CN108727775A - It is resistance to combustion modification type styrene maleic resin curing agent preparation method and epoxy resin composition and its in copper clad laminate and film application - Google Patents
It is resistance to combustion modification type styrene maleic resin curing agent preparation method and epoxy resin composition and its in copper clad laminate and film application Download PDFInfo
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- CN108727775A CN108727775A CN201710265211.1A CN201710265211A CN108727775A CN 108727775 A CN108727775 A CN 108727775A CN 201710265211 A CN201710265211 A CN 201710265211A CN 108727775 A CN108727775 A CN 108727775A
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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
- 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
- B32B15/08—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 synthetic resin
- B32B15/082—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 synthetic resin comprising vinyl resins; comprising acrylic 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
- B32B15/08—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 synthetic resin
- B32B15/092—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 synthetic resin comprising 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- 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
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- 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
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- 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
- C09J7/00—Adhesives in the form of films or foils
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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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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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
- 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
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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
- 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
Abstract
The resistance to combustion modification type maleic anhydride resin of one kind of the present invention, it is after being reacted with the Halogen prime system epoxy resin with hydroxyl (OH) with the copolymer of maleic anhydride using styrene, as a kind of composition of the copolymer-maleic anhydride of the resistance to combustion characteristic modification of tool, include copolymer, (C) additive and (D) inorganic filling material of the epoxy resin composition of (A) one or more, (B) modification type of resistance to combustion maleic anhydride of styrene.When the weight of wherein ingredient (A), (B) and (C) adds up to 100%, ingredient (A) epoxy resin composition, account for composition solid content weight 60%-80%, ingredient (B) modifies the copolymer of the type of resistance to combustion maleic anhydride of styrene, accounts for composition solid content weight 10%-40%.Using the composition epoxy resin of the present invention, in addition to good heat resistance and excellent electrical characteristic, it is more suitable for making prepreg, bonding sheet, copper clad laminate, can be applied to general or high frequency field printed circuit board.
Description
【Technical field】
The present invention relates to a kind of composition epoxy resin, have high glass-transition temperature, excellent heat-resisting property and
Excellent electrical characteristic is suitble to make prepreg, bonding sheet, copper clad laminate, can be applied to the print of electronic building brick and high frequency field
Printed circuit board or the carrier plate material of encapsulation.
【The prior art】
Epoxy resin, which is used on copper clad laminate and printed circuit board, has history for many years, with the progress in epoch and right
The requirement of environmental protection increasingly increases, and electronic equipment high frequency is the trend of development, while also based on halogen-free environmental plank
Want demand, especially wireless network, satellite communication it is growing under, the product of signal transmission and information has moved towards high speed and height
Frequencyization；Communication product moves towards voice, video signal and the data of capacity wireless transmission fireballing greatly to standardize, therefore develops new
The product of a generation all needs halogen-less high frequency substrate.
At present copper clad laminate used in printed circuit board (Copper Clad Laminate, CCL) no matter in quantity or
On technological layer, still based on FR-4 planks, but the development of electronics industry is advanced by leaps and bounds, its opposite important relevant group
Part-printed circuit board also has to the step kept pace with the times.For system product, light, thin, short, the small durable electricity-saving of product,
For electronic building brick, what is come along with processing procedure size reduction is that working frequency is continuously improved, operating voltage persistently reduces,
Transistor power consumption reduce again and again and more and more small etc. effects of voltage adaptable noise under, when leading to script low frequency regardless of
The problem of emerge, the printed circuit board to only belonging to interconnection lines (interconnection) industry has generated two main developments
Direction；One, highdensity printed circuit board：Its major technique is filament, aperture, blind hole, buried via hole.Secondly, high-frequency electrical subgroup
The circuit board of part support plate and high speed electric products：Major technique is low dielectric constant (LOW DK), low loss factor (LOW DF)
Plank and film dielectric layer plank and accurate impedance control etc..
