CN108456397B - Halogen-free epoxy resin composition with low dielectric loss - Google Patents
Halogen-free epoxy resin composition with low dielectric loss Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
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Abstract
The invention discloses a halogen-free epoxy resin composition with low dielectric loss, which comprises the following components in part by weight: (A)100 parts by weight of an epoxy resin; (B)10-30 parts by weight of DOPO modified hardener; (C)1-10 parts by weight of benzoxazine resin; (D)60-90 parts by weight of an active ester compound; (E)20-50 parts by weight of a flame retardant; and (F)0.5 to 10 parts by weight of a hardening accelerator. The invention adopts the active ester as the hardener of the epoxy resin, so that the hardened product can achieve the circuit substrate characteristics of low dielectric constant, low dielectric loss, high heat resistance, low water absorption, flame retardance, no halogen and the like. The halogen-free epoxy resin composition can be prepared into a semi-cured film or a resin film and is applied to the preparation of metal laminated plates and printed circuit boards.
Description
Technical Field
The present invention relates to a halogen-free epoxy resin composition, and more particularly to a halogen-free epoxy resin composition with low dielectric loss.
Background
With the high speed and multi-functionalization of electronic product information processing, the application frequency is continuously increased, and 3-6GHz will become the mainstream, and the requirements for the dielectric constant and the dielectric loss value are lower and lower besides the requirement for maintaining higher heat resistance of the laminated plate material.
The conventional epoxy glass fiber cloth laminated board (FR-4) is difficult to meet the use requirements of high frequency and high speed development of electronic products, and meanwhile, the substrate material no longer plays a role of mechanical support under the conventional meaning, and becomes an important way for improving the product performance of designers of Printed Circuit Boards (PCBs) and terminal manufacturers together with electronic components. Since the high dielectric constant (Dk) slows down the signal transmission rate and the high dielectric loss value (Df) partially converts the signal into heat energy to be lost in the substrate material, the reduction of the dielectric constant and dielectric loss value has been the focus of attention of substrate manufacturers. The traditional epoxy glass fiber cloth laminated board material mostly adopts dicyandiamide as a hardening agent, the hardening agent has good operability due to the tertiary reaction amine, but the hardening agent is easy to crack at high temperature due to the weak carbon-nitrogen bond, so that the heat-resistant decomposition temperature of the hardened substance is low, and the heat-resistant requirement of the lead-free technology cannot be met. In view of this background, with the wide range of lead-free technologies implemented several years ago, the industry began to employ phenolic resins as hardeners for epoxy resins, which have a high-density benzene ring heat-resistant structure, so that the heat resistance of the epoxy-cured system is very excellent, but at the same time, the dielectric properties of the cured product tend to be deteriorated.
It has been reported that a series of active ester hardeners containing benzene ring, naphthalene ring or biphenyl structure are synthesized as hardeners of epoxy resin, such as IAAN, IABN, TriABN and TAAN, and the obtained hardened products can obviously reduce the dielectric constant and dielectric loss value compared with the traditional phenolic resin.
Although the above reported techniques propose the use of an active ester as a hardener for epoxy resins to improve the moisture resistance of the hardened product, to reduce the water absorption, and to reduce the dielectric constant and dielectric loss value of the hardened product, they have the disadvantage that it is difficult to achieve a good balance between the heat resistance and the dielectric properties, so that the hardened product has both a high glass transition temperature and a low dielectric loss value, and the dielectric properties are stable with frequency changes, and the water absorption is lower.
Disclosure of Invention
The invention aims to provide a halogen-free epoxy resin composition with low dielectric loss, which adopts active ester as a hardening agent of epoxy resin, so that the hardened product can reach the circuit substrate characteristics of high glass transition temperature, low dielectric property, high heat resistance, flame retardancy, no halogen and the like.
