CN111500016B - Black resin composition, prepreg and laminated board - Google Patents

Black resin composition, prepreg and laminated board Download PDF

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Publication number
CN111500016B
CN111500016B CN202010236236.0A CN202010236236A CN111500016B CN 111500016 B CN111500016 B CN 111500016B CN 202010236236 A CN202010236236 A CN 202010236236A CN 111500016 B CN111500016 B CN 111500016B
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black
epoxy resin
parts
curing agent
additive
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CN111500016A (en
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陈运
彭康
沈宗华
徐达
田堃
盛佳炯
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Hangzhou Wazam New Materials Co ltd
Zhejiang Huazheng New Material Group Co ltd
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Hangzhou Wazam New Materials Co ltd
Zhejiang Huazheng New Material Group Co ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/68—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 catalysts used
    • C08G59/686—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 catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • Manufacturing & Machinery (AREA)
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Abstract

The invention discloses a black resin composition, a prepreg and a laminated board. The black resin composition comprises the following components in parts by weight: 100 parts of epoxy resin; 0.001-60 parts of curing agent; 0.001-5 parts of a curing accelerator; 10-100 parts of a filler; 0.001-50 parts of black additive; 0.001-50 parts of other additives; the black additive is composed of a black additive I and a black additive II according to any proportion, wherein the black additive I comprises any one of aniline black additive, iron oxide black additive, copper chromium black, iron chromium black and insulating carbon black, and the black additive II comprises any one of acid black, cation sulfur BK, sulfur black and trinitrogen additive. The laminated board prepared from the black resin composition has the advantages of high blackness, high Tg, excellent insulating property, good heat resistance, good flame retardant property and the like.