The application of high-frequency high-speed has been the important development trend of printed circuit board (PCB), is gradually increased with demand, in material
Using and cost consideration under, common product with standard type FR-4 substrates can meet demand, but to the product of high-frequency transmission, substrate
Material requirements is higher, low dielectric constant, low loss factor substrate exactly coordinate this information products move towards high speed and high frequency and
Communication product trend largely can quickly transmit voice, the requirements such as video signal data again；In view of environmental protection problem, this type production
Product develop final trend and move towards non-halogen development.
Copper foil base plate materials are mainly made of reinforcing material and resin combination, and outer layer is bonded copper foil again, so resin group
It will be one of the principal element for influencing electrical property of substrate to close object.This patent using the exploitation of resin combination, changes explanation except reaching
Outside the effect of kind electrical property of substrate, and ecological requirements are taken into account simultaneously.
In patent BE-627887 it has been suggested that：Using the copolymer of maleic anhydride and styrene as epoxy resin
Curing agent, but be that glass transition temperature (Tg) is low, heat-resisting property is poor the shortcomings that composition epoxy resin, it makes it unsuitable for applying
It is manufactured in copper clad laminate (CCL) and printed circuit board (PCB).
Acid anhydrides type curing agent is with epoxy resin in use, normal-temperature reaction is extremely fast not appropriate for applying in the case where adding accelerating agent
In art of printed circuit boards.
It is phosphorus system epoxy resin currently used for the Halogen resin system of copper clad laminate and printed circuit board, generally uses standard
FR4 substrates, main component be phosphorous epoxy resin and add inorganic filler non-halogen epoxy resin be Primary resins
Ingredient with dicyandiamide as curing agent, then adds accelerating agent and solvent, the glass transition temperature of such composition epoxy resin
(Tg) height (150~170 DEG C) is spent, but its heat-resisting property is poor, and too many contribution is had no for the electrical properties of substrate (material).
Being disclosed in United States Patent (USP) US6509414 uses the copolymer (SMA) of styrene and maleic anhydride to be used as hardening of resin
Agent can make the epoxy resin of general bifunctional base improve the heat resistance of material, the method for recycling co-crosslinker, such as use benzene
The copolymer (SMA) of ethylene and maleic anhydride and co-crosslinker system tetrabromobisphenol A (TBBA), tetrabromobisphenol A diglycidyl ether
(TBBADGE), plank glass transition temperature (Tg) is improved；Acid anhydrides and aromatic hydroxyl (OH) and epoxy wherein in resin mixing
Epoxy equivalent ratio is 50%-150%.In its disclosed example it can be appreciated that when equivalents ratio increases to 110% by 70%, DSC
Glass transition temperature (Tg) increases to 155 DEG C by 122 DEG C, then when equivalents ratio is increased to 150% by 110%, and DSC vitrifyings turn
Temperature (Tg) is down to 137 DEG C by 155 DEG C instead.Thus phenomenon learns that equivalent proportion is more than 110% or so, and crosslinking agent will be unable to again
Promoting crosslink density makes DSC glass transition temperatures (Tg) improve.
Also the copolymer using styrene and maleic anhydride is disclosed in US publication US2012002458024A1
(SMA) it is used as hardening of resin agent；Its styrene is styrene 1 using proportioning with maleic anhydride:Maleic anhydride 4 (EF-40), and
The use of dicyclopentadiene (DCPD) is main resin, and it is non-halogen to reach to be added to phosphorus containing phenolic resin and phosphor nitrogen combustion inhibitor,
So that its resistance to combustion is reached outside the flame retardant effect of 94-V0, also promotes the electric characteristics of plank to apply in halogen-less high frequency material, however work as
When EF-40 usage amounts are more than 60%, though electrical characteristic slightly promotion is outer, glass transition temperature Tg (DMA) can be 186 DEG C by drop
170 DEG C or so are fallen to approximately, while the decline of plank toughness is also unable to reach flame retardant effect.
As known from the above, when the use of styrene and copolymer-maleic anhydride being curing agent, additive amount is more, except in proportioning
Outside being limited, when developing the plank of Halogen system, the additive amount of phosphorus containing phenolic resin and phosphor nitrogen combustion inhibitor has to carry
High usage amount.
