CN112266576A - Brominated epoxy resin composition for paper substrate - Google Patents
Brominated epoxy resin composition for paper substrate Download PDFInfo
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- CN112266576A CN112266576A CN202011213242.0A CN202011213242A CN112266576A CN 112266576 A CN112266576 A CN 112266576A CN 202011213242 A CN202011213242 A CN 202011213242A CN 112266576 A CN112266576 A CN 112266576A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a brominated epoxy resin composition for a paper substrate, relates to the technical field of paper substrates, and mainly aims to solve the problem that the existing paper substrate is poor in humidity resistance and heat resistance. The brominated epoxy resin composition for the paper substrate comprises the following components: tetrabromobisphenol A type epoxy resin, tetraphenolethane type epoxy resin, dihydroxy naphthalene type epoxy resin, mineral anionic layered compound hydrotalcite particles, a curing agent containing a compound with at least one primary amino group obtained by the reaction of an isocyanate compound and hydrazine, an inorganic filler consisting of titanium dioxide, glass powder and kaolin, a flame-retardant filler consisting of aluminum hydroxide and phosphate, and a solvent consisting of xylene, ethyl acetate and cyclohexanone; the brominated epoxy resin composition for paper substrates of the present invention combines a tetraphenylethylene epoxy resin with a naphthalene epoxy resin, and can effectively improve the moist heat resistance of the material.
Description
Technical Field
The invention relates to a paper substrate, in particular to a brominated epoxy resin composition for the paper substrate.
Background
The paper substrate is usually a copper-clad plate, which is an extremely important basic material of printed circuit boards, and various printed circuit boards with different forms and different functions are manufactured into different printed circuits (single-sided, double-sided and multilayer) by selectively performing the working procedures of processing, etching, drilling, copper plating and the like on the copper-clad plate. The copper-clad plate is used as a substrate material in the manufacture of the printed circuit board, mainly plays roles of interconnection conduction, insulation and support for the printed circuit board, and has great influence on the transmission speed, energy loss, characteristic impedance and the like of signals in a circuit, so that the performance, the quality, the processability in the manufacture, the manufacture level, the manufacture cost, the long-term reliability and the stability of the printed circuit board are greatly dependent on the copper-clad plate. The copper-clad plate manufacturing industry is a sunrise industry, has wide development prospect along with the development of electronic information and communication industry, and the manufacturing technology is a high and new technology with multiple disciplines of interdisciplinary, interpenetration and mutual promotion. It is developed synchronously with the electronic information industry, especially with the printed circuit industry, and is not divisible. Its progress and development are driven by the innovation and development of electronic complete machine products, semiconductor manufacturing technology, electronic mounting technology, and printed circuit board manufacturing technology.
Most of the existing copper clad laminates are prepared by taking brominated epoxy resin compositions as raw materials, and have certain wet heat resistance, flame retardance, caking property, insulativity, dielectricity and the like, wherein the wet heat resistance of the copper clad laminates has higher use requirements all the time; although the existing copper clad laminate has a certain humidity resistance, the humidity resistance is general, and the improvement is always aimed at, so the invention aims to provide the brominated epoxy resin composition for the paper substrate with ultrahigh humidity resistance.
Disclosure of Invention
The present invention has an object to provide a brominated epoxy resin composition for a paper substrate, which has excellent ultrahigh moist heat resistance and can solve the problems mentioned in the background art.
In order to achieve the purpose, the invention provides the following technical scheme:
a brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight:
(1) 5-20 parts of brominated epoxy resin;
(2) 10-30 parts of tetraphenylethylene epoxy resin;
(3) 20-40 parts of naphthalene epoxy resin;
(4) 10-20 parts of hydrotalcite particles;
(5) 30-60 parts of a curing agent;
(6) 1-20 parts of an inorganic filler;
(7) 5-15 parts of a flame-retardant filler;
(8) 10-20 parts of a solvent.
