CN108727775B - 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 - Google Patents
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 Download PDFInfo
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- B32B15/00—Layered products comprising a layer of metal
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- 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
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
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- 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
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- 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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- B32B2457/00—Electrical equipment
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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
- 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 flame-retardant modified maleic anhydride resin is a composition of a copolymer of styrene and maleic anhydride and halogen-free epoxy resin with hydroxyl (OH) to obtain a modified maleic anhydride copolymer with flame-retardant property, and comprises (A) one or more epoxy resin mixtures, (B) a modified flame-retardant styrene maleic anhydride copolymer, (C) an additive and (D) an inorganic filling material. Wherein when the total weight of the components (A), (B) and (C) is 100%, the component (A) epoxy resin mixture accounts for 60-80% of the solid weight of the composition, and the component (B) modified flame-retardant styrene maleic anhydride copolymer accounts for 10-40% of the solid weight of the composition. The epoxy resin composition of the present invention has good heat resistance and excellent electrical characteristics, and is suitable for producing prepregs, adhesive sheets and copper foil substrates, and can be applied to printed wiring boards in general or high frequency fields.
Description
Technical Field
The invention relates to an epoxy resin composition, which has high glass transition temperature, excellent heat resistance and excellent electrical characteristics, is suitable for manufacturing prepreg, adhesive sheets and copper foil substrates, and can be applied to printed circuit boards in the fields of electronic components and high frequency or carrier plate materials for packaging.
Background
Epoxy resin is applied to copper foil substrates and printed circuit boards for years, along with the progress of times and the increasing requirements on environmental protection, the high frequency of electronic equipment is a development trend, and halogen-free environment-friendly boards are also taken as main requirements, so that particularly under the increasing development of wireless network and satellite communication, the signal transmission and information products are high-speed and high-frequency; communication products are moving to standardization of voice, video and data with large capacity and high speed for wireless transmission, so that new generation products need halogen-free high-frequency substrates.
At present, the Copper Clad Laminate (CCL) used in the printed circuit board is mainly FR-4 board, either in quantity or in technical level, but the development of the electronic industry is drastic and the printed circuit board, which is an important related component, must keep pace with the era. For system products, the products are light, thin, short, small, power-saving and durable, for electronic components, along with the reduction of the process size, the working frequency is continuously improved, the working voltage is continuously reduced, the power consumption of transistors is continuously reduced, and the voltage tolerance noise is smaller and smaller, so that the problems which are not considered in the original low frequency are revealed, and two main development directions are generated for printed circuit boards which only belong to the interconnection industry; first, high density printed circuit board: the main technology is fine line, small hole, blind hole and buried hole. Secondly, a high frequency electronic component carrier and a circuit board of a high speed electronic product: the main techniques are LOW dielectric constant (LOW DK), LOW loss factor (LOW DF) plate, thin dielectric layer plate and precise impedance control.
The application of high frequency and high speed is an important development trend of Printed Circuit Boards (PCB), and the demand is gradually increased, under the consideration of material use and cost, the demand can be met by a general product by using a standard FR-4 substrate, but for the product of high frequency transmission, the substrate material requirement is higher, and the low dielectric constant and low loss factor substrate is matched with the information product to move towards high speed and high frequency and the communication product to be capable of transmitting voice, video data and the like in a large quantity and fast manner; the final trend in the development of this type of product is towards non-halogenated development, considering environmental protection issues.
The copper foil substrate material mainly comprises a reinforcing material and a resin composition, and a copper foil is attached to the outer layer, so that the resin composition is one of the main factors influencing the electrical property of the substrate. This patent will describe the development of resin compositions that can improve the electrical properties of the substrate while meeting environmental requirements.
It has been proposed in patent BE-627887: a copolymer of maleic anhydride and styrene is used as a hardener for epoxy resin, but the epoxy resin composition has disadvantages of low glass transition temperature (Tg) and poor heat resistance, making it unsuitable for use in the manufacture of Copper Clad Laminate (CCL) and Printed Circuit Board (PCB).
