq、280g/eq、300g/eq、350g/eq、
400g/eq, 450g/eq, 500g/eq, 550g/eq, 600g/eq, 650g/eq or 700g/eq, preferably 100~250g/eq.
Curing agent in the present invention is only common linear phenolic resin, and cross linking of epoxy resin is made to be formed by curing net vertical
The dosage of body structure, curing agent not only influences solidification rate, has an effect on the performance of product after solidifying, and hardener dose must satisfy
Epoxy group all participates in reaction, could obtain ideal effect.
Have halogen without in antimony resin combination of the invention, the content of the curing accelerator can for 0.05 parts by weight,
0.08 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 weight
Measure part, 0.8 parts by weight, 0.9 parts by weight or 1 parts by weight.
Preferably, the curing accelerator is tertiary amine, three-level phosphine, metal-organic complex, quaternary ammonium salt or imidazoles
Close object in any one or at least two combination.
Preferably, the glyoxaline compound is 2-methylimidazole, -4 methylimidazole of 2- ethyl, 2- phenylimidazole, 2- benzene
In -4 methylimidazole of base or 1- 1-cyanoethyl-2-methylimidazole any one or at least two mixture.
In the present invention, curing accelerator additive amount should not be excessive, will excessively will lead to the reaction of epoxy resin component
Fastly, by-product can be excessive, and the reduced performance of cured product, craftsmanship is deteriorated；If curing accelerator dosage it is very few, if reacted
Slowly, it is unfavorable for the production of prepreg, should ensure that the gelation time of glue should be 100~300s.
It is preferably, described that have halogen without antimony resin combination also include filler.
Preferably, the filler is aluminium hydroxide, aluminium oxide, magnesium hydroxide, magnesia, alchlor, silica, carbon
Sour calcium, aluminium nitride, boron nitride, silicon carbide, titanium dioxide, zinc borate, zinc molybdate, barium metaborate, zinc sulphide, alumina silicate, oxidation
In zinc, zirconium oxide, mica, boehmite, talcum powder, CaCl2 or kaolin any one or at least two combination.
On the other hand, the present invention provides a kind of resin adhesive liquid, and the resin adhesive liquid is that have halogen without antimony tree as described above
Oil/fat composition is dissolved or dispersed in solvent and obtains.
Preferably, the solvent is the solvent that boiling point is 50 DEG C~180 DEG C.The boiling point and paper base bonding sheet half of the solvent
Solidification processing temperature matches, meet the semi-solid preparation stage except solvent requirement, meanwhile, solvent meet to the impregnability of paper base and with
The compatibility of resin.
Preferably, the solvent be methanol, ethyl alcohol, acetone, butanone, ethylene glycol monobutyl ether, methyl acetate, ethyl acetate or
In cyclohexanone any one or at least two mixing.
Preferably, the solid content of the resin adhesive liquid is 60%~80%, particularly preferred 65%~75%, has the range
The impregnability to reinforcing material, available half with high uniformity resin layer thickness can be improved in the resin adhesive liquid of solid content
Cured sheets.
On the other hand, the present invention provides a kind of prepreg, after the prepreg includes reinforcing material and passes through impregnation drying
Attachment thereon as described above have halogen without antimony resin combination.
Preferably, the reinforcing material is wood pulp paper or rag paper.
On the other hand, the present invention provides a kind of laminate, and the laminate includes an at least prepreg as described above.
On the other hand, the present invention provides a kind of metal-clad laminate, and the metal-clad laminate contains at least one
The metal foil of prepreg as described above and the prepreg one or both sides being overlying on after overlapping.
On the other hand, the present invention provides a kind of printed circuit board, and the printed circuit board includes laminate as described above
Or metal-clad laminate.
Compared with the existing technology, the invention has the following advantages:
(1) in the present invention, cooperated using fire-retardant epoxy resin and non-flame resistant type epoxy resin, be can be enhanced
The anti-flammability of CEM-1 copper-clad laminate, resistance to dip solderability, heat resistance, and there is lower water absorption rate；Especially fire-retardant type ring
Brominated epoxy resin, phosphorous epoxy resin and nitrogen-containing epoxy thermoset three cooperation, make it possible to reach the bromo- nitrogen of phosphorus-in oxygen resin
Synergistic flame retardant effect can assign CEM-1 copper-clad laminate with good anti-flammability, and having broken tradition has halogen CEM-1 to cover copper foil
Halogen antimony cooperative flame retardant system can not substituted technical bottleneck in laminate.Halogen antimony composite flame retardant system is converted into no antimony to answer
Flame-retardant system is closed, the antimony containing compounds in halogen CEM-1 copper-clad laminate has been completely removed, has reached international environment regulation pair
The limitation requirement of antimonial.