In order to achieve the above object, the present invention provides a halogen-free epoxy resin composition with low dielectric loss, comprising: (A)100 parts by weight of an epoxy resin; (B)10-30 parts by weight of DOPO modified hardener; (C)1-10 parts by weight of benzoxazine resin; (D)60-90 parts by weight of an active ester compound; (E)20-50 parts by weight of a flame retardant; and (F)0.5 to 10 parts by weight of a hardening accelerator.
In one aspect of the invention, the epoxy resin is selected from: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, diglycidyl ether compound of polyfunctional phenols and condensed ring aromatics, trifunctional and tetrafunctional epoxy resins having 3 or 4 epoxy groups in the molecule, and phosphorus-containing epoxy resin, preferably dicyclopentadiene type epoxy resin having a glass transition temperature Tg (175 DEG) effectively increased, Low water absorption, and improved dimensional stability.
The DOPO modified hardener of the invention is selected from: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)) and derivatives or resins thereof, for example DOPO resin may be DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN, DOPO-bonded epoxy resin, etc., wherein the DOPO-PN is DOPO-phenolic novolac, DOPO-BPN may be DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac), DOPO-BPSN (DOPO-bisphenol S novolac), etc., DOPO-modified hardener is mainly used as a hardener in combination with epoxy resin in the present resin composition, the hardener providing excellent thermal and low dielectric properties in addition to excellent thermal and thermal stability, it also has the function of helping to retard flame.
The benzoxazine resin of the present invention is selected from: one selected from the group consisting of bisphenol F (BPF) type benzoxazine, bisphenol S (BPS) type benzoxazine, diaminodiphenylmethane (DDM) type benzoxazine, diaminodiphenyl ether (ODA) type benzoxazine and polyimidized benzoxazine with polyimide, preferably ODA type benzoxazine, which can reduce the dielectric constant Dk (1 to 10GHz, average of about 4.0), dielectric dissipation factor Df (1 to 10GHz, average of about 0.0065), improve heat resistance, and reduce water absorption of the cured product. The halogen-free epoxy resin composition adopts ODA type benzoxazine resin, the benzoxazine resin contains an ODA type structure, and has excellent dielectric properties besides the advantages of high glass transition temperature (Tg), low water absorption, high dimensional stability, low thermal expansion coefficient, good heat resistance and flame retardance and the like of the traditional benzoxazine, and the benzoxazine resin is mixed in the epoxy resin, so that the dielectric constant, dielectric loss value, water absorption and the like of a hardened substance can be reduced, and the adhesive force can be kept not to be reduced; the matching of the benzoxazine and non-dopo phosphorus-containing flame retardant can also help to increase the flame retardant effect, reduce the flame retardance of the hardened product to reach the phosphorus content required by UL 94V-0, and further reduce the water absorption.
The active ester compounds of the present invention are selected from: contains at least one ester group having high reactivity, which can participate in a hardening reaction of the epoxy resin, and the reaction provides excellent low dielectric constant, low dielectric dissipation factor, high heat resistance, and low water absorption rate since no polar group is generated. The active lipid compound has the following structure: the active ester hardening system is a function of taking active ester as an epoxy resin hardening agent, can react with epoxy resin to form a network cross-linked structure without secondary alcoholic hydroxyl, and has lower dielectric property and low water absorption property compared with the network structure of secondary alcoholic hydroxyl generated by ring-opening reaction of a common epoxy resin system. Further, as is known from the prior art, for example, Japanese patent laid-open Nos. 2002-012650, 2003-082063, and 2003-252958, when an active ester compound having a benzene ring, a naphthalene ring, or a biphenyl structure is used as a curing agent for an epoxy resin, the cured product obtained from the epoxy resin composition has a lower dielectric constant and dielectric loss value than conventional phenol resins.