As a further scheme of the invention: the paint comprises the following components in parts by weight:
(1) 8-17 parts of brominated epoxy resin;
(2) 15-25 parts of tetraphenylethylene epoxy resin;
(3) 25-35 parts of naphthalene epoxy resin;
(4) 12-17 parts of hydrotalcite particles;
(5) 40-50 parts of a curing agent;
(6) 5-15 parts of an inorganic filler;
(7) 8-13 parts of a flame-retardant filler;
(8) 12-17 parts of a solvent.
As a further scheme of the invention: the paint comprises the following components in parts by weight:
(1)15 parts of a brominated epoxy resin;
(2)20 parts of a tetraphenolethane epoxy resin;
(3)30 parts of naphthalene epoxy resin;
(4)15 parts of hydrotalcite particles;
(5)45 parts of a curing agent;
(6)10 parts of an inorganic filler;
(7)10 parts of a flame retardant filler;
(8)15 parts of a solvent.
Wherein the naphthalene epoxy resin is dihydroxy naphthalene epoxy resin or condensed ring naphthalene epoxy resin, and the brominated epoxy resin is tetrabromobisphenol A epoxy resin.
As a further scheme of the invention: the hydrotalcite particles are anionic layered compounds.
As a further scheme of the invention: the hydrotalcite particles are mineral or synthetic.
As a further scheme of the invention: the curing agent comprises a compound generated by the reaction of an isocyanate compound and hydrazine, and the number of primary amino groups in the compound is more than one.
As a further scheme of the invention: the isocyanate compound is a diisocyanate compound, a triisocyanate compound or a tetraisocyanate compound.
As a further scheme of the invention: the inorganic filler comprises titanium dioxide, glass powder and kaolin.
As a further scheme of the invention: the flame-retardant filler comprises aluminum hydroxide and phosphate.
As a further scheme of the invention: the solvent comprises xylene, ethyl acetate and cyclohexanone.
Compared with the prior art, the invention has the beneficial effects that:
(1) the brominated epoxy resin adopts tetrabromobisphenol A type epoxy resin, has good flame retardance, and can improve the safety of the material in use;
(2) according to the brominated epoxy resin composition for the paper substrate, the tetraphenol ethane epoxy resin and the naphthalene epoxy resin are combined, so that the moisture and heat resistance of the material can be effectively improved, the material is prevented from being deformed by heating or being layered and exploded due to wetting, and the comprehensive performance is excellent;
(3) the brominated epoxy resin composition for paper substrates uses hydrotalcite particles as an auxiliary raw material, and can further improve the heat resistance of the material, so that the material can be continuously used under severe conditions.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, if the description of "first", "second", etc. is referred to in the present invention, it is used for descriptive purposes only and is not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The brominated epoxy resin adopts tetrabromobisphenol A type epoxy resin, has good flame retardance, and can improve the safety of the material in use; the tetraphenylethylene epoxy resin and the naphthalene epoxy resin are combined, so that the humidity resistance and the heat resistance of the material can be effectively improved, the material is prevented from being subjected to thermal deformation or being subjected to moisture to layer explosion, and the comprehensive performance is excellent; the hydrotalcite particles are used as auxiliary raw materials, so that the heat resistance of the material can be further improved, and the material can be continuously used under severe conditions.
Example 1
A brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight: 6 parts of tetrabromobisphenol A type epoxy resin, 12 parts of tetraphenolethane epoxy resin, 22 parts of dihydroxy naphthalene type epoxy resin, 10 parts of mineral anionic layered compound hydrotalcite particles, 35 parts of curing agent containing compound obtained by reaction of isocyanate compound and hydrazine and having at least one primary amino group, 2 parts of inorganic filler consisting of titanium dioxide, glass powder and kaolin, 1:1:1 parts by weight of the inorganic filler, 6 parts of flame-retardant filler consisting of aluminum hydroxide and phosphate, 1:2 parts by weight of the flame-retardant filler, and 10 parts of solvent consisting of xylene, ethyl acetate and cyclohexanone, 2:1:3 parts by weight of the flame-retardant filler.