【Invention content】
The present invention is mainly to disclose the composition of a kind of resistance to combustion modification type maleic anhydride curing agent and epoxy resin, composition
Including one or more kinds of epoxy resin compositions, the copolymer for modifying the type of resistance to combustion maleic anhydride of styrene, additive and
Inorganic filling material.The weight of its epoxy resin mixture, the copolymer for modifying the type of resistance to combustion maleic anhydride of styrene, additive
When adding up to 100%, epoxy resin composition accounts for composition solid content weight 60%-80%, modifies the type of resistance to combustion styrene Malaysia
The copolymer of acid anhydrides accounts for composition solid content weight 10%-40%.The present invention using styrene and maleic anhydride copolymer with
It carries out being reacted to a kind of resistance to combustion type copolymer-maleic anhydride curing agent with hydroxyl (OH) modification agent, with hydroxyl (OH)
Non-halogen substance；Using the composition epoxy resin of the present invention, there is good heat resistance and excellent electrical characteristic, fit
It closes and makes prepreg, bonding sheet, copper clad laminate, can be applied to general or high frequency field printed circuit board.
That is, the resistance to combustion modification type maleic anhydride resin of the present invention, it is the copolymer and tool using styrene and maleic anhydride
After thering is the Halogen prime system epoxy resin of hydroxyl (OH) to be reacted, become a kind of copolymer-maleic anhydride of the resistance to combustion characteristic modification of tool
Composition, including the epoxy resin composition of (A) one or more, (B) modification type of resistance to combustion maleic anhydride of styrene
Copolymer, (C) additive and (D) inorganic filling material.When the weight of wherein ingredient (A), (B) and (C) adds up to 100%, at
Divide (A) epoxy resin composition, account for composition solid content weight 60%-80%, ingredient (B) modifies the type of resistance to combustion styrene maleic acid
The copolymer of acid anhydride accounts for composition solid content weight 10%-40%.
【Embodiment】
One, the preparation of resistance to combustion modification type copolymer-maleic anhydride curing agent：
The present invention is to obtain a kind of novel modification type copolymer-maleic anhydride curing agent by the way of synthesis, using this
Novel agent, then epoxy resin of arranging in pairs or groups, inorganic filling material and accelerating agent and become a kind of resin combination, can be applied to copper
Foil substrate (Copper Clad Laminate, CCL) and printed circuit board (PCB) manufacture.
The copolymer of the modification type of the resistance to combustion maleic anhydride of styrene has the structural formula as shown in formula (I)：
M, n are positive integer, can be identical or different number.
R1Can be bisphenol A epoxide resin, bisphenol F epoxy resin, novolac epoxy resin and two rings for epoxide resin polymer chain
Pentadiene epoxy resin.
R2For DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) derivative of phosphorus series compound, including DOPO
(miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies), DOPO-HQ (10- (2,5- dihydroxy phenyls) -10H-9- oxygen
Miscellaneous -10- phospho hetero phenanthrenes -10- oxides), the DOPO-NQ (naphthoquinones of the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies
Close object) etc..
The modification type copolymer-maleic anhydride curing agent preparation method of the present invention, includes the following steps：1. taking phosphorus series compound
DOPO or DOPO derivatives；2. the epoxy resin of certain equivalent proportion is taken to be reacted with phosphorus series compound；3. appropriate catalysis is added
Agent is reacted；4. reaction generate after prepolymer, then reacted with SMA maleic anhydride resins, form such as structure (I)
Shown in modify the type of resistance to combustion maleic anhydride of styrene copolymer.The phosphorus series compound can be the derivative of DOPO, including：
DOPO (miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies), DOPO-HQ (10- (2,5- dihydroxy phenyls) -10H-9-
Oxa- -10- phospho hetero phenanthrene -10- oxides), the DOPO-NQ (naphthoquinones of the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies
Compound).