(2) the CEM-1 copper-clad laminate for having halogen to be prepared without antimony resin combination of the invention, anti-flammability are used
The peer for reaching halogen antimony collaboration system is horizontal, i.e. V-0 grade in UL-94, meanwhile, 288 DEG C of thermal stress are increased to 133~
140s, the halogen antimony collaboration system that compares improve 41%~44%；Water absorption rate is reduced to 0.07%~0.08%, and compare halogen antimony
Collaboration system reduces 38%~46%；T260 is increased to 50~58min, and the halogen antimony collaboration system that compares improves 38%~
47%.Thus this have halogen without antimony CEM-1 copper-clad laminate guarantee it is fire-retardant while, also have high heat resistance, high wet-heat resisting etc. dash forward
Comprehensive performance advantage out.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Examples 1 to 8 and comparative example 1~11
The concrete component and constituent content (in parts by weight) of the resin combination of Examples 1 to 8 and comparative example 1~11 are such as
Shown in Tables 1 and 2.
The concrete component and constituent content of the resin combination of 1 Examples 1 to 8 of table
The concrete component and constituent content of the resin combination of 2 comparative example 1~11 of table
Each component code name and its corresponding ingredient names are as follows in Tables 1 and 2:
A fire-retardant epoxy resin: where phosphorous epoxy resin, brominated epoxy resin and nitrogenous asphalt mixtures modified by epoxy resin in A-1~A-3
The weight ratio of rouge is (1.3:1.5:1)；Weight ratio in A-8 is (1.5:1.75:1.2)；Weight ratio in A-9 be (1.4:
1.6:1.1)；Weight ratio in A-10 is (0.8:2.5:0.5)；
A-1: BPA epoxy resin that DOPO base epoxy that phosphorus content is 3%, bromine content are 48%, nitrogen content 5%
Para-aminophenol epoxy resin three combination；
A-2: BPA epoxy resin that ODOPB base epoxy that phosphorus content is 2%, bromine content are 50%, nitrogen content are
The combination of 6% para-aminophenol epoxy resin three；
A-3: BPA epoxy resin that DOPO base epoxy that phosphorus content is 2.5%, bromine content are 46%, nitrogen content are
The combination of 14% cyanuric acid three-glycidyl amine epoxy resin three；
A-4: the group of both para-aminophenol epoxy resin that BPA epoxy resin that bromine content is 48%, nitrogen content are 5%
It closes；
A-5: the BPA epoxy resin combination that ODOPB base epoxy that phosphorus content is 2%, bromine content are 50%；
A-6: the cyanuric acid three-glycidyl amine that DOPO base epoxy that phosphorus content is 2.5%, nitrogen content are 14%
Epoxy resin combination；
A-7: the BPA epoxy resin that bromine content is 48%；
A-8: BPA epoxy resin that DOPO base epoxy that phosphorus content is 3%, bromine content are 48%, nitrogen content 5%
Para-aminophenol epoxy resin three combination；
A-9: BPA epoxy resin that DOPO base epoxy that phosphorus content is 3%, bromine content are 48%, nitrogen content 5%
Para-aminophenol epoxy resin three combination；
A-10: BPA epoxy resin that DOPO base epoxy that phosphorus content is 3%, bromine content are 48%, nitrogen content are
The combination of 5% para-aminophenol epoxy resin three；
B trifunctional epoxy resin (non-flame resistant type epoxy resin):
B-1: epoxide equivalent is the tris phenol type epoxy of 162g/eq；
B-2: epoxide equivalent is the tris phenol type epoxy of 167g/eq；
B-3: epoxide equivalent is the tris phenol type epoxy of 172g/eq；
C curing agent: phenol Linear phenolic resin.
D curing accelerator: 2-methylimidazole.
E filler:
E-1: magnesium hydroxide；
E-2: antimony oxide；
It is as follows using Examples 1 to 8 and the method for the resin combination production copper-clad laminate of comparative example 1~11:
Fire-retardant epoxy resin, non-flame resistant type epoxy resin (tris phenol type epoxy), curing agent, curing accelerator are pressed
Proportional quantity is added to the container, and stirring is uniformly mixed it, is added the filler of proportional quantity, is stirred evenly with high speed disperser, most
Glue is made with solvent adjustment solution solids content to 72 ± 2% afterwards.