The active ester compound used in the present invention may be an active ester compound having an active ester group, but in the present invention, a compound having at least two active ester groups in its molecule is preferable. The active ester compound may be obtained by reacting a carboxylic acid compound with a hydroxyl compound and/or a thiol compound, preferably, an active ester compound may be obtained by reacting a carboxylic acid compound with one or more compounds selected from a free phenol compound and a naphthol compound, and particularly preferably, an aromatic compound having a phenolic hydroxyl group and at least two active ester groups in a molecule, which is obtained by reacting an active ester compound with both a carboxylic acid compound and a naphthol compound. The active ester compound may be linear or multi-branched. Such as a compound in which the active ester compound has at least two carboxylic acids in its molecule and the compound having at least two carboxylic acids in its molecule contains an aliphatic chain, it can improve the compatibility with an epoxy resin by itself, and when it has an aromatic ring, it can improve heat resistance.
Specific examples of the carboxylic acid compound forming the active ester compound may include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Among them, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, phthalic acid, isophthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable.
specific examples of the hydroxyl compound forming the active ester compound may include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol-m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglycine, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, and the like, wherein, from the viewpoint of improving the heat resistance of the active ester compound, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol and phenol novolac are preferred, and dihydroxy benzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol and phenol novolac are more preferred, dicyclopentadienyl diphenol and phenol novolac are particularly preferred, and the dicyclopentadiene and phenol novolac structure has an effect of suppressing the warpage due to the heat resistance of the substrate and also has an advantage of suppressing the thermal expansion of the wire.
The active ester compound of the invention also comprises an amine structure, which can increase the compatibility of the active ester compound with epoxy resin and other hardeners, and the amine structure can be obtained by reacting and crosslinking with monomers containing amino, particularly preferred is a diamine monomer, which comprises: p-phenylenediamine (p-phenylene diamine; abbreviated as PPDA), 4'-Oxydianiline (4, 4' -Oxydianiline; abbreviated as 4,4 '-ODA), 3, 4' -Oxydianiline (3, 4 '-Oxydianiline; abbreviated as 3, 4' -ODA), 2-Bis (4- [4-aminophenoxy ] phenyl) propane (2, 2-Bis (4- [4-aminophenoxy ] phenyl) propane; abbreviated as BAPP), 2-Bis (4- [3-aminophenoxy ] phenyl) sulfone (2, 2-Bis (4- [3-aminophenoxy ] phenyl) sulfone; abbreviated as m-BAPS), 1, 3-Bis (4-aminophenoxy) benzene (1, 3-Bis (4-aminophenoxy) bezene; abbreviated as TPE-R), etc., 4 is particularly preferable, 4' -oxydianiline-4,4' -oxydianiline (4, 4' -ODA for short, the structure is shown as the following formula).
The active ester compound may be a resin having 1 or more ester groups in 1 molecule, or may be obtained by modifying a commercially available product by synthesis. For example, the modified products can be synthesized from "EXB-9460", "EXB-9470", "EXB-9480", "EXB-9420", and the like, manufactured by DIC corporation.
The method for producing the active ester compound is not particularly limited. It can be prepared by known methods after synthesis. For example, it can be obtained by a condensation reaction between a carboxylic acid compound and a hydroxyl compound.
The active ester is used as the hardener of the epoxy resin, two or more ester groups with high activity exist in the molecules of the active ester hardener, the active ester hardener can carry out hardening reaction with the epoxy resin, and the active ester can form a network structure without secondary hydroxyl and is not easy to generate polar groups when reacting with the epoxy resin, so that the hardened epoxy resin has low water absorption rate, low dielectric loss and excellent heat resistance.
An example of the active ester compound of the present invention is represented by the following formula 1:
x is benzene ring or naphthalene ring, l, m, k is 0 or 1, n is 0.25-2. In formula 1
The (dicyclopentadiene, DCPD) can be substituted by naphthol, phenol, biphenol, bisphenol A, bisphenol F or bisphenol S, and the like, and mainly can be matched with the structure of the epoxy resin in the composition to increase the compatibility between the two.
The halogen-free epoxy resin composition takes the active ester compound as the hardening agent, and fully exerts the advantages that the active ester and the epoxy resin do not generate polar groups after reaction, so that the dielectric property is excellent and the moisture and heat resistance is good.
