CN109851997B - Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same - Google Patents
Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same Download PDFInfo
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- CN109851997B CN109851997B CN201811587914.7A CN201811587914A CN109851997B CN 109851997 B CN109851997 B CN 109851997B CN 201811587914 A CN201811587914 A CN 201811587914A CN 109851997 B CN109851997 B CN 109851997B
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Abstract
The invention provides a thermosetting resin composition, and a prepreg, a laminated board and a metal foil-clad laminated board using the thermosetting resin composition. The thermosetting resin composition comprises epoxy resin, cyanate ester resin and an ester curing agent with a structure shown in a formula I. According to the invention, the ester curing agent with the structure shown in the formula I and the cyanate ester resin are used for curing the epoxy resin in a synergistic manner, so that polar groups such as secondary hydroxyl groups are not generated in the curing process, and a large number of hydrophobic groups are contained in the cured product, so that the water absorption rate and the dielectric loss factor of the cured product can be obviously reduced while the cured product is ensured to have higher glass transition temperature. The laminated board and the metal foil-clad laminated board prepared by the thermosetting resin composition have good heat resistance, moisture resistance, peeling strength, dielectric property, flame retardance, processability and chemical resistance.
Description
Technical Field
The invention belongs to the technical field of printed circuit boards, and particularly relates to a thermosetting resin composition, and a prepreg, a laminated board and a metal foil-clad laminated board using the thermosetting resin composition.
Background
With the increasing speed and multi-function of electronic product information processing, the application frequency is increasing, and the dielectric constant (Dk) and dielectric loss (Df) are required to be lower, so reducing Dk/Df has become a pursuing hot spot for substrate manufacturers. In order to achieve a high glass transition temperature (Tg) and a low Df, various low polarity resins such as cyanate ester resin (CE), active ester are widely used. The epoxy resin/cyanate ester/active ester ternary system is widely used in the industry aiming at the low-loss material with the Df 0.0060-0.0080 level, and the plate prepared by adopting the ternary system formula has high Tg, high heat resistance and excellent dielectric property, but the cyanate ester and the active ester have the problem of high water absorption.
In addition, under the global strong "green" and "environmental protection", the development of the halogen-free flame retardant copper clad laminate becomes a hot spot in the industry, and various manufacturers of the copper clad laminate have bought about their own halogen-free flame retardant copper clad laminate. At present, the most commonly used halogen-free flame retardant in the industry is still mainly phosphorus flame retardant, and phosphorus flame retardant is easier to absorb moisture than bromine flame retardant, so that the defect of higher water absorption of general halogen-free plates is more obvious than bromine plates.
The high water absorption rate may cause the dielectric properties of the board to be significantly deteriorated due to moisture absorption, and may also cause the board to be broken due to heat after moisture absorption when a Printed Circuit Board (PCB) is processed. Therefore, on the premise of ensuring high Tg and excellent dielectric property, how to reduce the water absorption of the cyanate ester halogen-free system becomes a technical problem.
Benzoxazine resin is commonly used in the copper-clad plate industry to reduce the water absorption of a cured substance, however, the dielectric property of the benzoxazine resin is poor, and the molecular structure contains polar groups, so that the dielectric property and the heat resistance of a cyanate ester system can be seriously deteriorated.
Therefore, how to reduce the water absorption and dielectric loss of the copper-clad plate while ensuring the copper-clad plate to have higher glass transition temperature is an urgent problem to be solved in the field.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide a thermosetting resin composition, and a prepreg, a laminate and a metal-clad laminate using the same. The laminated board and the metal foil-clad laminated board prepared by the thermosetting resin composition have high glass transition temperature, high peel strength, low water absorption, low dielectric constant, low dielectric loss factor, high heat resistance and good chemical resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a thermosetting resin composition, characterized in that the thermosetting resin composition comprises the following components: epoxy resin, cyanate ester resin and ester curing agent;
the ester curing agent has a structure of formula I:
wherein R is1-R8Each independently selected from hydrogen atom, C1-C10Aliphatic hydrocarbon group, C3-C10Alicyclic hydrocarbon radicals or C6-C10Aromatic hydrocarbon group, and not all hydrogen atoms;
x is selected from-O-, -S-, -CH2-or-C (CH)3)2-one of the above;
y is selected from C1-C10Aliphatic hydrocarbon group, C3-C10Alicyclic hydrocarbon radicals or C6-C10One of aromatic hydrocarbon groups;
n is an integer of 1 to 10.
The invention takes epoxy resin and cyanate ester resin as main resin, and matches with ester curing agent with structure of formula I to form thermosetting resin composition, the thermosetting resin composition does not generate secondary hydroxyl and other polar groups in the curing process, and the cured product contains a large amount of hydrophobic groups, so that the water absorption rate and dielectric loss factor of the cured product can be obviously reduced while the cured product is ensured to have higher glass transition temperature, and the dielectric constant and dielectric loss factor of the cured product are more stable. The laminated board and the metal foil-clad laminated board prepared by the thermosetting resin composition have high glass transition temperature, high peel strength, low water absorption, low dielectric constant, low dielectric loss factor, high heat resistance and good chemical resistance.