When the anhydride type hardener is used with epoxy resin, the reaction is very fast at normal temperature under the condition of adding an accelerant, and the anhydride type hardener is not suitable for the field of printed circuit boards.
The halogen-free resin system used for copper foil base plate and printed circuit board is phosphorus epoxy resin, and the standard FR4 base plate is generally used, the main components of the base plate are phosphorus epoxy resin and non-halogenated epoxy resin added with inorganic filler, the main components are phosphorus epoxy resin, dicyandiamide is used as a hardening agent, and an accelerating agent and a solvent are further added, the glass transition temperature (Tg) of the epoxy resin composition is high (150-170 ℃), but the heat resistance quality is poor, and the halogen-free resin composition does not contribute much to the electrical property of the base plate (material).
U.S. Pat. No. 6,6509414 discloses that a copolymer of Styrene and Maleic Anhydride (SMA) is used as a resin hardener, and a common bifunctional epoxy resin can improve the heat resistance of the material, and a method of reusing a co-crosslinking agent is disclosed, for example, a copolymer of Styrene and Maleic Anhydride (SMA) and a co-crosslinking agent system of tetrabromobisphenol A (TBBA) and tetrabromobisphenol A diglycidyl ether (TBBADGE) are used to increase the glass transition temperature (Tg) of a plate material; wherein the equivalent ratio of acid anhydride, aromatic hydroxyl (OH) and epoxy resin in the resin mixture is 50-150%. As can be appreciated from the disclosed examples, when the equivalent proportion is increased from 70% to 110%, the DSC glass transition temperature (Tg) is increased from 122 ℃ to 155 ℃, and when the equivalent proportion is increased from 110% to 150%, the DSC glass transition temperature (Tg) is decreased from 155 ℃ to 137 ℃. This phenomenon indicates that when the equivalent ratio exceeds about 110%, the crosslinking agent cannot increase the crosslinking density any more and the DSC glass transition temperature (Tg) is increased.
The use of a copolymer of Styrene and Maleic Anhydride (SMA) as a resin hardener is also disclosed in U.S. published patent No. US2012002458024a 1; the styrene and the maleic anhydride are used according to the proportion of 1: 4(EF-40) and dicyclopentadiene (DCPD) as main resin, and phosphorus-containing phenolic resin and phosphorus-nitrogen flame retardant are added to achieve non-halogenation, so that the flame resistance of the flame-retardant halogen-free high-frequency flame-retardant halogen-free high-.
From the above, when the copolymer of styrene and maleic anhydride is used as the hardening agent, the addition amount is large, and besides the limit of the mixture ratio, when the halogen-free system board is developed, the addition amount of the phosphorus-containing phenolic resin and the phosphorus-nitrogen flame retardant is required to be increased.
Disclosure of Invention
The invention mainly discloses a flame-retardant modified maleic anhydride hardener and epoxy resin composition, which comprises one or more than one epoxy resin mixture, a copolymer of modified flame-retardant styrene maleic anhydride, an additive and an inorganic filling material. Wherein when the total weight of the epoxy resin mixture, the modified flame-retardant styrene maleic anhydride copolymer and the additive is 100%, the epoxy resin mixture accounts for 60-80% of the solid weight of the composition, and the modified flame-retardant styrene maleic anhydride copolymer accounts for 10-40% of the solid weight of the composition. The invention uses the copolymer of styrene and maleic anhydride to react with modifier with hydroxyl (OH) to form a flame-proof maleic anhydride copolymer hardener which is a non-halogen substance with hydroxyl (OH); the epoxy resin composition of the present invention has good heat resistance and excellent electrical characteristics, is suitable for producing prepregs, adhesive sheets and copper foil substrates, and can be applied to printed wiring boards in general or high frequency fields.