The resin composition of the present invention does not use a maleic anhydride-modified curing agent because the addition of a maleic anhydride resin composition causes the substrate to become brittle (lower in strength) and poor in heat resistance, and the active ester compound used in the present invention is effective in improving the heat resistance of the entire resin composition and providing an excellent low dielectric loss factor (Df).
The flame retardant of the present invention, such as non-dopo flame retardant, is a compound containing phosphorus and/or vinyl, and is selected from one of the group consisting of the flame retardants having the following structural formula, which has a flame retardant function;
is like
Wherein R is selected from:
one of the group consisting;
formula II
Wherein X is selected from:
one of the group consisting;
y is selected from:
n is an integer from 0 to 500;
formula III
Wherein X is selected from:
one of the group consisting;
a is selected from:
one of the group consisting;
when n is 0, Y is:
when n is an integer from 1 to 500, Y is selected from:
m ≧ 0 for one of the groups;
a is selected from:
one of the group consisting;
z is selected from:
m ≧ 0 is one of the groups.
Wherein X is selected from:
one of the group consisting;
a is selected from:
one of the group of components.
The halogen-free epoxy resin composition of the invention adopts DOPO modified hardener, and has the defect that P-O-C bonding in the DOPO structure is easy to hydrolyze into P-OH, so that the dielectric constant and low dielectric loss of the material are increased, and the Dk/Df of the material is prevented from being improved by selecting Non-DOPO type flame retardant, and the water absorption of the material is prevented from being improved by adding the active ester hardener.
In addition to the Non-dopo type flame retardant, at least one specific flame retardant compound selected from the following compounds may be optionally added. The selected flame retardant compound may be a phosphate compound or a nitrogen-containing phosphate compound, but is not limited thereto, for example: one or more of resorcinol dixylylphosphates (RDXP (e.g., PX-200)), melamine polyphosphate (melamine polyphosphate), tris (2-carboxyethyl) phosphine (tri (2-carboxyethyl) phosphine, TCEP), trimethyl phosphate (TMP), tris (isopropylchloride) phosphate, dimethyl methyl phosphate (DMMP), bisphenol diphenyl phosphate (biphenol diphenyl phosphate), ammonium polyphosphate (ammonium polyphosphate), hydroquinone-bis- (diphenyl phosphate) (hydroquinone bis- (diphenyl phosphate)), bisphenol a-bis- (diphenyl phosphate) (biphenol a bis- (diphenyl phosphate)).
The hardening accelerator of the present invention is selected from: one or more of imidazole (imidazole), boron trifluoride amine complex, 2-ethyl-4-methylimidazole (2E4MI)), 2-methylimidazole (2MI)), 2-phenylimidazole (2-phenyl-1H-imididazole (2PZ)), ethyltriphenylphosphonium chloride (ethyltriphenylphosphonium chloride), Triphenylphosphine (TPP)), and 4-Dimethylaminopyridine (DMAP)), low-molecular-weight terminal bromine-based liquid butadiene rubber BTPB (tertiary bromine-based liquid butadiene rubber).
The halogen-free epoxy resin composition of the present invention may further comprise an inorganic filler to increase the thermal conductivity of the resin composition and improve the thermal expansion and mechanical strength thereof. The inorganic filler is preferably uniformly distributed in the resin composition. The inorganic filler may be previously surface-treated via a silane coupling agent. The inorganic filler may be spherical, flaky, granular, columnar, plate-like, needle-like or irregular. The inorganic filler may comprise one or more of silica (molten, non-molten, porous or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconia, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, graphene.
So that those skilled in the art can easily understand the objects and advantages of the present invention based on the disclosure of the present specification and the scope of the claims, the detailed features and advantages of the present invention will be described in detail in the embodiments without limiting the present invention.
Detailed Description
In order to make the aforementioned and other objects, features and advantages of the invention more comprehensible, several embodiments accompanied with figures are described in detail below: the resin compositions of examples 1 to 5(E1 to E5) are listed in table one, and the resin compositions of comparative examples 1 to 4(C1 to C4) are listed in table three, respectively.