In the present invention, said C1-C10Aliphatic hydrocarbyl refers to aliphatic hydrocarbyl groups containing 1-10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms; for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or the like can be mentioned.
Said C is3-C10By cycloaliphatic hydrocarbon group is meant a cycloaliphatic hydrocarbon group containing from 3 to 10 (e.g., 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms; for example, it may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or the like.
Said C is6-C10Aromatic hydrocarbon group means an aliphatic hydrocarbon group containing 6 to 10 (e.g., 6, 7, 8, 9 or 10) carbon atoms; for example, phenyl, benzyl, phenethyl, phenylpropyl, etc.
In formula I n may be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
As a preferred technical solution of the present invention, the thermosetting resin composition comprises, based on 100 parts by weight of the total weight of the epoxy resin, the cyanate ester resin and the ester curing agent: 40-70 parts of epoxy resin, 10-35 parts of cyanate ester resin and 5-25 parts of ester curing agent.
Unless otherwise specified, the term "ester curing agent" used herein refers to an ester curing agent having a structure of formula I.
In the present invention, the epoxy resin may be 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, or the like by weight.
The parts by weight of the cyanate ester resin may be 10 parts, 12 parts, 13 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 23 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 33 parts, 35 parts, or the like.
The weight portion of the ester curing agent can be 5, 6, 8, 10, 12, 13, 15, 16, 18, 20, 22, 23 or 25 parts.
According to the invention, the epoxy resin, the cyanate ester resin and the ester curing agent are matched with each other at the specific ratio, so that the comprehensive performance of the cured product and the laminated board prepared from the cured product can be further improved. If the content of the epoxy resin is too small, the processability of the laminated board is poor; if the amount of the epoxy resin added is too large, the glass transition temperature of the cured product and the laminate is low, and the dielectric properties are poor. If the content of the cyanate ester resin is too low, the glass transition temperature of the cured product is low, and the dielectric property is poor; if the content of the cyanate ester resin is too large, the cured product and the laminate obtained are brittle and have poor processability. If the content of the ester curing agent is too small, the improvement effect on the water absorption rate and the dielectric property of the cured product is not obvious, and if the content of the ester curing agent is too large, the brittleness and the processability of the cured product and the laminated board are high.
As a preferred technical scheme of the invention, the epoxy resin is halogen-free epoxy resin.
Preferably, the halogen-free epoxy resin is selected from one or a combination of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, o-cresol novolac epoxy resin, bisphenol a type novolac epoxy resin, triphenol type novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl type novolac epoxy resin, alkylbenzene type novolac epoxy resin or naphthol type novolac epoxy resin.
Preferably, the halogen-free epoxy resin has the structure of formula II:
wherein, X1、X2And X3Each independently is
R9Selected from hydrogen atoms, substituted or unsubstituted C1-C5Straight chain alkyl or substituted or unsubstituted C3-C5One of the branched alkyl groups;
Y1and Y2Each independently selected from a single bond, -CH2-、
One of (1), R10Selected from hydrogen atoms, substituted or unsubstituted C1-C5Straight chain alkyl or substituted or unsubstituted C3-C5One of the branched alkyl groups;
m is an integer of 1 to 10; for example, it may be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
In the present invention, said C1-C5Straight chain alkyl refers to straight chain alkyl groups containing 1 to 5 (e.g., 1, 2, 3, 4, or 5) carbon atoms; for example, methyl, ethyl, propyl, butyl or pentyl.
Said C is3-C5Branched alkyl refers to branched alkyl groups containing 3 to 5 (e.g., 3, 4, or 5) carbon atoms; for example, isopropyl, isobutyl, tert-butyl, isopentyl, etc. may be mentioned.
The halogen-free epoxy resin with the structure of the formula II has higher functionality and good dielectric property, and is beneficial to further improving the glass transition temperature of a cured product and reducing dielectric loss and water absorption.
In a preferred embodiment of the present invention, the cyanate ester resin is selected from the group consisting of bisphenol a type cyanate ester resin, bisphenol F type cyanate ester resin, tetramethylbisphenol F type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol P type cyanate ester resin, novolac type cyanate ester resin, cresol novolac type cyanate ester resin, naphthol novolac type cyanate ester resin, dicyclopentadiene type cyanate ester resin, phenolphthalein type cyanate ester resin, aralkyl type cyanate ester resin, bisphenol a type cyanate ester prepolymer, bisphenol F type cyanate ester prepolymer, tetramethylbisphenol F type cyanate ester prepolymer, bisphenol M type cyanate ester prepolymer, bisphenol S type cyanate ester prepolymer, bisphenol E type cyanate ester prepolymer, bisphenol P type cyanate ester prepolymer, bisphenol F type cyanate ester prepolymer, bisphenol M type cyanate ester, Any one or a mixture of at least two of a novolac type cyanate prepolymer, a cresol novolac type cyanate prepolymer, a naphthol novolac type cyanate prepolymer, a dicyclopentadiene type cyanate prepolymer, a phenolphthalein type cyanate prepolymer, an aralkyl type cyanate prepolymer or an aralkyl type cyanate prepolymer, preferably any one or a mixture of at least two of a novolac type cyanate resin, a naphthol novolac type cyanate resin, a phenolphthalein type cyanate resin, an aralkyl type cyanate resin, a novolac type cyanate prepolymer, a naphthol type cyanate prepolymer, a phenolphthalein type cyanate prepolymer, an aralkyl type cyanate prepolymer or an aralkyl type cyanate prepolymer, further, any one of or a mixture of at least two of the novolac type cyanate ester resin, the naphthol novolac type cyanate ester resin, the aralkyl novolac type cyanate ester resin, the novolac type cyanate ester prepolymer, the naphthol novolac type cyanate ester prepolymer, and the aralkyl novolac type cyanate ester prepolymer is preferable.