Institute using epoxy resin can be selected from its epoxide equivalent between 150~4000, preferably epoxide equivalent between 180~
1000。
Epoxy resin and phosphorous compound can be with 1 used in aforementioned：0.2~1：2.0 relative equivalent ratio is anti-together
It answers, most appropriate amount ratio is 1：0.5~1.1.5；The molecule of the copolymer of the modification type of resistance to combustion maleic anhydride of styrene after synthesized
Amount ranging from can be between 2000-15000.
It is aforementioned using catalyst can be selected from pyrovinic acid, trifluoromethane sulfonic acid, p-methyl benzenesulfonic acid, triphenyl phosphorus, vinegar
At least one of sour sodium, potassium acetate, cobalt acetate, ferric acetate, zinc acetate or lead acetate.
The Macroscopic single crystal mode of the present invention is as described below：
By the bisphenol A epoxide resin of 340g, 220g DOPO (miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies)
And appropriate catalyst (cobalt acetate) is placed in the four neck reactors equipped with blender, temperature controller, condenser and nitrogen device, profit
With the mode of stirring, temperature is risen to 150 DEG C and carries out reaction 5 hours, you can obtains phosphorous epoxy resin prepolymer (A), reacted
The variation for being tracked its DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) signal strength in journey using GPC, is made
For the index of DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) remaining quantity, the terminal reacted with determination.
By the copolymer resin (EF40) of 360 grams of commercial styrene and maleic anhydride and phosphorous epoxy resin prepolymer (A)
60 grams are placed in four neck reaction bulbs, and after being dissolved at room temperature with 500 grams of toluene, 0.5 gram of diethylaniline (benzyl is added
Dimethyl amine) it stirs 30 minutes, it is warming up at 140 DEG C and reacts 5 hours again later, you can must have the modification type of resistance to combustion benzene second
Alkene copolymer-maleic anhydride (B), structural formula is as follows.
Or
Or
Two, resistance to combustion modification type copolymer-maleic anhydride curing agent is applied to copper clad laminate and its film production：
The present invention is to utilize this novel hardening using a kind of resistance to phosphorous copolymer-maleic anhydride curing agent of combustion modification type
Agent, then arrange in pairs or groups epoxy resin, inorganic filling material, additive and accelerating agent appropriate and become a kind of resin combination, therefore
It can be applied to copper clad laminate (Copper Clad Laminate, CCL) and printed circuit board (PCB) manufacture.
The resin combination ingredient, including one or more kinds of epoxy resin compositions, account for composition solid
Object weight 60%-80%, modification type copolymer-maleic anhydride account for composition solid content weight 10%-35%, additive and nothing
Machine packing material.
The epoxy resin that the resin compound is selected can be monofunctional, bifunctional base epoxy, and epoxy is worked as
Amount is 150-4000g/eq, is selected from bisphenol A epoxide resin, bisphenol F epoxy resin.Promote glass transition temperature and heat resistance
Polyfunctional epoxy resin can be selected, epoxide equivalent 150-3000g/eq is selected from phenolic aldehyde Novolac types resin, nitrogen system ring
Oxygen resin, epoxide equivalent 150-3000g/eq.Also can be the epoxy resin with heterocycle structure, such as dicyclopentadiene class
(DCPD epoxy, dicyclophentadiene) epoxy resin, electricity of addition dicyclopentadiene class (DCPD) resin to system
The effect that property and water absorption rate all have clear improvement.
In addition, benzo series plastics can be added by promoting plank processing characteristics；Structural formula intention is as follows, such as the life of Kun Meng enterprises
The resin with benzo system class of production, trade name KB-610F, addition this type resin is to glass transition temperature, electrical and stripping
All all there is the effect being obviously improved from intensity.
Dimethyl phenolic aldehyde (2,6DMP) epoxy resin can be added in terms of promoting plank electrical characteristic, structural formula is intended to such as
Under, for example, South Asia plastics-production dimethyl phenol formaldehyde epoxy resin, trade name NPPN-260, (EEW=200eq/g)；Addition
2,6DMP resins electrically and in terms of Resin Flow also all have plank the effect of promotion.
The selection of the epoxy resin composition can regard processability, physical property etc. and select above-mentioned wherein one or more
Resin use.