Example 2
A brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight: 7 parts of tetrabromobisphenol A type epoxy resin, 13 parts of tetraphenolethane epoxy resin, 24 parts of dihydroxy naphthalene type epoxy resin, 11 parts of mineral anionic layered compound hydrotalcite particles, 38 parts of curing agent containing a compound obtained by reacting an isocyanate compound with hydrazine and having at least one primary amino group, 4 parts of 1:1:1 inorganic filler composed of titanium dioxide, glass powder and kaolin, 7 parts of 1:2 flame-retardant filler composed of aluminum hydroxide and phosphate, and 11 parts of 2:1:3 solvent composed of xylene, ethyl acetate and cyclohexanone.
Example 3
A brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight: 8 parts of tetrabromobisphenol A type epoxy resin, 15 parts of tetraphenolethane epoxy resin, 25 parts of dihydroxy naphthalene type epoxy resin, 12 parts of mineral anionic layered compound hydrotalcite particles, 40 parts of curing agent containing compound obtained by reaction of isocyanate compound and hydrazine and having at least one primary amino group, 5 parts of inorganic filler consisting of titanium dioxide, glass powder and kaolin, 1:1:1 parts by weight of the inorganic filler, 8 parts of flame-retardant filler consisting of aluminum hydroxide and phosphate, 1:2 parts by weight of the flame-retardant filler, and 12 parts of solvent consisting of xylene, ethyl acetate and cyclohexanone, 2:1:3 parts by weight of the solvent.
Example 4
A brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight: 10 parts of tetrabromobisphenol A type epoxy resin, 17 parts of tetraphenolethane epoxy resin, 27 parts of dihydroxy naphthalene type epoxy resin, 13 parts of mineral anionic layered compound hydrotalcite particles, 42 parts of curing agent containing compound obtained by reaction of isocyanate compound and hydrazine and having at least one primary amino group, 7 parts of inorganic filler composed of titanium dioxide, glass powder and kaolin, in parts by weight, 1:1:1, 9 parts of flame-retardant filler composed of aluminum hydroxide and phosphate, in parts by weight, 1:2, and 13 parts of solvent composed of xylene, ethyl acetate and cyclohexanone, in parts by weight, 2:1: 3.
Example 5
A brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight: 12 parts of tetrabromobisphenol A type epoxy resin, 19 parts of tetraphenolethane epoxy resin, 29 parts of dihydroxy naphthalene type epoxy resin, 14 parts of mineral anionic layered compound hydrotalcite particles, 44 parts of curing agent containing compound obtained by reaction of isocyanate compound and hydrazine and having at least one primary amino group, 9 parts of inorganic filler composed of titanium dioxide, glass powder and kaolin, 1:1:1 by weight, 10 parts of flame-retardant filler composed of aluminum hydroxide and phosphate, 1:2 by weight, and 14 parts of solvent composed of xylene, ethyl acetate and cyclohexanone, 2:1:3 by weight.
Example 6
A brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight: 15 parts of tetrabromobisphenol A type epoxy resin, 20 parts of tetraphenolethane epoxy resin, 30 parts of dihydroxy naphthalene type epoxy resin, 15 parts of mineral anionic layered compound hydrotalcite particles, 45 parts of curing agent containing compound obtained by reaction of isocyanate compound and hydrazine and having at least one primary amino group, 10 parts of inorganic filler composed of titanium dioxide, glass powder and kaolin, 1:1:1 by weight, 11 parts of flame-retardant filler composed of aluminum hydroxide and phosphate, 1:2 by weight, and 15 parts of solvent composed of xylene, ethyl acetate and cyclohexanone, 2:1:3 by weight.