As a preferred embodiment of the present invention, the thermosetting resin composition further comprises a flame retardant.
Preferably, the flame retardant is a phosphorus-containing flame retardant.
Preferably, the phosphorus-containing flame retardant is added in an amount of 1-50 parts, such as 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc., based on 100 parts of the total weight of the epoxy resin, cyanate ester resin and ester curing agent; more preferably 1 to 30 parts.
Preferably, the phosphorus-containing flame retardant is selected from one or a combination of at least two of tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a phenoxyphosphazene compound, a phosphate ester, a polyphosphate ester, a phosphonate ester, or a polyphosphonate ester.
In a preferred embodiment of the present invention, the thermosetting resin composition further comprises a curing accelerator to cure the resin composition and accelerate the curing speed of the resin composition.
Preferably, the addition amount of the curing accelerator is 0.05-1 part by taking the total weight parts of the epoxy resin, the cyanate ester resin and the ester curing agent as 100 parts; for example, it may be 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part, etc.
Preferably, the curing accelerator is one or a combination of at least two of imidazole compounds, triphenylphosphine, dimethylaminopyridine, boron trifluoride monoethylamine or zinc octoate.
Preferably, the imidazole compound is selected from one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole.
Preferably, the thermosetting resin composition further includes a filler to further reduce the Coefficient of Thermal Expansion (CTE) and water absorption of the cured product and the laminate, increasing thermal conductivity.
Preferably, the filler is added in an amount of 1-150 parts, for example, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, etc., based on 100 parts of the total weight of the epoxy resin, cyanate ester resin and ester curing agent; more preferably 1 to 100 parts.
Preferably, the filler is an organic filler and/or an inorganic filler.
Preferably, the inorganic filler is selected from one or a combination of at least two of silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
Preferably, the organic filler is selected from one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyether sulfone powder.
In the present invention, the filler is most preferably silica, and may be, for example, fused silica, crystalline silica, spherical silica, hollow silica or the like; the median particle diameter is 1 to 15 μm, and may be, for example, 1 μm, 2 μm, 3 μm, 5 μm, 6 μm, 8 μm, 10 μm, 12 μm, 13 μm or 15 μm; more preferably 1 to 10 μm. The filler having a particle size distribution within the above range has better dispersibility in the thermosetting resin composition.
In a second aspect, the present invention provides a resin glue solution, wherein the resin glue solution is obtained by dissolving or dispersing the thermosetting resin composition provided by the first aspect of the present invention in a solvent.
In a third aspect, the present invention provides a prepreg comprising a reinforcing material, and the thermosetting resin composition provided by the first aspect of the present invention attached to the reinforcing material by impregnation drying.
In the present invention, the prepreg can be prepared by the following method:
dissolving the thermosetting resin composition in a solvent to form a resin glue solution, then impregnating a reinforcing material with the resin glue solution, and drying to obtain the prepreg.
Wherein the solvent is preferably Methyl Ethyl Ketone (MEK), the solid content of the glue solution is preferably 60-70%, the reinforcing material is preferably glass cloth, and the impregnation amount of the glue solution is preferably 200-230g/m2The drying temperature is preferably 155 ℃ and the drying time is preferably 5-10 min.
In a fourth aspect, the present invention provides a laminate comprising one or at least two prepregs according to the third aspect of the present invention in stacked relationship.
In a fifth aspect, the present invention provides a metal foil-clad laminate comprising one or at least two stacked prepregs according to the third aspect of the present invention and a metal foil clad on one or both sides of the outer side of the prepreg.
The metal foil-clad laminate is prepared by the steps of firstly laminating one or at least two prepregs, then attaching a metal foil to one side or two sides of the outermost side of each prepreg, and finally heating, pressurizing and curing.
The heating and pressing operation can be performed by a laminating machine, and the laminating machine has the following requirements: firstly, the heating rate of lamination is controlled to be 1.5-2.5 ℃/min when the material temperature is 80-120 ℃; setting the laminating pressure, wherein the outer layer material temperature is 120 ℃ and 150 ℃, and full pressure is applied, and the full pressure is about 350 psi; thirdly, during curing, the material temperature is controlled at 220 ℃ and is kept for 60-120 min.
The metal foil may be a copper foil, a nickel foil, an aluminum foil, or a SUS foil (stainless steel foil), or the like.