Resin combination composition glue liquid obtained above is impregnated using the dedicated wood pulp paper of CEM-1 or rag paper, through oven drying system
Core material prepreg is obtained, by above-mentioned core material semi-solid preparation the piece number overlapping, fabric prepreg is equipped on the outside of lamination, then in fabric
Copper foil is arranged in one or both sides on the outside of prepreg, is not particularly limited for the process conditions of heat pressure forming process, generally
It is under 130~190 DEG C of program setting temperature, 4~8MPa of programmed pressure, program setting time 120min, through hot pressing
At the copper-clad laminate of 1.6mm.
For above-mentioned manufactured copper-clad laminate, its anti-flammability, 288 DEG C of thermal stress, water absorption rate, T260 DEG C of heat point are tested
Layer time, bending strength, test result are as shown in Table 3 and Table 4.
Each performance test methods are as follows:
A: it anti-flammability: is tested according to UL-94 standard.
B: it resistance to immersed solder: is immersed in the tin furnace that temperature is 288 DEG C, when recording corresponding when substrate occurs and blisters or divide
Between.
C: it water absorption rate: is measured according to IPC-TM-650 2.6.2.1 method.
The D:T260 thermally stratified layer time: refer to plate under 260 DEG C of set temperature, since the effect of heat layering occurs now
As duration before this.If the time is greater than 60min, just terminate to test.
E: it bending strength: is measured according to IPC-TM-650 2.4.4B method.
The test result of 3 copper-clad laminate of table
The test result of 4 copper-clad laminate of table
Pass through table 3 and the available following of table 4:
Examples 1 to 8 all shows plate with preferable anti-flammability, resistance to dip solderability, heat resistance and lower water suction
Rate.
The comparison of comparative example 1 and embodiment 1 can be seen that due to not using non-flame resistant type epoxy resin, comparative example 1
Resistance to dip solderability, heat resistance declines to a great extent, and water absorption rate also increases very much.
Comparative example 2 and embodiment 2 compare it is found that since using fire-retardant epoxy resin, the anti-flammability of comparative example 2 does not become
Difference, heat resistance also slightly reduce.
Comparative example 7 is compared with embodiment 1 it is found that since fire-retardant epoxy resin dosage is very little, and the anti-flammability of comparative example 7 becomes
Difference, resistance to dip solderability, heat resistance decrease.
Comparative example 8 and embodiment 4 compare the resistance to immersed solder of comparative example 8 it is found that since fire-retardant epoxy resin dosage is too many
Property, heat resistance decrease, and water absorption rate is increased.
Comparative example 9 and embodiment 1 compare the resistance to immersed solder of comparative example 9 it is found that since non-flame resistant type content of epoxy resin is very little
Property, heat resistance decline to a great extent, and water absorption rate also increases very much.
Comparative example 10 and embodiment 4 compare it is found that since non-flame resistant type content of epoxy resin is too many, comparative example 10 it is fire-retardant
Property be deteriorated, resistance to dip solderability, heat resistance slightly reduces, and bending strength increases very much.
Comparative example 11 and embodiment 1-8 compare respectively it is found that due to each component in fire-retardant epoxy resin weight ratio not
Within the scope of the claims, the anti-flammability of comparative example 11 is deteriorated, and resistance to dip solderability, heat resistance declines to a great extent, and water absorption rate also increases very
It is more.
Comparative example 3 and embodiment 4 compare it is found that due to not using phosphorous epoxy (DOPO base epoxy), comparative example 3
Anti-flammability be deteriorated, resistance to dip solderability, heat resistance decreases, and water absorption rate slightly increases.
Comparative example 4 and embodiment 2 compare it is found that due to not using nitrogenous epoxy (para-aminophenol epoxy resin), than
Anti-flammability compared with example 4 is deteriorated, and resistance to dip solderability, heat resistance decreases, and water absorption rate is increased.
Comparative example 5 and embodiment 3 compare it is found that due to not using brominated epoxy (brominated BPA epoxy resin), comparative example
5 anti-flammability is deteriorated, and resistance to dip solderability, heat resistance decreases, and water absorption rate is increased.
Comparative example 6 and embodiment 1 compare it is found that the water absorption rate of embodiment 1, resistance to dip solderability, heat resistance are superior to comparative example
1.Illustrate that fire-retardant epoxy resin and polyfunctional epoxy resin collocation use, not only can achieve flame retardant effect, moreover it is possible to effectively mention
The crosslink density of high solidification object improves heat resistance, the resistance to dip solderability and water imbibition of plate.