Description

Black resin composition, prepreg and laminated board
Technical Field
The invention belongs to the technical field of resin materials for printed circuit boards, and particularly relates to a black resin composition, a prepreg and a laminated board.
Background
With the development of the PCB industry, the matrix copper-clad plate of the composite material needs heat resistance and high Tg to meet the application requirements of various high-end products such as multilayer plates, HDI, LED light sources and the like, and simultaneously has requirements on the light shading property and color of the substrate material, and the light shading property and application field of the black copper-clad plate are generally larger than those of other colors.
However, at present, although the conventional black plate uses carbon black or other black additives, the black plate can meet the requirement of black dyeing, but the electrical property and the light-shielding property can not be considered at the same time, so that the black dyeing capability and the light-shielding property of the black plate are urgently needed to be improved under the condition of ensuring the good electrical property of the black plate, and the application field of the black plate is wider.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a black resin composition, a prepreg and a laminated board.
In order to achieve the purpose, the invention adopts the following technical scheme:
the black resin composition comprises the following components in parts by weight:
Figure BDA0002431065930000011
the black additive is composed of a black additive I and a black additive II according to any proportion, wherein the black additive I comprises any one of aniline black additives, iron oxide black additives, copper chromium black, iron chromium black and insulating carbon black, and the black additive II comprises any one of acid black, cation sulfur BK, sulfur black and trinitrogen additives.
According to the invention, the black additives I and II of different types are used in proportion, so that the electrical property and the light shielding property of the product can be improved.
Further, the black additive I accounts for 10-50% of the weight of the black additive; preferably, the black additive I accounts for 10-30% of the weight of the black additive. The content of the black additive I is too high, so that the prepared laminated board has low whiteness, but the electrical property can not meet the corresponding requirement; the black additive is used in a low amount, and the electrical property of the laminated board meets the requirement but the whiteness is higher. Therefore, the black additive prepared according to the proportion can give consideration to both the black dyeing capability and the electrical property.
Further, the epoxy resin is one or a combination of more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol a novolac epoxy resin, novolac modified epoxy resin, isocyanate modified epoxy resin, DCPD modified epoxy resin, polyfunctional modified epoxy, alicyclic epoxy resin, biphenyl epoxy resin, glycidyl ester epoxy resin, dicyclopentadiene epoxy resin, and naphthalene ring epoxy resin.
The curing agent is one or a combination of more of o-cresol type phenolic resin, linear phenolic resin, bisphenol A type phenolic resin, phenol type phenolic resin, aromatic amine curing agent, carboxyl amine curing agent, alicyclic amine curing agent, polyamine curing agent, aromatic acid anhydride curing agent, fatty acid anhydride curing agent and halogenated acid anhydride curing agent.
Further, the filler is one or a combination of more of crystalline silica, fused silica, spherical silica, calcium silicate, silicon carbide, calcium carbonate, alumina, aluminum hydroxide, aluminum nitride, boron nitride, calcined kaolin, titanium dioxide, barium titanate, barium sulfate, talcum powder and polytetrafluoroethylene.
Preferably, the filler consists of crystalline silica, calcined kaolin and titanium dioxide. The calcined kaolin is low in price, but has good light-shielding property, and the production cost can be reduced on the basis of ensuring the light-shielding property of the laminated board through the matching of the three fillers.
Further, the other additives are one or a combination of more of a coupling agent, a dispersing agent, a toughening agent, a defoaming agent and a solvent.
Further, the black resin composition further includes a flame retardant; the flame retardant is a halogen flame retardant and a halogen-free flame retardant, and can be one or a combination of more of a chlorine-containing flame retardant, a bromine-containing flame retardant, a phosphorus-nitrogen flame retardant, decabromodiphenyl ether, decabromodiphenyl ethane, brominated epoxy resin and tetrabromobisphenol A.
The invention also provides a prepreg which comprises a reinforcing material and the black additive composition attached to the reinforcing material after impregnation and drying. Preferably, the reinforcing material is E-type glass cloth or NE-type glass cloth. Preferably, the drying temperature is 120 to 190 ℃.
The present invention also provides a laminate comprising a metal foil and one or more layers of prepreg as described above.
Further, the preparation process of the laminated board comprises the following steps: and (3) stacking 1-12 prepregs together, respectively placing a copper foil (HOZ-2 OZ) on each prepreg, and placing the prepregs in a vacuum hot press for pressing to obtain the copper-clad laminate. The specific pressing process comprises the following steps: pressing for 0.5-2 hours at the curing temperature of 180-220 ℃ under the pressure of 1-3 MPa.
The invention has the following technical characteristics:
1) According to the invention, two different types of black additives are matched according to a proper proportion, so that the electrical property and the light shielding property of the laminated board are considered.
2) The laminated board prepared from the black resin composition has the advantages of good heat resistance, high Tg, good moisture resistance, excellent insulating property, good flame retardant property, high blackness, good color consistency, good light shielding property, high environmental resistance, good aging resistance and excellent PCB processing property, and is very suitable for multi-layer printed circuits with high blackness, high Tg, excellent insulativity and high requirement on aging resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few 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 described embodiments of the invention without inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The raw materials used in the specific embodiment of the present invention are listed in table 1.
TABLE 1 raw Material compositions
Figure BDA0002431065930000041
The black additive composition, prepreg and laminate in the examples and comparative examples of the present invention were prepared as follows.
1. Preparation of Black additive composition
According to parts by weight, 20 parts of epoxy resin 1, 10 parts of epoxy resin 2,5 parts of epoxy resin 3,5 parts of epoxy resin 4, 10 parts of curing agent 1,5 parts of curing agent 2,0.05 part of curing accelerator, 0.5 part of black additive 1,0.5 part of black additive 2,0.2 part of silane coupling agent, 15 parts of filler 1, 10 parts of filler 2 and 15 parts of filler 3 are taken.
Dissolving the mixture by using an organic solvent, uniformly stirring (high-speed stirring or ball milling and other methods can be used in the process of uniformly dispersing the combined solution), and adjusting the solid content of the resin composition to about 60wt% to prepare the black additive combined solution.
2. Preparation of prepreg
And (3) uniformly coating the black resin combined solution on a reinforcing material by using a glass cloth stretcher, wherein the reinforcing material is E-shaped glass cloth, and baking in a 160 ℃ oven to obtain the prepreg.
3. Preparation of copper clad laminate
And (3) stacking ten prepared prepregs, placing copper foils (HOZ) on the upper part and the lower part respectively, and putting the laminates in a vacuum hot press for pressing to obtain the copper foil-clad laminates. The specific pressing process comprises the following steps: pressing for 1 hour at 190 ℃ under the pressure of 2 MPa.
Specific composition ratios of the examples of the present invention and the comparative examples are shown in table 2.
TABLE 2 concrete composition ratios of examples and comparative examples
Figure BDA0002431065930000051
The copper clad laminates prepared in examples 1 to 3 and comparative examples 1 to 7 were subjected to the performance test, and the specific test contents and standards are shown below, and the test results are shown in Table 3.
Gel time, test method IPC-TM-6502.3.18;
high Pot, test method IPC-TM-6502.5.7, 1000V, hold for 30s;
peel strength, test method according to IPC-TM-6502.4.9;
glass transition temperature (Tg), test method differential scanning calorimetry;
flammability, measured according to the us UL94 vertical burning method;
blackness, transmittance, according to the detection standards of the transmittance and whiteness of the plastic;
electrical Properties, test methods network Analyzer SPDR method.
TABLE 3 test results of Properties of copper clad laminates prepared in examples 1 to 3 and comparative examples 1 to 7
Figure BDA0002431065930000061
As can be seen from table 3:
(1) Examples 1 and 2 show that the prepreg prepared by the invention has good insulation property and excellent High Pot property, the prepared copper clad laminate has excellent comprehensive performance, and the copper clad laminate has good heat resistance, high Tg, good moisture resistance, excellent insulation property, good flame retardant property, high blackness, good color consistency, good shading property, high environmental resistance, good aging resistance and excellent PCB processing property, and is very suitable for multilayer printed circuits with High blackness, high Tg, excellent insulation property and High requirement on aging resistance.
(2) Comparison of example 1 and comparative example 7, and example 2 with comparative example 6, shows that: and (3) filler 2: the calcined kaolin has excellent shading performance, is cheaper than titanium dioxide, can be combined with the titanium dioxide, and has relatively poor shading performance when not used.
(3) The black additive 1 has a strong black dyeing ability but the electrical properties are deteriorated, while the black additive 2 has a good electrical properties but a weak black dyeing ability. For example, when the black additive 2 is used in an amount of 0%, i.e., only the black pigment is used, the substrate has a low whiteness but the electrical properties do not meet the corresponding requirements, and when the black additive 1 is used in an amount of 0%, i.e., only the black dye is used, the substrate has the electrical properties but has a high whiteness. The black dyeing ability and the electrical property of the black pigment can be considered after the black additive 1 and the black additive 2 are used in combination, and according to the experimental result, the black additive 1 accounts for 10-30% of the total amount of the black additive, and the black additive 2 accounts for 70-90% of the total amount.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (6)