In a sixth aspect, the present invention provides a printed circuit board comprising at least one prepreg according to the third aspect of the present invention.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes epoxy resin and cyanate ester resin as main resin, and is matched with the ester curing agent with the structure of formula I to form the thermosetting resin composition, the thermosetting resin composition does not generate secondary hydroxyl and other polar groups in the curing process, and the cured product contains a large amount of hydrophobic groups, so that the glass transition temperature of the cured product can be effectively improved, and the water absorption rate and the dielectric loss factor of the cured product can be reduced. The glass transition temperature of the laminated board prepared by the thermosetting resin composition is 178-2The flame-retardant property reaches V-0 grade, and the flame-retardant polyester film has good heat resistance, moisture resistance, peeling strength, dielectric property, flame retardance, processability and chemical resistance.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources/preparation methods of the materials involved in the examples of the invention and the comparative examples are as follows:
(A) halogen-free epoxy resin
(A-1) Dicyclopentadiene novolac epoxy HP-7200H (trade name for Large Japanese ink);
(A-2) a biphenyl type novolac epoxy resin NC-3000 (trade name of Nippon Chemicals);
(A-3) naphthalene-containing epoxy resin HP-9900 (trade name for Dainippon ink).
(B) Cyanate ester resin
(B-1) bisphenol A type cyanate ester prepolymer CE01PS (trade name, Yangzhou Tianji);
(B-2) a novolak type cyanate ester resin PT-30 (trade name of Lonza, Switzerland);
(B-3) DCPD phenolic cyanate resin CY-40 (trade name of Wu bridge Jiangsu).
(C) Curing agent
(C-1) the ester curing agent with the structure of formula I, wherein the structure is as follows:
wherein the average repeat unit n is 1.25;
the preparation method comprises the following steps:
a flask equipped with a thermometer, a dropping funnel and a stirrer was charged with 2mol (568.78g) of tetramethylbisphenol A and 1500g of tetrahydrofuran, and the mixture was stirred with nitrogen gas until it was completely dissolved. Then, 1mol (203.02g) of terephthaloyl chloride was added and dissolved by stirring, and then, 2mol (202.38g) of triethylamine (prepared as a 20% triethylamine/tetrahydrofuran solution) was slowly added dropwise (more than 0.5 hour) while controlling the system temperature to 20 ℃ or lower. Then, the reaction is continued for 2 to 3 hours at a temperature of 20 ℃. Then, 2mol (381.25g) of 2-naphthoyl chloride is added, the temperature of the system is controlled below 15 ℃, then 2mol (202.38g) of triethylamine (prepared into a 20% triethylamine/tetrahydrofuran solution for dropwise addition) is slowly added dropwise, and the stirring reaction is continued for 2-5 hours at the temperature below 15 ℃. And standing after the reaction is finished, filtering to remove triethylamine hydrochloride solid, carrying out reduced pressure distillation concentration on the solution, then adding methanol to separate out a resin product, filtering, washing with water until the pH value of a final water layer is 7, then washing with methanol, and drying to obtain a product. The ester equivalent of the prepared active ester resin is 252g/eq according to the feeding ratio.
(C-2) an ester curing agent having the structure of formula I, which has the structure:
wherein the average repeat unit n is 1.25;
the preparation method comprises the following steps:
a flask equipped with a thermometer, a dropping funnel and a stirrer was charged with 2mol (568.78g) of tetramethylbisphenol A and 1500g of tetrahydrofuran, and the mixture was stirred with nitrogen gas until it was completely dissolved. Then, 1mol (203.02g) of terephthaloyl chloride was added and dissolved by stirring, and then, 2mol (202.38g) of triethylamine (prepared as a 20% triethylamine/tetrahydrofuran solution) was slowly added dropwise (more than 0.5 hour) while controlling the system temperature to 20 ℃ or lower. Then, the reaction is continued for 2 to 3 hours at a temperature of 20 ℃. Then, 2mol (281.14g) of benzoyl chloride is added, the system temperature is controlled below 15 ℃, then 2mol (202.38g) of triethylamine (prepared into a 20% triethylamine/tetrahydrofuran solution for dropwise addition) is slowly added dropwise, and the stirring reaction is continued below 15 ℃ for 2-5 hours. And standing after the reaction is finished, filtering to remove triethylamine hydrochloride solid, carrying out reduced pressure distillation concentration on the solution, then adding methanol to separate out a resin product, filtering, washing with water until the pH value of a final water layer is 7, then washing with methanol, and drying to obtain a product. The ester equivalent of the prepared active ester resin is 226g/eq according to the feeding ratio.