The resin compositions of examples 1 to 5 and comparative examples 1 to 4 were mixed in a stirring tank in batches and then placed in an impregnation tank, and then glass fiber cloth was passed through the impregnation tank to adhere the resin compositions to the glass fiber cloth, and then the mixture was heated and baked to be in a semi-cured state to obtain a prepreg.
And taking four semi-cured films and two copper foils with the thickness of 18 mu m from the same batch of semi-cured films, laminating the semi-cured films and the copper foils in sequence, and pressing the semi-cured films and the copper foils at 220 ℃ for 2 hours under a vacuum condition to form a copper foil substrate, wherein the four semi-cured films are cured to form an insulating layer between the two copper foils.
The physical properties of the copper-containing substrate and the copper-free substrate after copper foil etching are measured, and the physical properties include glass transition temperature (Tg), heat resistance (T288) of the copper-containing substrate, a post-PCT wicking test of the copper-free substrate, a tensile force between the copper foil and the substrate (P/S), a dielectric constant (the lower the Dk is, the better the dielectric loss (the lower the Df is), and flame resistance (UL 94, wherein the order of grade is V-0> V-1> V-2).
Wherein the results of measuring the physical properties of the substrates prepared from the resin compositions of examples 1 to 5 are shown in table two, and the results of measuring the physical properties of the substrates prepared from the resin compositions of comparative examples 1 to 4 are shown in table four. From the second and fourth tables, it can be seen that, when the resin compositions disclosed in the present invention are added in the proportions of the respective components, substrates having good physical properties can be obtained, and the substrates of comparative examples 1 to 4 have poor physical properties. Among them, examples 1 to 5(E1 to E5) using an active ester compound in combination with a DOPO-modified hardener and a benzoxazine resin showed that the dielectric loss (Df) decreased as the amount of the active ester compound added was decreased. As shown in E1, the substrate with the addition of the active ester compound and benzoxazine resin but without the DOPO modified hardener gave a high Tg; as shown in E5, the substrate with the addition of the active ester compound and the DOPO modified hardener but without the benzoxazine resin gave a higher copper foil tensile force (P/S) and a lower dielectric constant (Dk).
Comparative examples 1 to 4(C1 to C4) in which styrene maleic anhydride (EF60) was used in combination with benzoxazine resin, showed poor heat resistance of the substrates (Tg, T288) as the amount of styrene maleic anhydride (EF60) was increased. It can be seen from comparison of examples 1 to 5 and comparative examples 1 to 4 that the active ester compounds used in examples 1 to 5 of the present invention are effective in improving the heat resistance of the resin composition as a whole and providing an excellent low dielectric dissipation factor (Df).
Watch 1
Watch two
Watch III
Watch four
The halogen-free resin composition comprises the specific components and the specific proportion, so that the halogen-free resin composition can achieve low dielectric constant, low dielectric loss, high heat resistance and high flame resistance; the semi-cured film or the resin film can be manufactured, and the purpose of being applied to a copper foil substrate and a printed circuit board is achieved; in terms of industrial applicability, the products derived from the invention can fully meet the current market demands.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A halogen-free epoxy resin composition with low dielectric loss, comprising:
(A)100 parts by weight of an epoxy resin;
(B)10-30 parts by weight of DOPO modified hardener;
(C)1-10 parts by weight of benzoxazine resin;
(D)60-90 parts by weight of an active ester compound;
(E)20-50 parts by weight of a flame retardant; and
(F)0.5 to 10 parts by weight of a hardening accelerator;
wherein the active ester compound is represented by the following formula 1:
x is benzene ring or naphthalene ring, l, m, k is 0 or 1, n is 0.25-2;
in the formula 1
The functional group is substituted with naphthol, phenol, biphenol, bisphenol A, bisphenol F, or bisphenol S structure.