The visual resin combination of selection of copolymer with regard to modifying the type of resistance to combustion maleic anhydride of styrene forms, therefore in response to environmental protection
Trend is using non-halogen system as main application.
The additive because resin combination harden after property requirements, addition come reach improvement or reinforce working properties,
Engineering properties and plank physical property.The additive can be high molecular weight phenoxy resin (Phenoxy resin), rubber
(Rubber) and incombustible agent ... etc..Such as addition INCHEMREZ PKHS high molecular weight phenoxy resin (Phenoxy resin) can
It improves the obdurability in prescription system and promotes impact strength；Such as it adds1300 × 8 rubber of CTBN (Rubber)
The Bonding strength between copper foil can be improved；Such as addition A187S silicon Anhui coupling agent is to increase the adhesion of base material interlayer；Such as add
The nonflammable characteristic etc. of plank can be increased by increasing tomb chemistry SPB-100 incombustible agents.
The purpose of inorganic filling material addition is the rigidity promoted after resin combination hardening of the invention, reduces and thermally expands
Coefficient increases fire retardant characteristic.The inorganic filling material can be the silica of crystal type, ball-type and fusion, hydroxide
One or more kinds of mixtures of aluminium, magnesium hydroxide, aluminium oxide, account for composition solid content weight 10%-40%.Such as：
Addition silica can reduce the coefficient of thermal expansion of hardening thing；Magnesium hydroxide, oxidationization aluminium can increase flame retardancy；Aluminium oxide can change
Kind heat transfer etc..
The purpose of the present invention is to provide the novel modification type of the resistance to combustion maleic anhydrides and asphalt mixtures modified by epoxy resin of a kind of application of halogen-less high frequency
The compositions of thermosetting resin of fat, the composition can be completely dissolved with solvent, be deployed into and stablize homogeneous varnish at normal temperatures
(varnish), with it come manufacture preimmersion base material (Prepreg), copper foil base plate materials (Copper Clad Laminate,
CCL), it can be used for printed circuit board.
The preimmersion base material (Prepreg) is after the resin combination of the present invention is deployed into varnish (varnish), to utilize
Reinforcing material is anti-by the solvent volatilization part of resin combination progress simultaneously via the composition containing epoxy resin dipping, then by heated oven
Semi-solid preparation film (B-stage) should be presented.The reinforcing material can be glass fibre, carbon fiber, kelvar fibers, paper fiber, such as
Aromatic polyamide paper etc.；The preimmersion base material (Prepreg), which can be pressed further, is fabricated to copper clad laminate, pre- with one or more
Leaching base material is combined, and two sides is descended to place copper foil on it, and repressurization heats the composition and finally obtains the compound of copper clad laminate
Material.There is high glass-transition temperature (Tg), excellent heat-resisting property and excellent after the resin combination hardening of the present invention
Outside electrical characteristic, adhesion between low-expansion coefficient and high level is had more；It can be applied to general or high frequency field printed circuit board.
Following embodiment is that reference is described further by the present invention.
Embodiment one：
Use 20 grams of benzo system heat stable resin (Kun Meng company KB-610F), dimethyl phenol urea formaldehyde, (South Asia plastics NPPN-
260) 20 grams and (South Asia plastics NPPN-433) the 60g elder generations predissolve of benzaldehyde type resin form one in methyl ethyl ketone (MEK)
70% solution is separately added into the copolymer (B) of 15 grams of the modification type of resistance to combustion maleic anhydride of styrene in this solution (such as preceding institute
Show)；In addition 15 grams of phosphorus containing phenolic resin (South Korea SHIN ' A LC950) and phosphorus nitrogen flame retardant (big tomb chemistry SPB-100) 15 is added
After gram, and surface treatment type inorganic fill powder SIO is being added2The silicon Anhui coupling that 62 grams and 1 gram of (silicon is than section company 525ARI)
Agent (A187S)；All additives are fully dissolved in solution and the accelerating agent 2E4MZ that methyl ethyl ketone (MEK) forms one 60%
0.150 gram, relative to whole resin solid content, modify the copolymer (B) and epoxy resin of the type of resistance to combustion maleic anhydride of styrene
Equivalents ratio is 20%.