(C-3) the ester curing agent with the structure of formula I, wherein the structure is as follows:
wherein the average repeat unit n is 1.25;
the preparation method comprises the following steps:
a flask equipped with a thermometer, a dropping funnel and a stirrer was charged with 2mol (512.66g) of tetramethylbisphenol F and 1500g of tetrahydrofuran, and the mixture was stirred with nitrogen gas until it was completely dissolved. Then, 1mol (203.02g) of terephthaloyl chloride was added and dissolved by stirring, and then, 2mol (202.38g) of triethylamine (prepared as a 20% triethylamine/tetrahydrofuran solution) was slowly added dropwise (more than 0.5 hour) while controlling the system temperature to 20 ℃ or lower. Then, the reaction is continued for 2 to 3 hours at a temperature of 20 ℃. Then, 2mol (157g) of acetyl chloride is added, the temperature of the system is controlled below 15 ℃, then 2mol (202.38g) of triethylamine (prepared into a 20% triethylamine/tetrahydrofuran solution for dropwise addition) is slowly added dropwise, and the stirring reaction is continued below 15 ℃ for 2-5 hours. And standing after the reaction is finished, filtering to remove triethylamine hydrochloride solid, carrying out reduced pressure distillation concentration on the solution, then adding methanol to separate out a resin product, filtering, washing with water until the pH value of a final water layer is 7, then washing with methanol, and drying to obtain a product. The ester equivalent of the prepared active ester resin is 181g/eq according to the feeding ratio.
(C-4) an ester curing agent V-575 (trade name of NITIKA) having the following structure:
wherein the average repeat unit n is 1.25;
(C-5) Dicyclopentadienol-type active ester HPC-8000T65 (trade name for Dainippon ink);
(C-6) Dicyclopentadiene-type benzoxazine LZ 8260N70 (trade name HUNTSMAN).
(D) Flame retardant
(D-1) a phosphorus-containing phenol aldehyde XZ92741 (trade name of Dow in USA);
(D-2) Phenoxyphosphazene Compound SPB-100 (trade name of Mitsubishi Japan).
(E) Curing accelerator
(E-1) Zinc isooctanoate (leading chemical trade name in Shanghai);
(E-2) 4-dimethylaminopyridine (trade name of Kwangschem).
(F) Filler material
(F-1) spherical silica micropowder (average particle diameter of 1-10 μm, purity of 99% or more)
(F-2) alumina (average particle diameter of 1-10 μm, purity of 99% or more).
Examples 1 to 16
Examples 1 to 16 provide thermosetting resin composition glue solutions, prepregs and copper clad laminates using the same, the preparation methods are as follows:
(1) preparation of thermosetting resin composition glue solution:
preparing solutions with solid contents of 60%, 50% and 25% from the component (B) cyanate ester resin, (C) curing agent and the component (D-2) phenoxyphosphazene compound SPB-100 by using MEK solvent, sequentially adding the solutions into a 1000mL beaker, sequentially adding the (A) halogen-free epoxy resin, (D-1) phosphorus-containing phenolic XZ92741 and the (F) filler, adding a proper amount of (E) curing accelerator, adjusting the Gelation Time (GT) to 200 and 300s, adding the MEK solvent to control the solid content to 65%, and continuously stirring for 2h for curing to obtain thermosetting resin composition glue solution;
the kinds and amounts (in parts by weight) of the respective components are shown in tables 1 and 2.
(2) Preparation of prepreg:
6 pieces of 2116 glass cloth (manufacturer: Taiwan Hubei Co., Ltd.) were prepared, and the size: 320mm × 380mm, coating the glue solution of the thermosetting resin composition on each glass cloth, infiltrating the glass cloth with the glue solution, adhering resin on the two surfaces, then scraping the two surfaces of the infiltrated glass cloth through a rolling clamping shaft, removing part of the glue solution, and controlling the sum of the weight of the glass cloth and the resin composition after solvent removal to be 200-2And (3) obtaining the pre-impregnated glass cloth, and then putting the glass cloth into an oven at 155 ℃ for baking for 6-8min to obtain the pre-impregnated material.
(3) Manufacturing a copper-clad plate:
2 pieces of electrolytic copper foil (manufacturer: Suzhou Futian) having a thickness of 35 μm and a size of 410mm × 410mm were prepared, 6 pieces of the above prepregs were stacked while keeping 4-degree alignment, and the upper and lower surfaces of the stacked prepregs were covered with one prepared electrolytic copper foil, respectively, and placed in a laminator and laminated under the following conditions: firstly, the temperature rising rate of lamination is controlled to be 1.5-2.5 ℃/min when the material temperature is 80-120 ℃; setting the laminating pressure, wherein the outer layer material temperature is 120 ℃ and 150 ℃ and full pressure is applied, and the full pressure is 350 psi; and thirdly, controlling the material temperature to be 200 ℃ during curing, and preserving the heat for 90min to obtain the copper-clad plate.
Comparative examples 1 to 3
Comparative examples 1 to 3 are different from example 2 in the kind of the curing agent of the component (C), and are specifically shown in the following Table 3.
Comparative examples 4 to 6
Comparative examples 4 to 6 are different from example 16 in the kind of the curing agent of the component (C), and are specifically shown in the following Table 3.
The performance of the copper-clad plates provided by the above examples and comparative examples is tested, and the test standards/methods are as follows:
(a) glass transition temperature (Tg): the measurement was carried out by Differential Scanning Calorimetry (DSC) according to the DSC method defined by IPC-TM-6502.4.25.