Example 7
A brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight: 16 parts of tetrabromobisphenol A type epoxy resin, 23 parts of tetraphenolethane epoxy resin, 33 parts of dihydroxy naphthalene type epoxy resin, 16 parts of mineral anionic layered compound hydrotalcite particles, 47 parts of curing agent containing a compound obtained by reacting an isocyanate compound with hydrazine and having at least one primary amino group, 13 parts of 1:1:1 inorganic filler composed of titanium dioxide, glass powder and kaolin, 12 parts of 1:2 flame-retardant filler composed of aluminum hydroxide and phosphate, and 17 parts of 2:1:3 solvent composed of xylene, ethyl acetate and cyclohexanone.
Example 8
A brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight: 17 parts of tetrabromobisphenol A type epoxy resin, 25 parts of tetraphenolethane epoxy resin, 35 parts of dihydroxy naphthalene type epoxy resin, 17 parts of mineral anionic layered compound hydrotalcite particles, 50 parts of curing agent containing compound obtained by reaction of isocyanate compound and hydrazine and having at least one primary amino group, 15 parts of inorganic filler consisting of titanium dioxide, glass powder and kaolin, 1:1:1 parts by weight of the inorganic filler, 13 parts of flame-retardant filler consisting of aluminum hydroxide and phosphate, 1:2 parts by weight of the flame-retardant filler, and 18 parts of solvent consisting of xylene, ethyl acetate and cyclohexanone, 2:1:3 parts by weight of the flame-retardant filler.
Example 9
A brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight: 18 parts of tetrabromobisphenol A type epoxy resin, 27 parts of tetraphenolethane epoxy resin, 37 parts of dihydroxy naphthalene type epoxy resin, 18 parts of mineral anionic layered compound hydrotalcite particles, 54 parts of curing agent containing compound obtained by reaction of isocyanate compound and hydrazine and having at least one primary amino group, 17 parts of inorganic filler composed of titanium dioxide, glass powder and kaolin, 1:1:1 by weight, 14 parts of flame-retardant filler composed of aluminum hydroxide and phosphate, 1:2 by weight, and 19 parts of solvent composed of xylene, ethyl acetate and cyclohexanone, 2:1:3 by weight.
Example 10
A brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight: 19 parts of tetrabromobisphenol A type epoxy resin, 18 parts of tetraphenolethane epoxy resin, 39 parts of dihydroxy naphthalene type epoxy resin, 19 parts of mineral anionic layered compound hydrotalcite particles, 58 parts of curing agent containing compound obtained by reaction of isocyanate compound and hydrazine and having at least one primary amino group, 19 parts of inorganic filler consisting of titanium dioxide, glass powder and kaolin, in parts by weight, 1:1:1, 14 parts of flame-retardant filler consisting of aluminum hydroxide and phosphate, in parts by weight, 1:2, and 19 parts of solvent consisting of xylene, ethyl acetate and cyclohexanone, in parts by weight, 2:1: 3.
Example 11
A brominated epoxy resin composition for a paper substrate comprises the following components in parts by weight: 20 parts of tetrabromobisphenol A type epoxy resin, 30 parts of tetraphenolethane epoxy resin, 40 parts of dihydroxy naphthalene type epoxy resin, 20 parts of mineral anionic layered compound hydrotalcite particles, 60 parts of curing agent containing compound obtained by reaction of isocyanate compound and hydrazine and having at least one primary amino group, 20 parts of inorganic filler consisting of titanium dioxide, glass powder and kaolin, in parts by weight, 1:1:1, 15 parts of flame-retardant filler consisting of aluminum hydroxide and phosphate, in parts by weight, 1:2, and 20 parts of solvent consisting of xylene, ethyl acetate and cyclohexanone, in parts by weight, 2:1: 3.