1. The black resin composition is characterized by comprising the following components in parts by weight:
100 parts of epoxy resin;
0.001-60 parts of curing agent;
0.001-5 parts of a curing accelerator;
10-100 parts of a filler;
0.001-50 parts of black additive;
0.001-50 parts of other additives;
wherein the black additive consists of aniline black and acid black;
the nigrosine accounts for 30-50% of the weight of the black additive;
the filler is composed of crystalline silica, calcined kaolin and titanium dioxide.
2. The black resin composition according to claim 1, wherein the epoxy resin is one or more selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A novolac epoxy resin, isocyanate modified epoxy resin, DCPD modified epoxy resin, polyfunctional modified epoxy, alicyclic epoxy resin, biphenyl epoxy resin, glycidyl ester epoxy resin, dicyclopentadiene epoxy resin, and naphthalene ring epoxy resin.
3. The black resin composition according to claim 1, wherein the curing agent is one or a combination of more of o-cresol type phenol-formaldehyde resin, phenol-formaldehyde novolac resin, bisphenol a type phenol-formaldehyde resin, aromatic amine type curing agent, carboxamide type curing agent, alicyclic amine type curing agent, polyamine type curing agent, aromatic acid anhydride curing agent, fatty acid anhydride curing agent, and halogenated acid anhydride curing agent.
4. The black resin composition according to claim 1, further comprising a flame retardant.
5. A prepreg comprising a reinforcing material and the black resin composition according to any one of claims 1 to 4 attached to the reinforcing material by impregnation drying.
6. A laminate comprising a metal foil and one or more layers of the prepreg of claim 5.
CN202010236236.0A 2020-03-30 2020-03-30 Black resin composition, prepreg and laminated board Active CN111500016B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008133412A (en) * 2006-10-26 2008-06-12 Hitachi Chem Co Ltd Thermosetting resin composition, prepreg, metal-clad laminate and printed wiring board
CN108410132A (en) * 2018-02-12 2018-08-17 浙江华正新材料股份有限公司 A kind of low dielectric halogen-free resin composition and its low fluidity prepreg

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110305445A (en) * 2019-05-16 2019-10-08 浙江华正新材料股份有限公司 A kind of black-colored resin composition, prepreg and laminate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008133412A (en) * 2006-10-26 2008-06-12 Hitachi Chem Co Ltd Thermosetting resin composition, prepreg, metal-clad laminate and printed wiring board
CN108410132A (en) * 2018-02-12 2018-08-17 浙江华正新材料股份有限公司 A kind of low dielectric halogen-free resin composition and its low fluidity prepreg

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