In conclusion the bromo- phosphorus-nitrogen coordinated fire-retardant technology of phosphorus-of the present invention, having broken tradition has halogen CEM-1 to cover copper foil
In laminate halogen antimony cooperative flame retardant system can not substituted technical bottleneck, completely removed the antimony containing compounds in CEM-1, reached
Limitation requirement of the international environment regulation to antimonial is arrived.
There is halogen without the preparation-obtained CEM-1 copper-clad laminate of antimony resin combination, anti-flammability using of the invention
The peer for having reached halogen antimony synergistic is horizontal, the V-0 grade standard in UL-94, meanwhile, 288 DEG C of thermal stress are mentioned compared with halogen antimony collaboration system
Height is to 133~140s, compared to improving 41~44%；Water absorption rate is reduced to 0.07~0.08% compared with halogen antimony collaboration system, compares
Reduce 38~46%；T260 is increased to 50~58min compared with halogen antimony collaboration system, compared to improving 38~47%.Thus, this has
Halogen while guaranteeing fire-retardant, also has a comprehensive performances outstanding such as high heat resistance, high wet-heat resisting without antimony CEM-1 copper-clad laminate
Advantage.
The Applicant declares that the present invention is explained by the above embodiments of the invention have halogen without antimony resin combination, uses
Its prepreg, laminate and printed circuit board, but the present invention is not limited to the above embodiments, that is, does not mean that the present invention must
Above-described embodiment, which must be relied on, to be implemented.It should be clear to those skilled in the art, any improvement in the present invention, right
The equivalence replacement of each raw material of product of the present invention and addition, the selection of concrete mode of auxiliary element etc., all fall within guarantor of the invention
It protects within range and the open scope.
Claims (10)
1. one kind has halogen without antimony resin combination, which is characterized in that described to have halogen without antimony resin combination include following parts by weight
Component:
The non-flame resistant type epoxy resin of 25~70 parts by weight fire-retardant epoxy resins, 10~40 parts by weight, the solidification of 20~60 parts by weight
Agent, 0.05~1.0 parts by weight curing accelerator；
The fire-retardant epoxy resin includes the combination of phosphorous epoxy resin, brominated epoxy resin and nitrogen-containing epoxy thermoset three
Object.
2. according to claim 1 have halogen without antimony resin combination, which is characterized in that contain in the fire-retardant epoxy resin
The weight ratio of phosphorus epoxy resin, brominated epoxy resin and nitrogen-containing epoxy thermoset is (1.3~1.5): (1.5~1.75): (1~
1.2)；
Preferably, phosphorus content is 2%~4% in the phosphorous epoxy resin；
Preferably, bromine content is 19%~50% in the brominated epoxy resin；
Preferably, nitrogen content is 5~14% in the nitrogen-containing epoxy thermoset；
Preferably, the phosphorous epoxy resin is DOPO base epoxy, ODOPB base epoxy, three phosphonitrile base asphalt mixtures modified by epoxy resin of ring
In rouge or diphenyl phosphate oxidation epoxy resin any one or at least two combination；
Preferably, the brominated epoxy resin is any one in BPA epoxy resin, BPF epoxy resin or novolac epoxy resin
Kind or at least two combination；
Preferably, the nitrogen-containing epoxy thermoset is glycidyl amine epoxy resin, para-aminophenol epoxy resin, diamino hexichol
Methane type epoxy resins, poly-isocyanurate-oxazole alkanoic acid epoxy resin, cyanic acid ester epoxy resin, cyanuric acid three-glycidyl
In amine epoxy resin, the cyanuric acid three-glycidyl amine epoxy resin or nitrogenous novolac epoxy resin that triazine ring is nuclear skeleton
Any one or at least two combination.
3. according to claim 1 or 2 have halogen without antimony resin combination, which is characterized in that the non-flame resistant type asphalt mixtures modified by epoxy resin
Rouge is the group of any one or at least two in two functional epoxy resins, trifunctional epoxy resin or tetrafunctional epoxy resin
It closes；
Preferably, the non-flame resistant type epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy tree
Rouge, alkyl phenol epoxy resin, DCPD-containing epoxy resin, tris phenol type epoxy, o-cresol type novolac epoxy resin or benzene
In phenolic novolac epoxy resin any one or at least two combination；
Preferably, the epoxide equivalent of the fire-retardant epoxy resin is 100g/eq~800g/eq；
Preferably, the epoxide equivalent of the non-flame resistant type epoxy resin is 100g/eq~800g/eq.