It stirs this resin combination 3 hours, is later 250 seconds in testing gel time on 170 DEG C of hot plate；By this solution
It is sent into impregnating groove, is impregnated with using glass fabric (model 7628) continous way, solvent is volatilized while being set via heated oven
Oil/fat composition carries out part reaction and semi-solid preparation film (B-stage) is presented, and goes out this semi-solid preparation film after baking oven is cooled to room temperature
Cut slabbing；Each storehouse one under on 8 slim semi-solid preparation films is opened into copper foil (specification 1oz), recycles hot press heating
2.5 DEG C/min of rate rises to 200 DEG C and continues 60 to 120 minutes, and pressure uses 20-30kg/cm2, press and set via hot press
The reaction was continued for oil/fat composition to hardening completion (C-stage), and the glass transition up to 150 DEG C or more is proved via physical property measurement
Temperature (Tg) and excellent heat resistance etc..Physical property measurement data are listed in table two.
Embodiment two：
Use 20 grams of benzo system heat stable resin (Kun Meng company KB-610F), dimethyl phenol formaldehyde-based resin, (South Asia plastics
NPPN-260) 20 grams and (South Asia plastics NPPN-433) the 60g elder generations predissolve of benzaldehyde type resin are formed in methyl ethyl ketone (MEK)
One 70% solution is separately added into the copolymer (B) of 30 grams of the modification type of resistance to combustion maleic anhydride of styrene in this solution；In addition
After 15 grams of 15 grams of phosphorus containing phenolic resin (South Korea SHIN ' A LC950) and phosphorus nitrogen flame retardant (big tomb chemistry SPB-100) is added, and
Surface treatment type inorganic fill powder SIO is being added2The silicon Anhui coupling agent that 68 grams and 1 gram of (silicon is than section company 525ARI)
(A187S)；All additives are fully dissolved in solution and the accelerating agent 2E4MZ that methyl ethyl ketone (MEK) forms one 60%
0.05 gram, relative to whole resin solid content, the copolymer (B) and epoxy resin that modify the type of resistance to combustion maleic anhydride of styrene are worked as
Amount ratio is 40%；Physical property measurement data are listed in table two.
Embodiment three：
The copolymer (B) of the type of resistance to combustion maleic anhydride of styrene is modified according to the manufacturing method of embodiment one and epoxy resin is worked as
Amount ratio is 60%.Physical property measurement data are listed in table two.
Example IV：
The copolymer (B) of the type of resistance to combustion maleic anhydride of styrene is modified according to the manufacturing method of embodiment one and epoxy resin is worked as
Amount ratio is 80%.Physical property measurement data are listed in table two.
Embodiment five：
Use 20 grams of benzo system heat stable resin (Kun Meng company KB-610F), dimethyl phenol urea formaldehyde, (South Asia plastics NPPN-
260) 20 grams and dcpd resin (Japanese DIC 7200H) 60g elder generations predissolve form one in methyl ethyl ketone (MEK)
70% solution is separately added into the copolymer (B) of 45 grams of the modification type of resistance to combustion maleic anhydride of styrene in this solution；In addition it is added
After 20 grams of 15 grams of phosphorus containing phenolic resin (South Korea SHIN ' A LC950) and phosphorus nitrogen flame retardant (big tomb chemistry SPB-100), and adding
Enter surface treatment type inorganic fill powder SIO2The silicon Anhui coupling agent (A187S) that 70 grams and 1 gram of (silicon is than section company 525ARI)；Institute
There is additive to be fully dissolved in 0.125 gram of solution and accelerating agent 2E4MZ that methyl ethyl ketone (MEK) forms one 60%, phase
For whole resin solid content, the copolymer (B) and epoxy resin equivalents ratio that modify the type of resistance to combustion maleic anhydride of styrene are
66%.Physical property measurement data are listed in table two.