That is, the flame-retardant modified maleic anhydride resin of the present invention is a composition of modified maleic anhydride copolymer with flame-retardant property, which is obtained by reacting a copolymer of styrene and maleic anhydride with a halogen-free epoxy resin having hydroxyl (OH), and comprises (A) one or more epoxy resin mixture, (B) modified flame-retardant styrene maleic anhydride copolymer, (C) additive and (D) inorganic filler. Wherein when the total weight of the components (A), (B) and (C) is 100%, the component (A) epoxy resin mixture accounts for 60-80% of the solid weight of the composition, and the component (B) modified flame-retardant styrene maleic anhydride copolymer accounts for 10-40% of the solid weight of the composition.
Detailed Description
Firstly, preparing a flame-retardant modified maleic anhydride copolymer hardening agent:
the invention obtains a novel modified maleic anhydride copolymer hardening agent by adopting a synthesis mode, uses the novel hardening agent, and then is matched with epoxy resin, inorganic filling material and accelerating agent to form a resin composition which can be applied to the manufacture of Copper Clad Laminates (CCLs) and Printed Circuit Boards (PCBs).
The modified flame-retardant styrene maleic anhydride copolymer has a structural formula shown as a formula (I):
m and n are positive integers which can be the same or different numbers.
R1Is an epoxy resin polymer chain, which may be a bisphenol A epoxy resinEsters, bisphenol F epoxy resins, novolac epoxy resins, and dicyclopentadiene epoxy resins.
R2DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) derivatives as phosphorus-based compounds include DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), DOPO-HQ (10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide), DOPO-NQ (naphthoquinone compound of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), and the like.
The invention discloses a preparation method of a modified maleic anhydride copolymer hardening agent, which comprises the following steps: 1. taking a phosphorus compound DOPO or DOPO derivative; 2. reacting epoxy resin and a phosphorus compound in a certain equivalent ratio; 3. adding a proper amount of catalyst for reaction; 4. the prepolymer after reaction is reacted with SMA maleic anhydride resin to form the copolymer of modified flame-retardant styrene maleic anhydride shown in the structure (I). The phosphorus-based compound can be a derivative of DOPO, including: DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), DOPO-HQ (10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide), DOPO-NQ (naphthoquinone compound of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide).
The epoxy resin used may be selected from those having an epoxy equivalent of 150 to 4000, preferably 180 to 1000.
The epoxy resin and phosphorus-containing compound used as described above may be 1: 0.2-1: 2.0, optimal equivalent ratio of 1: 0.5 to 1.1.5; the molecular weight of the synthesized modified flame-retardant styrene maleic anhydride copolymer can be between 2000-15000.
The catalyst used can be at least one selected from methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, triphenylphosphine, sodium acetate, potassium acetate, cobalt acetate, iron acetate, zinc acetate and lead acetate.
The polymer of the invention is synthesized as follows:
putting 340g of bisphenol A epoxy resin, 220g of DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and a proper amount of catalyst (cobalt acetate) into a four-neck reactor provided with a stirrer, a temperature controller, a condenser and a nitrogen device, raising the temperature to 150 ℃ by stirring for reaction for 5 hours to obtain a phosphorus-containing epoxy resin prepolymer (A), and tracking the change of the signal intensity of the DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) by GPC in the reaction process to be used as an index of the residual amount of the DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) so as to determine the end point of the reaction.
Putting 360 g of commercial styrene-maleic anhydride copolymerized resin (EF40) and 60g of phosphorus-containing epoxy resin prepolymer (A) into a four-neck reaction bottle, dissolving the mixture in 500 g of toluene at room temperature, adding 0.5 g of diethyl aniline (benzyl dimethyl amine), stirring for 30 minutes, and then heating to 140 ℃ for reaction for 5 hours to obtain the modified flame-retardant styrene-maleic anhydride copolymer (B) with the structural formula shown below.
Wherein p and q are positive integers and are the same or different numbers;
secondly, applying the flame-retardant modified maleic anhydride copolymer hardener to the copper foil substrate and the film manufacture:
the invention relates to a flame-retardant modified phosphorus-containing maleic anhydride copolymer hardener, which is a resin composition prepared by using the novel hardener and matching with proper epoxy resin, inorganic filling material, additive and accelerator, so that the flame-retardant modified phosphorus-containing maleic anhydride copolymer hardener can be applied to the manufacture of Copper Clad Laminates (CCLs) and Printed Circuit Boards (PCBs).