4. according to any one of claim 1-3 have halogen without antimony resin combination, which is characterized in that the curing agent is
Linear phenolic resin class curing agent；
Preferably, the linear phenolic resin class curing agent is phenol type phenolic resin, bisphenol A type phenolic resin, o-cresol type
It is any in phenolic resin, triphenol phenolic resin, naphthalene type phenolic resin, biphenyl type phenolic resin or dicyclopentadiene phenolic resin
It is a kind of or at least two combination；
Preferably, the phenolic hydroxyl equivalent of the linear phenolic resin class curing agent is 100~700g/eq.
5. having halogen without antimony resin combination described in any one of -4 according to claim 1, which is characterized in that the solidification promotes
Agent is any one or at least two in tertiary amine, three-level phosphine, metal-organic complex, quaternary ammonium salt or glyoxaline compound
Combination；
Preferably, the glyoxaline compound is 2-methylimidazole, -4 methylimidazole of 2- ethyl, 2- phenylimidazole, 2- phenyl -4
In methylimidazole or 1- 1-cyanoethyl-2-methylimidazole any one or at least two mixture；
It is preferably, described that have halogen without antimony resin combination also include filler；
Preferably, the filler is aluminium hydroxide, aluminium oxide, magnesium hydroxide, magnesia, alchlor, silica, carbonic acid
Calcium, aluminium nitride, boron nitride, silicon carbide, titanium dioxide, zinc borate, zinc molybdate, barium metaborate, zinc sulphide, alumina silicate, zinc oxide,
In zirconium oxide, mica, boehmite, talcum powder, CaCl2 or kaolin any one or at least two combination.
6. a kind of resin adhesive liquid, which is characterized in that the resin adhesive liquid is that have halogen for according to any one of claims 1 to 5
No antimony resin combination, which is dissolved or dispersed in solvent, to be obtained；
Preferably, the solvent is the solvent that boiling point is 50 DEG C~180 DEG C；
Preferably, the solvent is methanol, ethyl alcohol, acetone, butanone, ethylene glycol monobutyl ether, methyl acetate, ethyl acetate or hexamethylene
In ketone any one or at least two mixing；
Preferably, the solid content of the resin adhesive liquid is 60%~80%, preferably 65%~75%.
7. a kind of prepreg, which is characterized in that the prepreg includes reinforcing material and adheres to thereon after being dried by impregnation
It is according to any one of claims 1 to 5 to have halogen without antimony resin combination；
Preferably, the reinforcing material is wood pulp paper or rag paper.
8. a kind of laminate, which is characterized in that the laminate includes an at least prepreg as claimed in claim 7.
9. a kind of metal-clad laminate, which is characterized in that the metal-clad laminate contains at least one such as claim 7
The metal foil of the prepreg and the prepreg one or both sides being overlying on after overlapping.
10. a kind of printed circuit board, which is characterized in that the printed circuit board include laminate as claimed in claim 8 or
Metal-clad laminate as claimed in claim 9.
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| CN201811160775.XA CN109306149B (en) | 2018-09-30 | 2018-09-30 | Halogen-containing antimony-free resin composition, prepreg using same, laminated board and printed circuit board |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811160775.XA CN109306149B (en) | 2018-09-30 | 2018-09-30 | Halogen-containing antimony-free resin composition, prepreg using same, laminated board and printed circuit board |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002060590A (en) * | 2000-08-22 | 2002-02-26 | Shin Kobe Electric Mach Co Ltd | Epoxy resin composition for imprregnating glass fiber substrate and prepreg, laminated sheet and printed wiring board using the same |
| CN105175994A (en) * | 2015-08-03 | 2015-12-23 | 广东生益科技股份有限公司 | Epoxy resin composition for copper-clad plate and application thereof |
| CN105273362A (en) * | 2015-11-12 | 2016-01-27 | 广东生益科技股份有限公司 | Epoxy resin composition and application thereof |
-
2018
- 2018-09-30 CN CN201811160775.XA patent/CN109306149B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002060590A (en) * | 2000-08-22 | 2002-02-26 | Shin Kobe Electric Mach Co Ltd | Epoxy resin composition for imprregnating glass fiber substrate and prepreg, laminated sheet and printed wiring board using the same |
| CN105175994A (en) * | 2015-08-03 | 2015-12-23 | 广东生益科技股份有限公司 | Epoxy resin composition for copper-clad plate and application thereof |
| CN105273362A (en) * | 2015-11-12 | 2016-01-27 | 广东生益科技股份有限公司 | Epoxy resin composition and application thereof |
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