Embodiment six：
Use 20 grams of benzo system heat stable resin (Kun Meng company KB-610F), dimethyl phenolic aldehyde trifunctional base resin, (South Asia
Plastics NPPN-260) 20 grams and biphenyl type phenolic resin (South Korea SHIN ' A SE5000) 60g elder generations predissolve be in methyl ethyl ketone
(MEK) solution for forming one 70% is separately added into the copolymerization of 45 grams of the modification type of resistance to combustion maleic anhydride of styrene in this solution
Object (B)；In addition 15 grams of phosphorus containing phenolic resin (South Korea SHIN ' A LC950) and phosphorus nitrogen flame retardant (big tomb chemistry SPB-100) is added
After 20 grams, and surface treatment type inorganic fill powder SIO is being added2The silicon Anhui that 70 grams and 1 gram of (silicon is than section company 525ARI) is even
Collaboration (A187S)；All additives are fully dissolved in the solution and accelerating agent that methyl ethyl ketone (MEK) forms one 60%
0.125 gram of 2E4MZ modifies the copolymer (B) and ring of the type of resistance to combustion maleic anhydride of styrene relative to whole resin solid content
Oxygen epoxy equivalent ratio is 63%.Physical property measurement data are listed in table two.
Comparative example one：
It is sayed with embodiment one, uses 20 grams of benzo system heat stable resin (Kun Meng company KB-610F), dimethyl phenolic aldehyde tree
Fat, 20 grams of (South Asia plastics NPPN-260) and benzaldehyde type resin (South Asia plastics NPPN-433) 60g elder generations predissolve is in methyl second
Base ketone (MEK) forms one 70% solution, and 45 grams of maleic anhydride of styrene curing agent (styrene are separately added into this solution:
1；Maleic anhydride:4)EF40；In addition 15 grams of phosphorus containing phenolic resin (South Korea SHIN ' A LC950) and phosphorus nitrogen flame retardant (big tomb is added
Chemical SPB-100) after 30 grams, and surface treatment type inorganic fill powder SIO is being added275 grams of (silicon is than section company 525ARI) and
1 gram of silicon Anhui coupling agent (A187S)；All additives are fully dissolved in the solution that methyl ethyl ketone (MEK) forms one 60%,
And 0.05 gram of accelerating agent 2E4MZ.According to the manufacturing method of example one, physical property measurement data are listed in table two.
Comparative example two：
Based on comparative example one, 60 grams of maleic anhydride of styrene curing agent (styrene will be added in solution:1；Maleic acid
Acid anhydride:4)EF40；Its physical property measurement data is listed in table two.
The resin combination equivalence ratio range of table one, each Examples and Comparative Examples
The substrate properties of table two, each Examples and Comparative Examples
The composition of the modification type of the resistance to combustion maleic anhydride curing agent and epoxy resin of the present invention, with its copper clad laminate obtained
Glass transition temperature (Tg), copper foil tear strength, heat decomposition temperature (Td), thermally stratified layer time are carried out with reference to IPC-TM650
(T288), the tests such as scolding tin heat resistance (288 DEG C), dielectric constant (Dk), dielectric loss factor (Df), via physical property measurement result
Illustrate the present invention, have glass transition temperature (Tg), excellent heat-resisting property and the excellent electrical property of multiregion, while can subtract
The additive amount of few outer addition phosphorus (nitrogen) flame retardant, you can reach 94-V0 grades, be suitble to make electronic building brick and printed circuit board
Baseplate material.
The composition of modification type maleic anhydride and epoxy resin provided by the invention has：
1. high glass-transition temperature (Tg), can be used for high layer printed circuit board or support plate；
2. excellent heat-resisting property, the resistance to Thermal test of scolding tin is more than 60 minutes or more, not will produce plate bursting, lamination；
T288 (cupric) separation time can be more than 40 minutes；
3. excellent thermal property, thermal cracking temperature (Td) is more than 375 DEG C, meets the requirement of current halogen-free and lead-free processing procedure；
4. having excellent electrical properties, therefore signal transmission delay can be made to reduce and reduce the distortion of signal in high frequency
Degree.