The resin composition comprises one or more than one epoxy resin mixture, modified maleic anhydride copolymer, additive and inorganic filling material, wherein the epoxy resin mixture accounts for 60-80% of the solid weight of the composition, and the modified maleic anhydride copolymer accounts for 10-35% of the solid weight of the composition.
The epoxy resin selected from the resin mixture can be monofunctional epoxy resin or bifunctional epoxy resin, has an epoxy equivalent of 150-4000g/eq, and is selected from bisphenol A epoxy resin and bisphenol F epoxy resin. The glass transition temperature and heat resistance can be improved by using a multifunctional epoxy resin, the epoxy equivalent is 150-3000g/eq, the multifunctional epoxy resin is selected from phenolic Novolac resin and nitrogen-based epoxy resin, and the epoxy equivalent is 150-3000 g/eq. The epoxy resin can also be epoxy resin with heterocyclic ring structure, such as dicyclopentadiene (DCPD) epoxy resin, and the addition of the DCPD resin has obvious effect of improving the electrical property and the water absorption of the system.
In addition, benzo series resin can be added to improve the processing characteristics of the plate; the structural formula is as follows, for example, the resin with benzo series produced by Kun union corporation is sold under the trade name KB-610F, and the addition of the resin has obvious effects of improving the glass transition temperature, the electrical property and the peeling strength.
The electric characteristics of the plate can be improved by adding dimethyl phenol formaldehyde (2,6DMP) epoxy resin, the structural formula of which is shown as the following, for example, the dimethyl phenol formaldehyde epoxy resin produced by south Asia plastics is under the trade name of NPPN-260, (EEW is 200 eq/g); the addition of 2,6DMP resin also has the effect of improving the electrical property and resin flowability of the plate.
The epoxy resin mixture may be selected from one or more of the above resins depending on processability, physical properties, and the like.
The copolymer of modified flame-retardant styrene maleic anhydride is made of a visible resin composition, so that a non-halogen system is mainly used in response to the trend of environmental protection.
The additive is added to improve or enhance the processing property, the mechanical property and the plate physical property according to the characteristic requirement of the resin composition after hardening. The additive can be Phenoxy resin (Phenoxy resin) with high molecular weight, Rubber (Rubber), flame retardant … and the like. For example, adding INCEMREZ PKHS high molecular weight Phenoxy resin (Phenoxy resin) can improve the toughness and impact strength in a formula system; e.g. adding
CTBN 1300 x 8 Rubber (Rubber) can improve the adhesion strength with copper foil; for example, adding a187S silicon wan coupling agent to increase the adhesion between substrate layers; for example, adding a large amount of tsukamur chemical SPB-100 flame retardant can increase the non-flammability characteristics of the board.
The inorganic filler is added to improve the rigidity of the resin composition of the present invention after curing, to reduce the coefficient of thermal expansion, or to increase the flame retardancy. The inorganic filling material can be one or a mixture of more than one of crystalline, spherical and fused silica, aluminum hydroxide, magnesium hydroxide and alumina, and accounts for 10-40% of the solid weight of the composition. For example: the addition of silicon dioxide can reduce the thermal expansion coefficient of the hardened substance; magnesium hydroxide and aluminum oxide can increase the flame resistance; alumina can improve heat conduction, etc.
The invention aims to provide a novel modified flame-retardant thermosetting resin composition of maleic anhydride and epoxy resin for halogen-free high-frequency application, which can be completely dissolved with a solvent at normal temperature to be prepared into stable homogeneous varnish (varnish), and a Prepreg base material (Prepreg) and a Copper foil substrate material (CCL) which are prepared from the composition can be used for a printed circuit board.