2. The halogen-free epoxy resin composition with low dielectric loss of claim 1, the epoxy resin is selected from one of the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, epoxy resin containing triazine skeleton, epoxy resin containing fluorene skeleton, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, diglycidyl ether compounds of polyfunctional phenols and condensed ring aromatics, trifunctional and tetrafunctional epoxy resins having 3 or 4 epoxy groups in the molecule, and phosphorus-containing epoxy resins.
3. The halogen-free epoxy resin composition with low dielectric loss of claim 1, wherein the DOPO modified hardener is a material selected from the group consisting of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof.
4. The halogen-free epoxy resin composition with low dielectric loss of claim 1, wherein the benzoxazine resin is a resin selected from the group consisting of bisphenol F benzoxazine, bisphenol S benzoxazine, diaminodiphenylmethane benzoxazine, diaminodiphenyl ether benzoxazine and polyimidized benzoxazine.
5. The halogen-free epoxy resin composition with low dielectric loss of claim 1, wherein the flame retardant is one selected from the group consisting of flame retardants with the following structural formula:
is like
Wherein R is selected from:
one of the group consisting;
formula II
Wherein X is selected from:
one of the group consisting;
y is selected from:
n is an integer from 0 to 500;
formula III
Wherein X is selected from:
one of the group consisting;
a is selected from:
one of the group consisting;
when n is 0, Y is:
when n is an integer from 1 to 500, Y is selected from:
one of the groups, m ≧ 0,
a is selected from:
one of the group consisting;
z is selected from:
n ≧ 0 for one of the groups,
wherein X is selected from:
one of the group consisting;
a is selected from:
one of the group of components.
6. The halogen-free epoxy resin composition with low dielectric loss of claim 5, further comprising a flame retardant compound selected from the group consisting of resorcinol dixylyl phosphate, melamine polyphosphate, tris- (2-carboxyethyl phosphine), trimethyl phosphate, tri-isopropyl chloro-phosphate, dimethyl-methyl phosphate, bisphenol biphenyl phosphate, ammonium polyphosphate, hydroquinone-bis-biphenyl phosphate, and bisphenol A-bis-biphenyl phosphate.
7. The halogen-free epoxy resin composition with low dielectric loss of claim 1, wherein the hardening accelerator is one selected from the group consisting of imidazole, boron trifluoride-amine complex, 2-ethyl-4-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphonium chloride, triphenylphosphine, and 4-dimethylaminopyridine.
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| CN108456397B true CN108456397B (en) | 2020-06-02 |
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| CN109608828B (en) * | 2018-12-20 | 2020-10-27 | 广东生益科技股份有限公司 | Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same |
| CN110724366A (en) * | 2019-11-18 | 2020-01-24 | 联茂(无锡)电子科技有限公司 | Prepreg, laminate, and printed wiring board |
| CN111205595A (en) * | 2020-02-18 | 2020-05-29 | 联茂(无锡)电子科技有限公司 | Halogen-free low dielectric composition, laminate and printed wiring board |
| CN111440424A (en) * | 2020-06-03 | 2020-07-24 | 山东科技大学 | Flame-retardant master batch and preparation method and application thereof |
| WO2024065363A1 (en) * | 2022-09-29 | 2024-04-04 | 上纬创新育成股份有限公司 | Aminolysable benzoxazine resin cured product, and preparation method and aminolysis method therefor |
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| CN105482452A (en) * | 2015-12-25 | 2016-04-13 | 广东生益科技股份有限公司 | Halogen-free resin composition as well as prepreg, laminated board and printed circuit board containing halogen-free resin composition |
| CN105778430A (en) * | 2014-12-26 | 2016-07-20 | 广东生益科技股份有限公司 | Epoxy resin composition, and prepreg and laminated board with epoxy resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778430A (en) * | 2014-12-26 | 2016-07-20 | 广东生益科技股份有限公司 | Epoxy resin composition, and prepreg and laminated board with epoxy resin composition |
| CN105482452A (en) * | 2015-12-25 | 2016-04-13 | 广东生益科技股份有限公司 | Halogen-free resin composition as well as prepreg, laminated board and printed circuit board containing halogen-free resin composition |
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