Test example 1
Preparing 6 parts of tetrabromobisphenol A type epoxy resin, 12 parts of tetraphenolethane epoxy resin, 22 parts of dihydroxy naphthalene type epoxy resin, 10 parts of mineral hydrotalcite particles, 35 parts of curing agent containing compound with at least one primary amino group obtained by reaction of isocyanate compound and hydrazine, 2 parts of inorganic filler consisting of titanium dioxide, glass powder and kaolin in parts by weight of 1:1:1, 6 parts of flame-retardant filler consisting of aluminum hydroxide and phosphate in parts by weight of 1:2, and 10 parts of solvent consisting of xylene, ethyl acetate and cyclohexanone in parts by weight of 2:1: 3. Adding tetrabromobisphenol A type epoxy resin, tetraphenolethane epoxy resin, dihydroxy naphthalene type epoxy resin, mineral hydrotalcite particles, a curing agent containing a compound with at least one primary amino group obtained by reacting an isocyanate compound and hydrazine, an inorganic filler consisting of titanium dioxide, glass powder and kaolin and a flame-retardant filler consisting of aluminum hydroxide and phosphate into a solvent consisting of xylene, ethyl acetate and cyclohexanone, and stirring by using a stirrer to obtain a uniformly mixed liquid of an epoxy resin composition; pre-soaking the obtained epoxy resin mixed solution in non-woven glass fiber cloth or woven glass fiber cloth, then placing the non-woven glass fiber cloth or woven glass fiber cloth into a gluing machine for heating and drying, and simultaneously keeping the temperature in the gluing machine between 130-170 ℃ until the epoxy resin mixed solution is manufactured into a sheet in a semi-cured state; then, a plurality of sheets are overlapped, copper foil is overlapped on one side or two sides of the overlapped layers, and then the paper substrate is placed on a laminating machine with the temperature of 150 ℃ and 180 ℃ for hot press and fixation, thus the paper substrate is manufactured.
The paper substrate thus produced was tested for heat resistance and moisture resistance by the following methods:
(1) 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.
(2) Peel Strength (PS): 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.
(3) Combustibility: measured according to the UL94 vertical burning method.
(4) Thermal stratification time T-260, T288: the measurement was carried out according to the IPC-TM-6502.4.24.1 method.
(5) Thermal decomposition temperature Td: the measurement was carried out according to the IPC-TM-6502.4.26 method.
(6) Dip-soldering resistant time: a double-sided copper foil-clad plate having a size of 100X 100mm was immersed in a solder bath heated to 288 ℃, and the time from the immersion to the occurrence of delamination and plate explosion of the plate was calculated.
(7) PCT water absorption: the sample is pre-dried, weighed, and then put into a pressure cooker to be steamed for 4 hours, and the mass change rate is calculated.
Test example 2
The materials were prepared according to the components of example 2 in parts by weight, and the concrete operation and test method were the same as those of test example 1.
Test example 3
The materials were prepared according to the components in example 3 by weight, and the concrete operation and test method were the same as those in test example 1.
Test example 4
The materials were prepared according to the components in example 4 by weight, and the concrete operation and test method were the same as those in test example 1.
Test example 5
The materials were prepared according to the components in example 5 in parts by weight, and the concrete operation and test method were the same as those in test example 1.
Test example 6
The materials were prepared according to the components in example 6 by weight, and the concrete operation and test method were the same as those in test example 1.
Test example 7
The materials were prepared according to the components in example 7 by weight, and the concrete operation and test method were the same as those in test example 1.
Test example 8
The materials were prepared according to the components in example 8, and the concrete operation and test method were the same as those in test example 1.
Test example 9
The materials were prepared according to the components in example 9 in parts by weight, and the concrete operation and test method were the same as those in test example 1.
Test example 10
The materials were prepared according to the components in example 10 in parts by weight, and the concrete operation and test method were the same as those in test example 1.
Test example 11
The materials were prepared according to the components in example 11 by weight, and the concrete operation and test method were the same as those in test example 1.