The Prepreg base material (Prepreg) is prepared by blending the resin composition into varnish (varnish), impregnating the epoxy resin composition with a reinforcing material, volatilizing the solvent by a heating oven, and partially reacting the resin composition to form a Prepreg (B-stage). The reinforcing material can be glass fiber, carbon fiber, kelvar fiber, paper fiber, such as aromatic polyamide paper, etc.; the pre-impregnated substrate (Prepreg) can be further pressed to form a copper foil substrate, one or more pre-impregnated substrates are combined, copper foils are placed on the upper surface and the lower surface of the pre-impregnated substrate, and the composition is pressurized and heated to finally obtain the composite material of the copper foil substrate. The resin composition has high glass transition temperature (Tg), excellent heat resistance and excellent electrical characteristics after being hardened, and has low expansion coefficient and high adhesion between layers; can be applied to the printed circuit board in the general or high-frequency field. The invention is further illustrated by reference to the following examples.
The first embodiment is as follows:
20g of benzo heat-resistant resin (Kun union company KB-610F), 20g of dimethyl phenol resin (south Asia plastics NPPN-260) and 60g of benzaldehyde resin (south Asia plastics NPPN-433) are pre-dissolved in Methyl Ethyl Ketone (MEK) to form a 70% solution, and 15 g of modified flame-resistant styrene maleic anhydride copolymer (B) (shown above) is added to the solution; further, 15 g of a phosphorus-containing phenol resin (SHIN' a LC950, korea) and 15 g of a phosphorus-nitrogen flame retardant (tsukamur chemical SPB-100) were added, and a surface-treated inorganic filler powder SIO was added2(Silybidae 525ARI)62 g and 1 g of Silhui coupling agent (A187S); all additives were dissolved in Methyl Ethyl Ketone (MEK) to form a 60% solution, and accelerator 2E4MZ 0.150.150 g, with a 20% equivalent ratio of copolymer of modified flame retardant styrene maleic anhydride (B) to epoxy resin relative to the total resin solids content.
The resin composition was stirred for 3 hours, and then the gel time was measured on a hot plate at 170 ℃ for 250 seconds; feeding the solution into soaking tank, continuously soaking with glass fiber cloth (model 7628), volatilizing solvent via heating oven, and resinThe composition is partially reacted to form a semi-solidified film (B-stage), and the semi-solidified film is cut into sheets after being taken out of an oven and cooled to room temperature; stacking a copper foil (specification 1oz) on each of the upper and lower 8 thin semi-solidified films, heating to 200 deg.C at a heating rate of 2.5 deg.C/min for 60-120 min, and applying a pressure of 20-30kg/cm2The resin composition is pressed by a hot press and continuously reacted until the curing is completed (C-stage), and physical property tests prove that the glass transition temperature (Tg) of more than 150 ℃ and excellent heat resistance can be achieved. The physical property test data are shown in Table II.
Example two:
20g of benzo heat-resistant resin (Kun union company KB-610F), 20g of dimethyl phenol-based resin (south Asia plastics NPPN-260) and 60g of benzaldehyde type resin (south Asia plastics NPPN-433) are pre-dissolved in Methyl Ethyl Ketone (MEK) to form a 70% solution, and 30 g of modified flame-resistant styrene maleic anhydride copolymer (B) is added to the solution; further, 15 g of a phosphorus-containing phenol resin (SHIN' a LC950, korea) and 15 g of a phosphorus-nitrogen flame retardant (tsukamur chemical SPB-100) were added, and a surface-treated inorganic filler powder SIO was added2(Silybac 525ARI)68 g and 1 g of Silhui coupling agent (A187S); all the additives were dissolved in Methyl Ethyl Ketone (MEK) to form a 60% solution, and accelerator 2E4MZ 0.05.05 g, with a 40% equivalent ratio of copolymer of modified flame-retardant styrene maleic anhydride (B) to epoxy resin relative to the total resin solids content; the physical property test data are shown in Table II.
Example three:
the equivalent ratio of the copolymer (B) of modified flame-retardant styrene maleic anhydride and the epoxy resin according to the production method of example one was 60%. The physical property test data are shown in Table II.