(b) Coefficient of Thermal Expansion (CTE)
Measured according to the Z-directed CTE test method specified in IPC-TM-6502.4.24.
(c) Water absorption
After a sample of 100mm multiplied by 100mm is placed in a constant temperature and humidity box with the temperature of 85 ℃ and the humidity of 85 percent for treatment for 168 hours, the water absorption rate of the treated sample is tested.
(d) Dielectric constant and dielectric dissipation factor
The dielectric loss and dielectric dissipation factor at 1GHz were measured by IPC-TM-6502.5.5.5 according to the resonance method using a strip line.
(e) Dielectric constant, dielectric dissipation factor (after moisture)
After the sample is placed in a constant temperature and humidity box with the temperature of 85 ℃ and the humidity of 85 percent for treatment for 168 hours, the dielectric loss and the dielectric loss factor under 1GHz are measured according to IPC-TM-6502.5.5.5.
(f) Resistance to dip soldering
The delamination foaming time was observed according to IPC-TM-6502.4.13.1.
(g) Peel strength
The peel strength of the metal cap was tested according to the "post thermal stress" experimental conditions in the IPC-TM-6502.4.8 method.
(h) Area of drop hammer impact crack
Adopting a drop hammer impact tester for testing, wherein the test method comprises the following steps: the height of the drop weight was 1m, the weight of the drop weight was 0.75kg, the drop weight was released, and the plate crack area was measured. The fracture area of the plate can preliminarily reflect the toughness of the plate, and generally speaking, the smaller the fracture area is, the better the toughness of the plate is.
(i) Fire resistance property
Measured according to the UL94 vertical burning method.
The copper-clad plate provided by each example and each comparative example has the following properties shown in the following tables 1 to 3:
TABLE 1
TABLE 2
TABLE 3
From the performance data of tables 1-3, it can be seen that: in examples 1-10, 5-25 parts of the ester curing agent having the structure of formula I and 10-35 parts of cyanate ester are compounded and cured with 40-70 parts of the halogen-free epoxy resin, and the obtained sheet has high Tg, low CTE, low water absorption, excellent dielectric properties, high heat resistance, peel strength, and excellent toughness, and can realize halogen-free flame retardation at V-0 level.
In example 11, 75 parts of dicyclopentadiene novolac epoxy HP-7200H is cured by compounding the ester curing agent with the structure of formula I and the bisphenol A cyanate ester prepolymer CE01PS, the plate has high Tg and low CTE, but the dicyclopentadiene novolac epoxy HP-7200H is excessive, so that the curing is incomplete, and the final plate has high water absorption, poor dielectric properties and unsatisfactory heat resistance.
In example 12, 38 parts of dicyclopentadiene novolac epoxy HP-7200H was cured with 27 parts of ester curing agent having the structure of formula I and the bisphenol A cyanate ester prepolymer CE01PS, the board had high Tg, low CTE, low water absorption and excellent dielectric properties, but the board had unsatisfactory heat resistance, and the area of crack in falling weight impact test, which is used to characterize toughness, was large, the board toughness was poor, and it was not favorable for downstream PCB processing.
In example 13, 3 parts of the ester curing agent having the structure of formula I and the bisphenol a cyanate ester prepolymer CE01PS were used to cure dicyclopentadiene novolac epoxy resin HP-7200H, and the board has high Tg, low CTE, excellent heat resistance and toughness, but high water absorption, and the dielectric properties of the board after moisture absorption are seriously deteriorated.
In example 14, 40 parts of bisphenol a cyanate ester prepolymer CE01PS and the ester curing agent with the structure of formula I are compounded to cure dicyclopentadiene novolac epoxy resin HP-7200H, the board has high Tg, low CTE, low water absorption and excellent dielectric properties, but the board toughness is poor due to too high addition of CE01PS, which is not favorable for downstream PCB processing.
In example 15, 8 parts of the bisphenol a cyanate ester prepolymer CE01PS was compounded with the ester curing agent having the structure of formula I to cure dicyclopentadiene novolac epoxy HP-7200H, and the sheet had low CTE, low water absorption, and excellent dielectric dissipation factor, but the sheet had a low Tg, a high dielectric constant, and unsatisfactory heat resistance.
In example 16, the ester curing agent with the structure of formula I is used to cure dicyclopentadiene novolac epoxy resin HP-7200H in combination with bisphenol a cyanate ester prepolymer CE01PS, without adding filler, the CTE and water absorption of the board are raised, but the CTE and water absorption of the board are still maintained at a desirable level, and the board has high Tg, excellent dielectric properties, heat resistance and toughness.
As described above, compared with a general halogen-free laminate, the laminate prepared by using the thermosetting resin composition provided by the present invention has higher Tg, lower CTE, lower water absorption, and more excellent dielectric properties, peel strength, heat resistance, and toughness, and is suitable for high-speed application fields. In addition, the halogen content of the invention can reach the V-0 standard in a flame retardant test UL94 within the halogen-free standard requirement range of JPCA, and the invention has the effect of environmental protection.