The material components used in test examples 1 to 11 and the corresponding parts by weight are listed in the following table:
wherein, the component names represented by each letter in the table are as follows:
a: tetrabromobisphenol A type epoxy resin;
b: a tetraphenolethane epoxy resin;
c: a dihydroxynaphthalene type epoxy resin;
d: mineral hydrotalcite particles;
e: a curing agent comprising a compound having at least one primary amino group obtained by reacting an isocyanate compound with hydrazine;
f: inorganic filler composed of titanium dioxide, glass powder and kaolin;
g: a flame retardant filler consisting of aluminum hydroxide and a phosphate;
h: a solvent consisting of xylene, ethyl acetate and cyclohexanone.
Three paper substrates were randomly purchased from the market, tested by the same test method as in test example 1, and the three test results were used as control groups 1 to 3, and the test results obtained from the control groups 1 to 3 and the test results obtained from the test examples 1 to 11 are listed in the following table:
wherein, the test items represented by A, B, C, D, E, F and G are as follows:
a: glass transition temperature (Tg);
b: peel Strength (PS);
c: combustibility;
d: thermal stratification times T-260, T288;
e, E: a thermal decomposition temperature Td;
already: dip soldering time resistance;
g: PCT water absorption rate;
as can be seen from the data results in Table 1, the test results of the test examples 1 to 11 are obviously superior to those of the control groups 1 to 3, the thermal delamination time of the paper substrate prepared from the brominated epoxy resin composition for the paper substrate is obviously prolonged, the thermal decomposition temperature is obviously improved, and the heat resistance is better; the dip soldering time of the paper substrate prepared from the brominated epoxy resin composition for the paper substrate is obviously prolonged, and the PCT water absorption is obviously reduced, so that the paper substrate has better moisture resistance.
Comparative example 1
Preparing 15 parts of tetrabromobisphenol A type epoxy resin, 15 parts of mineral hydrotalcite particles, 45 parts of curing agent containing compound obtained by reacting isocyanate compound with hydrazine and having at least one primary amino group, 10 parts of inorganic filler composed of titanium dioxide, glass powder and kaolin in parts by weight of 1:1:1, 11 parts of flame-retardant filler composed of aluminum hydroxide and phosphate in parts by weight of 1:2, and 15 parts of solvent composed of xylene, ethyl acetate and cyclohexanone in parts by weight of 2:1: 3; adding tetrabromobisphenol A type epoxy resin, tetraphenolethane epoxy resin, dihydroxy naphthalene type epoxy resin, mineral hydrotalcite particles, a curing agent containing a compound with at least one primary amino group obtained by reacting an isocyanate compound and hydrazine, an inorganic filler consisting of titanium dioxide, glass powder and kaolin and a flame-retardant filler consisting of aluminum hydroxide and phosphate into a solvent consisting of xylene, ethyl acetate and cyclohexanone, and stirring by using a stirrer to obtain a uniformly mixed liquid of an epoxy resin composition; pre-soaking the obtained epoxy resin mixed solution in non-woven glass fiber cloth or woven glass fiber cloth, then placing the non-woven glass fiber cloth or woven glass fiber cloth into a gluing machine for heating and drying, and simultaneously keeping the temperature in the gluing machine between 130-170 ℃ until the epoxy resin mixed solution is manufactured into a sheet in a semi-cured state; then, a plurality of sheets are overlapped, copper foil is overlapped on one side or two sides of the overlapped layers, and then the paper substrate is placed on a laminating machine with the temperature of 150 ℃ and 180 ℃ for hot press and fixation, thus the paper substrate is manufactured.