Example four:
the equivalent ratio of the copolymer (B) of modified flame-retardant styrene maleic anhydride and the epoxy resin was 80% according to the production method of example one. The physical property test data are shown in Table II.
Example five:
20g of a benzo heat-resistant resin (Kyun Co., Ltd.; KB-610F) and dimethylphenol were usedAldehyde resin (south Asia plastics NPPN-260)20 g and dicyclopentadiene resin (Japanese DIC 7200H)60g were pre-dissolved in Methyl Ethyl Ketone (MEK) to form a 70% solution, and 45 g of modified flame-retardant styrene maleic anhydride copolymer (B) was added to the solution; further, 15 g of a phosphorus-containing phenol resin (SHIN' a LC950, korea) and 20g of a phosphorus-nitrogen flame retardant (tsukamur chemical SPB-100) were added, and a surface-treated inorganic filler powder SIO was added2(Silybac 525ARI)70 g and 1 g of Silhui coupling agent (A187S); all of the additives were dissolved in Methyl Ethyl Ketone (MEK) to form a 60% solution, and accelerator 2E4MZ 0.125.125 g, with a ratio of the modified flame retardant styrene maleic anhydride copolymer (B) to the epoxy resin equivalent of 66% relative to the total resin solids content. The physical property test data are shown in Table II.
Example six:
using 20g of benzo heat-resistant resin (Kun union company KB-610F), 20g of dimethyl phenol aldehyde trifunctional resin, (Nanya plastic NPPN-260) and 60g of biphenyl type phenol aldehyde resin (Korean SHIN' A SE5000) were pre-dissolved in Methyl Ethyl Ketone (MEK) to form a 70% solution, and 45 g of modified flame-resistant type styrene maleic anhydride copolymer (B) was added to the solution; further, 15 g of a phosphorus-containing phenol resin (SHIN' a LC950, korea) and 20g of a phosphorus-nitrogen flame retardant (tsukamur chemical SPB-100) were added, and a surface-treated inorganic filler powder SIO was added2(Silicoco 525ARI)70 g and 1 g of Silhui coupling series (A187S); all of the additives were dissolved in Methyl Ethyl Ketone (MEK) to form a 60% solution, and accelerator 2E4MZ 0.125.125 g, with a 63% equivalent ratio of copolymer of modified flame retardant styrene maleic anhydride (B) to epoxy resin relative to the total resin solids content. The physical property test data are shown in Table II.
Comparative example one:
as for the first example, 20g of benzo heat-resistant resin (Kun union K.B. 610F), 20g of dimethyl phenol resin (Nanya plastics NPPN-260) and 60g of benzaldehyde resin (Nanya plastics NPPN-433) were previously dissolved in Methyl Ethyl Ketone (MEK) to form a 70% solution, and 45 g of styrene maleic anhydride hardener (styrene: 1; maleic anhydride: 4) was added to the solutionEF 40; further, 15 g of a phosphorus-containing phenol resin (SHIN' a LC950, korea) and 30 g of a phosphorus-nitrogen flame retardant (tsukamur chemical SPB-100) were added, and a surface-treated inorganic filler powder SIO was added2(Silybidae 525ARI)75 g and 1 g of Siliquan coupler (A187S); all of the additives were dissolved in Methyl Ethyl Ketone (MEK) to form a 60% solution, and accelerator 2E4MZ 0.05.05 g. Physical property test data according to the manufacturing method of example one are shown in table two.
Comparative example two:
based on comparative example one, 60 grams of styrene maleic anhydride hardener (styrene: 1; maleic anhydride: 4) EF40 was added to the solution; the physical property test data are shown in Table II.