In comparative example 1, the dicyclopentadiene novolac epoxy resin HP-7200H is cured by compounding the ester curing agent V-575 and the bisphenol A cyanate ester prepolymer CE01PS, so that the plate has high Tg, low CTE, excellent dielectric property and heat resistance, but the water absorption is high, and the dielectric property of the plate after moisture absorption is poor.
In comparative example 2, the dicyclopentadiene phenol epoxy resin HP-7200H is cured by compounding the dicyclopentadiene phenol active ester HPC-8000T65 with the bisphenol A cyanate prepolymer CE01PS, so that the plate has high Tg, low CTE, excellent dielectric properties and heat resistance, but high water absorption and poor dielectric properties after the plate absorbs moisture.
In comparative example 3, dicyclopentadiene novolac epoxy resin HP-7200H was cured by compounding dicyclopentadiene benzoxazine LZ 8260N70 with bisphenol a cyanate ester prepolymer CE01PS, but the sheet material had a higher Tg, a lower CTE, a low water absorption rate, and an excellent dielectric constant, but had a higher dielectric loss factor and unsatisfactory heat resistance.
In comparative example 4, the dicyclopentadiene novolac epoxy resin HP-7200H is cured by compounding the ester curing agent V-575 and the bisphenol A cyanate ester prepolymer CE01PS without adding filler, so that the plate has high Tg and excellent dielectric property, but the plate has high water absorption rate, poor dielectric property after moisture absorption and unsatisfactory heat resistance.
In comparative example 5, dicyclopentadiene phenol epoxy resin HP-7200H was cured by compounding dicyclopentadiene phenol active ester HPC-8000T65 with bisphenol A cyanate prepolymer CE01PS without adding filler, the sheet had high Tg and excellent dielectric properties, but the sheet had high water absorption, poor dielectric properties after moisture absorption, and poor heat resistance.
In comparative example 6, dicyclopentadiene novolac epoxy resin HP-7200H was cured by compounding dicyclopentadiene benzoxazine LZ 8260N70 with bisphenol a cyanate ester prepolymer CE01PS, and the sheet had a high Tg, low water absorption, and excellent dielectric constant without adding a filler, but the sheet had a high dielectric loss factor and unsatisfactory heat resistance.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (29)
1. A thermosetting resin composition characterized by comprising the following components: epoxy resin, cyanate ester resin and ester curing agent;
the thermosetting resin composition comprises the following components in parts by weight based on 100 parts by weight of the epoxy resin, the cyanate ester resin and the ester curing agent: 40-70 parts of epoxy resin, 10-35 parts of cyanate ester resin and 5-25 parts of ester curing agent;
the ester curing agent has a structure of formula I:
wherein R is1-R8Each independently selected from hydrogen atom, C1-C10Aliphatic hydrocarbon group, C3-C10Alicyclic hydrocarbon radicals or C6-C10Aromatic hydrocarbon group, and not all hydrogen atoms;
x is-CH2-or-C (CH)3)2-；
Y is selected from C1-C10Aliphatic hydrocarbon group, C3-C10Alicyclic hydrocarbon radicals or C6-C10One of aromatic hydrocarbon groups;
n is an integer of 1 to 10.
2. The thermosetting resin composition of claim 1, wherein the epoxy resin is a halogen-free epoxy resin.
3. The thermosetting resin composition according to claim 2, wherein the halogen-free epoxy resin is selected from one or a combination of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, o-cresol novolac epoxy resin, bisphenol a type novolac epoxy resin, triphenol type novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl type novolac epoxy resin, alkylbenzene type novolac epoxy resin, or naphthol type novolac epoxy resin.
4. The thermosetting resin composition of claim 2, wherein the halogen-free epoxy resin has the structure of formula II:
wherein, X1Is composed of
X2And X3Each independently is
R9Selected from hydrogen atoms, substituted or unsubstituted C1-C5Straight chain alkyl or substituted or unsubstituted C3-C5One of the branched alkyl radicals, Y1And Y2Each independently selected from a single bond, -CH2-、
One of (1), R10Selected from hydrogen atoms, substituted or unsubstituted C1-C5Straight chain alkyl or substituted or unsubstituted C3-C5One of the branched alkyl groups, m is an integer of 1 to 10.
5. The thermosetting resin composition according to claim 1, wherein the cyanate ester resin is selected from the group consisting of bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, tetramethylbisphenol F type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol P type cyanate ester resin, novolac type cyanate ester resin, cresol novolac type cyanate ester resin, naphthol novolac type cyanate ester resin, dicyclopentadiene type cyanate ester resin, phenolphthalein type cyanate ester resin, aralkyl type cyanate ester resin, bisphenol A type cyanate ester prepolymer, bisphenol F type cyanate ester prepolymer, tetramethylbisphenol F type cyanate ester prepolymer, bisphenol M type cyanate ester prepolymer, bisphenol S type cyanate ester prepolymer, bisphenol E type cyanate ester prepolymer, bisphenol A type cyanate, Any one or a mixture of at least two of bisphenol P type cyanate ester prepolymer, novolac type cyanate ester prepolymer, cresol novolac type cyanate ester prepolymer, naphthol novolac type cyanate ester prepolymer, dicyclopentadiene type cyanate ester prepolymer, phenolphthalein type cyanate ester prepolymer, aralkyl type cyanate ester prepolymer or aralkyl type cyanate ester prepolymer.