The paper substrate thus produced was subjected to the heat resistance and moisture resistance tests in the same manner as in test example 1;
comparative example 2
Preparing 15 parts of tetrabromobisphenol A type epoxy resin, 30 parts of dihydroxy naphthalene type epoxy resin, 15 parts of mineral hydrotalcite particles, 45 parts of curing agent containing compound with at least one primary amino group obtained by reaction of isocyanate compound and hydrazine, 10 parts of inorganic filler composed of titanium dioxide, glass powder and kaolin in parts by weight of 1:1:1, 11 parts of flame-retardant filler composed of aluminum hydroxide and phosphate in parts by weight of 1:2, and 15 parts of solvent composed of xylene, ethyl acetate and cyclohexanone in parts by weight of 2:1: 3; adding tetrabromobisphenol A type epoxy resin, tetraphenolethane epoxy resin, dihydroxy naphthalene type epoxy resin, mineral hydrotalcite particles, a curing agent containing a compound with at least one primary amino group obtained by reacting an isocyanate compound and hydrazine, an inorganic filler consisting of titanium dioxide, glass powder and kaolin and a flame-retardant filler consisting of aluminum hydroxide and phosphate into a solvent consisting of xylene, ethyl acetate and cyclohexanone, and stirring by using a stirrer to obtain a uniformly mixed liquid of an epoxy resin composition; pre-soaking the obtained epoxy resin mixed solution in non-woven glass fiber cloth or woven glass fiber cloth, then placing the non-woven glass fiber cloth or woven glass fiber cloth into a gluing machine for heating and drying, and simultaneously keeping the temperature in the gluing machine between 130-170 ℃ until the epoxy resin mixed solution is manufactured into a sheet in a semi-cured state; then, a plurality of sheets are overlapped, copper foil is overlapped on one side or two sides of the overlapped layers, and then the paper substrate is placed on a laminating machine with the temperature of 150 ℃ and 180 ℃ for hot press and fixation, thus the paper substrate is manufactured.
The paper substrate thus produced was subjected to the heat resistance and moisture resistance tests in the same manner as in test example 1;
comparative example 3
Preparing 15 parts of tetrabromobisphenol A type epoxy resin, 20 parts of tetraphenolethane epoxy resin, 15 parts of mineral hydrotalcite particles, 45 parts of curing agent containing compound with at least one primary amino group obtained by reaction of isocyanate compound and hydrazine, 10 parts of inorganic filler consisting of titanium dioxide, glass powder and kaolin in parts by weight of 1:1:1, 11 parts of flame-retardant filler consisting of aluminum hydroxide and phosphate in parts by weight of 1:2, and 15 parts of solvent consisting of xylene, ethyl acetate and cyclohexanone in parts by weight of 2:1: 3; adding tetrabromobisphenol A type epoxy resin, tetraphenolethane epoxy resin, dihydroxy naphthalene type epoxy resin, mineral hydrotalcite particles, a curing agent containing a compound with at least one primary amino group obtained by reacting an isocyanate compound and hydrazine, an inorganic filler consisting of titanium dioxide, glass powder and kaolin and a flame-retardant filler consisting of aluminum hydroxide and phosphate into a solvent consisting of xylene, ethyl acetate and cyclohexanone, and stirring by using a stirrer to obtain a uniformly mixed liquid of an epoxy resin composition; pre-soaking the obtained epoxy resin mixed solution in non-woven glass fiber cloth or woven glass fiber cloth, then placing the non-woven glass fiber cloth or woven glass fiber cloth into a gluing machine for heating and drying, and simultaneously keeping the temperature in the gluing machine between 130-170 ℃ until the epoxy resin mixed solution is manufactured into a sheet in a semi-cured state; then, a plurality of sheets are overlapped, copper foil is overlapped on one side or two sides of the overlapped layers, and then the paper substrate is placed on a laminating machine with the temperature of 150 ℃ and 180 ℃ for hot press and fixation, thus the paper substrate is manufactured.