TABLE I, resin composition equivalence ratio ranges of the respective examples and comparative examples
Table two, substrate characteristics of each example and comparative example
The modified flame-retardant maleic anhydride hardener and epoxy resin composition is used for preparing a copper foil substrate, and tests such as glass transition temperature (Tg), copper foil tear strength, thermal decomposition temperature (Td), thermal delamination time (T288), soldering tin heat resistance (288 ℃), dielectric constant (Dk), dielectric loss factor (Df) and the like are carried out by referring to IPC-TM650, and physical property test results show that the modified flame-retardant maleic anhydride hardener and epoxy resin composition has multiple ranges of glass transition temperature (Tg), excellent heat resistance and excellent electrical property, and simultaneously can reduce the addition amount of an external phosphorus (nitrogen) flame retardant, namely can reach 94-V0 level, and is suitable for preparing substrate materials of electronic components and printed circuit boards.
The modified maleic anhydride and epoxy resin composition provided by the invention comprises:
1. high glass transition temperature (Tg) and can be used for high-layer printed circuit boards or carrier boards;
2. the solder has excellent heat resistance, and the phenomena of plate explosion and delamination can not occur when the solder heat resistance test exceeds more than 60 minutes; t288 (copper containing) demixing times can exceed 40 minutes;
3. excellent thermal property, thermal cracking temperature (Td) is more than 375 ℃, and the requirement of the prior halogen-free lead-free process is met;
4. has excellent electrical properties, thereby reducing signal transmission delay and signal distortion at high frequency.
The composition combining the modified maleic anhydride curing agent and the epoxy resin has good heat resistance and excellent electrical characteristics, is suitable for manufacturing prepregs, adhesive sheets and copper clad laminates, and can be applied to printed circuit boards in general or high-frequency fields.
Claims (11)
1. A resin composition, characterized in that the resin composition comprises the following components: (A) one or more than one epoxy resin, (B) modified flame-retardant styrene maleic anhydride copolymer, (C) additive, (D) inorganic filling material, wherein, the molecular weight range of the (B) modified flame-retardant styrene maleic anhydride copolymer is 2000-15000, and the structure of the (B) modified flame-retardant styrene maleic anhydride copolymer is as follows:
wherein m and n are positive integers and are the same or different numbers;
r1 is: an epoxy polymer chain, wherein the epoxy polymer chain is bisphenol A epoxy resin, bisphenol F epoxy resin or novolac epoxy resin;
R2comprises the following steps: DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), DOPO-HQ (10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide) or DOPO-NQ (naphthoquinone compound of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide).
2. The resin composition according to claim 1, wherein the epoxy resin of component (A) is one or more resins selected from the group consisting of BPF (bisphenol F; dihydroxydiphenylmethane) type having an epoxy equivalent of 150-3000g/eq, BPA (bisphenol A; diphenolylpropane) type having an epoxy equivalent of 150-3000g/eq, and heterocyclic epoxy resins.
3. The resin composition of claim 1 wherein the epoxy resin of component (a) comprises 60% to 80% by weight of the composition solids.
4. The resin composition according to claim 1, wherein the component B) modified flame-retardant styrene maleic anhydride copolymer accounts for 10-40% of the solid content of the composition.
5. The resin composition according to claim 1, wherein the additive of component (C) is one or more of a high molecular weight phenoxy resin, a rubber, a phosphorus-containing phenol resin and a flame retardant.
6. The resin composition according to claim 1, wherein the inorganic filler as the component (D) is one or more selected from crystalline silica, spherical silica, fused silica, aluminum hydroxide, magnesium hydroxide and aluminum oxide, and is contained in an amount of 10 to 40% by weight based on the solid content of the composition.
7. The resin composition according to claim 1, wherein the equivalent ratio of the copolymer of modified flame-retardant styrene maleic anhydride as the component (B) to the epoxy resin is 0.2 to 0.8.
8. A prepreg obtained by impregnating or coating the reinforcing material with the resin composition according to claim 1.
9. An adhesive sheet obtained by impregnating or coating the reinforcing material with the resin composition according to claim 1.
10. A copper clad laminate produced by hot-pressing the prepreg according to claim 8.
11. A printed circuit board produced by subjecting the copper clad laminate according to claim 10 to a hot press and wet process.
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