In summary the composition for utilizing modification the type maleic anhydride curing agent and epoxy resin of the present invention, has good
Heat resistance and excellent electrical characteristic are suitble to make prepreg, bonding sheet, copper foil laminates, can be applied to general or high frequency
The printed circuit board in field.
Claims (12)
1. a kind of resin combination, it is characterised in that including following compositions：(A) one or more kinds of epoxy resin mixing
Object, (B) modifies the copolymer of the type of resistance to combustion maleic anhydride of styrene, (C) additive, (D) inorganic filling material, wherein (B) is modified
The structure of the copolymer of the type of resistance to combustion maleic anhydride of styrene is as follows：
Wherein m, n are positive integer, can be identical or different number；
R1For：Can be bisphenol A epoxide resin, bisphenol F epoxy resin, novolac epoxy resin for epoxide resin polymer chain；
R2For：For DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) derivative of phosphorus series compound, including
DOPO (miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies), DOPO-HQ (10- (2,5- dihydroxy phenyls) -10H-9-
Oxa- -10- phospho hetero phenanthrene -10- oxides), the DOPO-NQ (naphthoquinones of the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies
Compound).
2. resin combination as described in claim 1, wherein ingredient (A) epoxy resin composition can be BPF (Bisphenol Fs；Two
Hydroxy diphenyl methane) type, epoxide equivalent 150-3000g/eq or BPA (bisphenol-A；Diphenol propane) type, epoxide equivalent is
150-3000g/eq or polyfunctional epoxy resin, the one of epoxide equivalent 150-3000g/eq, and tool heterocyclic epoxy resin etc.
Kind or more than one resin compound.
3. resin combination as described in claim 1, wherein ingredient (A) epoxy resin composition accounts for composition solid content weight
60%-80% (be free of inorganic filling material).
4. resin combination as described in claim 1, wherein ingredient (B) modify the copolymer of the type of resistance to combustion maleic anhydride of styrene
Account for the 10%-40% (being free of inorganic filling material) of composition solid content weight.
Resin combination as described in claim 1, wherein ingredient 5. (C) additive visible combinations object property requirements and add,
It can be one or more kinds of mixtures of high molecular weight phenoxy resin, rubber, phosphorus containing phenolic resin and incombustible agent etc..
Resin combination as described in claim 1, wherein ingredient 6. (D) inorganic filling material can be crystal type, ball-type and
The silica of fusion, one or more kinds of mixtures of aluminium hydroxide, magnesium hydroxide, aluminium oxide, it is solid to account for composition
The 10%-40% of shape object weight.
7. resin combination as described in claim 1, wherein ingredient (B) modify the copolymer of the type of resistance to combustion maleic anhydride of styrene
Molecular weight ranges be 2000-15000.
8. resin combination as described in claim 1, wherein ingredient (B) modify the copolymer of the type of resistance to combustion maleic anhydride of styrene
Equivalent proportion with epoxy resin is 0.2~0.8.
9. a kind of prepreg, it is characterised in that be to be impregnated with or be coated on reinforcing material by resin combination as described in claim 1
Obtained by material.
10. a kind of bonding sheet, it is characterised in that be to be impregnated with or be coated on reinforcing material by resin combination as described in claim 1
Obtained by material.
11. a kind of copper foil laminates, which is characterized in that the copper foil laminates are by prepreg hot pressing as claimed in claim 9
Obtained by afterwards.
12. a kind of printed circuit board, which is characterized in that the printed circuit board is by copper foil laminates as claimed in claim 11
Obtained by hot pressing and wet process.
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| CN201710265211.1A CN108727775B (en) | 2017-04-21 | 2017-04-21 | Preparation method of flame-retardant modified styrene maleic anhydride resin hardener, epoxy resin composition and application of epoxy resin composition in copper foil substrate and film |
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| CN201710265211.1A CN108727775B (en) | 2017-04-21 | 2017-04-21 | Preparation method of flame-retardant modified styrene maleic anhydride resin hardener, epoxy resin composition and application of epoxy resin composition in copper foil substrate and film |
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