The paper substrate thus produced was subjected to the heat resistance and moisture resistance tests in the same manner as in test example 1;
the results of comparative examples 1 to 3 are listed in the following table:
| comparative example 1 | Comparative example 2 | Comparative example 3 | |
| A deg.C | 115 | 117 | 118 |
| Second N/mm | 0.50 | 0.59 | 0.61 |
| Third UL94 | V-0 | V-0 | V-0 |
| Ding min | 16 | 31 | 29 |
| Pentam temperature | 315 | 332 | 331 |
| Has been obtained | 300s | 465s | 443 |
| G type | 0.50 | 0.33 | 0.32 |
According to the results of the comparative example, it is found that the wet heat resistance of the obtained paper substrate is best only when the tetraphenolethane epoxy resin or the dihydroxynaphthalene epoxy resin is contained, and when any one of the above components is absent, the wet heat resistance of the obtained paper substrate is reduced, and the additive effect of the above components when the above components are used alone is smaller than the synergistic effect when the above components are used together, so that in the brominated epoxy resin composition for paper substrates of the present invention, the tetraphenolethane epoxy resin or the dihydroxynaphthalene epoxy resin has a synergistic effect, and the wet heat resistance of the paper substrate can be significantly improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The brominated epoxy resin composition for the paper substrate is characterized by comprising the following components in parts by weight:
(1) 5-20 parts of brominated epoxy resin;
(2) 10-30 parts of tetraphenylethylene epoxy resin;
(3) 20-40 parts of naphthalene epoxy resin;
(4) 10-20 parts of hydrotalcite particles;
(5) 30-60 parts of a curing agent;
(6) 1-20 parts of an inorganic filler;
(7) 5-15 parts of a flame-retardant filler;
(8) 10-20 parts of a solvent.
2. The brominated epoxy resin composition for a paper substrate according to claim 1, which comprises the following components in parts by weight:
(1) 8-17 parts of brominated epoxy resin;
(2) 15-25 parts of tetraphenylethylene epoxy resin;
(3) 25-35 parts of naphthalene epoxy resin;
(4) 12-17 parts of hydrotalcite particles;
(5) 40-50 parts of a curing agent;
(6) 5-15 parts of an inorganic filler;
(7) 8-13 parts of a flame-retardant filler;
(8) 12-17 parts of a solvent.
3. The brominated epoxy resin composition for a paper substrate according to claim 1, which comprises the following components in parts by weight:
(1)15 parts of a brominated epoxy resin;
(2)20 parts of a tetraphenolethane epoxy resin;
(3)30 parts of naphthalene epoxy resin;
(4)15 parts of hydrotalcite particles;
(5)45 parts of a curing agent;
(6)10 parts of an inorganic filler;
(7)10 parts of a flame retardant filler;
(8)15 parts of a solvent;
wherein the naphthalene epoxy resin is dihydroxy naphthalene epoxy resin or condensed ring naphthalene epoxy resin, and the brominated epoxy resin is tetrabromobisphenol A epoxy resin.
4. The brominated epoxy resin composition for a paper substrate according to any one of claims 1 to 3, wherein the hydrotalcite particles are anionic layered compounds.
5. The brominated epoxy resin composition for a paper substrate according to claim 4, wherein the hydrotalcite particles are mineral or synthetic.
6. The brominated epoxy resin composition for a paper substrate according to claim 1 to 3, wherein the curing agent contains a compound produced by reacting an isocyanate compound with hydrazine, and the number of primary amino groups in the compound is at least one.
7. The brominated epoxy resin composition for a paper substrate according to claim 6, wherein the isocyanate compound is a diisocyanate compound, a triisocyanate compound or a tetraisocyanate compound.
8. The brominated epoxy resin composition for a paper substrate according to claims 1 to 3, wherein the inorganic filler comprises titanium dioxide, glass powder, and kaolin.
9. The brominated epoxy resin composition for a paper substrate according to claim 1 to 3, wherein the flame retardant filler comprises aluminum hydroxide or a phosphate.
10. The brominated epoxy resin composition for a paper substrate according to claim 1 to 3, wherein the solvent comprises xylene, ethyl acetate, cyclohexanone.
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