6. The thermosetting resin composition according to claim 5, wherein the cyanate ester resin is selected from any one of or a mixture of at least two of novolac type cyanate ester resin, naphthol novolac type cyanate ester resin, phenolphthalein type cyanate ester resin, aralkyl type cyanate ester resin, novolac type cyanate ester prepolymer, naphthol novolac type cyanate ester prepolymer, phenolphthalein type cyanate ester prepolymer, aralkyl type cyanate ester prepolymer or aralkyl type cyanate ester prepolymer.
7. The thermosetting resin composition, according to claim 6, wherein the cyanate ester resin is selected from any one or a mixture of at least two of novolac type cyanate ester resin, naphthol novolac type cyanate ester resin, aralkyl novolac type cyanate ester resin, novolac type cyanate ester prepolymer, naphthol novolac type cyanate ester prepolymer, or aralkyl novolac type cyanate ester prepolymer.
8. The thermosetting resin composition of claim 1, further comprising a flame retardant.
9. The thermosetting resin composition of claim 8, wherein the flame retardant is a phosphorus-containing flame retardant.
10. The thermosetting resin composition of claim 9, wherein the phosphorus-containing flame retardant is added in an amount of 1-50 parts based on 100 parts by weight of the total amount of the epoxy resin, the cyanate ester resin and the ester curing agent.
11. The thermosetting resin composition of claim 10, wherein the phosphorus-containing flame retardant is added in an amount of 1-30 parts based on 100 parts by weight of the total amount of the epoxy resin, the cyanate ester resin and the ester curing agent.
12. The thermosetting resin composition of claim 9, wherein the phosphorus-containing flame retardant is one or a combination of at least two selected from tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a phenoxyphosphazene compound, a phosphate ester, a polyphosphate ester, a phosphonate ester, or a polyphosphonate ester.
13. The thermosetting resin composition of claim 1, further comprising a curing accelerator.
14. The thermosetting resin composition of claim 13, wherein the curing accelerator is added in an amount of 0.05 to 1 part based on 100 parts by weight of the total amount of the epoxy resin, the cyanate ester resin and the ester curing agent.
15. The thermosetting resin composition of claim 13, wherein the curing accelerator is one or a combination of at least two selected from the group consisting of imidazoles, triphenylphosphine, dimethylaminopyridine, boron trifluoride monoethylamine, and zinc octoate.
16. The thermosetting resin composition of claim 15, wherein the imidazole based compound is selected from one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-undecylimidazole.
17. The thermosetting resin composition of claim 1, further comprising a filler.
18. The thermosetting resin composition of claim 17, wherein the filler is added in an amount of 1-150 parts based on 100 parts by weight of the total of the epoxy resin, the cyanate ester resin and the ester curing agent.
19. The thermosetting resin composition of claim 18, wherein the filler is added in an amount of 1-100 parts based on 100 parts by weight of the total of the epoxy resin, the cyanate ester resin and the ester curing agent.
20. The thermosetting resin composition of claim 17, wherein the filler is an organic filler and/or an inorganic filler.
21. The thermosetting resin composition of claim 20, wherein the inorganic filler is selected from one or a combination of at least two of silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
22. The thermosetting resin composition of claim 20, wherein the organic filler is selected from one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, or polyethersulfone powder.
23. The thermosetting resin composition of claim 17, wherein the filler is silica and has a particle size median value of 1 to 15 μm.
24. The thermosetting resin composition of claim 17, wherein the filler is silica and has a particle size median value of 1 to 10 μm.
25. A resin cement obtained by dissolving or dispersing the thermosetting resin composition according to any one of claims 1 to 24 in a solvent.
26. A prepreg comprising a reinforcing material and the thermosetting resin composition according to any one of claims 1 to 24 attached to the reinforcing material after drying by impregnation.
27. A laminate comprising one or at least two superimposed prepregs according to claim 26.
28. A metal-clad laminate comprising one or at least two stacked prepregs according to claim 26 and a metal foil clad on one or both sides of the outer side of the prepregs.
29. A printed circuit board comprising at least one prepreg according to claim 26.
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| CN112409756A (en) * | 2020-10-20 | 2021-02-26 | 中电科芜湖钻石飞机制造有限公司 | Low-dielectric epoxy resin composition, preparation method thereof and composite material |
| CN114479012B (en) * | 2020-10-27 | 2023-08-15 | 广东生益科技股份有限公司 | Double-end cyano active ester, thermosetting resin composition, and preparation method and application thereof |
| CN116854892A (en) * | 2021-12-30 | 2023-10-10 | 广东盈骅新材料科技有限公司 | POSS modified urea derivative, preparation method thereof and epoxy resin composition |
| CN115322336A (en) * | 2022-08-12 | 2022-11-11 | 中国地质大学（北京） | Heat latent curing accelerator and preparation method thereof, epoxy laminated film and preparation method and application thereof |
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