阅读说明：本技术 一种绝缘基板及其制备方法和用途 (Insulating substrate and preparation method and application thereof ) 是由 胡革 于 2020-06-16 设计创作，主要内容包括：本发明提供了一种绝缘基板及其制备方法和用途,属于电子材料领域。该绝缘基板是将增强材料涂敷或含浸树脂组合物后而得；所述树脂组合物由包括如下重量配比的原料制备而成：含有一个或二个双键且至少含有一个桥环的环烯烃类化合物9000～10000份,钌卡宾催化剂0.1～10份。本发明采用特定的树脂组合物制备绝缘基板,进一步制备覆铜板,不仅有效提高了其玻璃化转变温度,在使用时可以有效减少介电损耗,满足高频高速通信应用要求。同时,制备的绝缘基板或覆铜板具有良好的耐燃烧性和耐浸焊性,不易吸水,更适用于制备电子材料。此外,制备方法安全环保。本发明树脂组合物制备绝缘基板,进而制备的覆铜板可用于高频高速通信,特别是5G通信,具有良好的应用前景。(The invention provides an insulating substrate and a preparation method and application thereof, belonging to the field of electronic materials. The insulating substrate is obtained by coating or impregnating a reinforcing material with a resin composition; the resin composition is prepared from the following raw materials in parts by weight: 9000-10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 0.1-10 parts of ruthenium carbene catalyst. The invention adopts the specific resin composition to prepare the insulating substrate and further prepare the copper-clad plate, thereby not only effectively improving the glass transition temperature, but also effectively reducing the dielectric loss when in use and meeting the application requirement of high-frequency high-speed communication. Meanwhile, the prepared insulating substrate or copper-clad plate has good combustion resistance and dip soldering resistance, is not easy to absorb water, and is more suitable for preparing electronic materials. In addition, the preparation method is safe and environment-friendly. The resin composition disclosed by the invention is used for preparing the insulating substrate, and the prepared copper-clad plate can be used for high-frequency high-speed communication, particularly 5G communication, and has a good application prospect.)

1. An insulating substrate, characterized in that: it is obtained by coating or impregnating a reinforcing material with a resin composition; the resin composition is prepared from the following raw materials in parts by weight: 9000-10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 0.1-10 parts of ruthenium carbene catalyst.

2. The insulating substrate according to claim 1, wherein: the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-6 parts of ruthenium carbene catalysts;

preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-4 parts of ruthenium carbene catalysts;

more preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 2 parts of ruthenium carbene catalyst.

3. The insulating substrate according to claim 1 or 2, wherein: the resin composition also comprises the following raw materials in parts by weight: 0-5000 parts of organic filler, 0-10000 parts of inorganic filler, 0-10000 parts of thermosetting resin and 0-10000 parts of organic solvent;

preferably, the resin composition further comprises the following raw materials in parts by weight: 0-1000 parts of organic filler, 0-5000 parts of inorganic filler, 0-10000 parts of thermosetting resin and 0-10000 parts of organic solvent.

4. The insulating substrate according to claim 1 or 2, wherein: the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-6 parts of ruthenium carbene catalysts;

preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-4 parts of ruthenium carbene catalysts;

more preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 2 parts of ruthenium carbene catalyst.

5. The insulating substrate according to claim 1 or 2, wherein: the cyclic olefin compound containing one or two double bonds and at least one bridged ring is one or a composition of more of dicyclopentadiene, cyclopentadiene trimer, cyclopentadiene tetramer and norbornene; the content of the dicyclopentadiene is 30-100%.

6. The insulating substrate according to claim 5, wherein: the cyclic olefin compound containing one or two double bonds and at least one bridged ring is dicyclopentadiene;

or the cyclic olefin compound containing one or two double bonds and at least one bridge ring consists of dicyclopentadiene and norbornene; the mass ratio of dicyclopentadiene to norbornene is (5-10): 1;

preferably, the dicyclopentadiene and norbornene contain one or two functional groups; the functional group is one or more of methyl, methoxy, hydroxyl, carboxylic acid group, acrylate group and methacrylate group;

more preferably, the mass ratio of dicyclopentadiene to norbornene is 9: 1.

7. the insulating substrate according to claim 1 or 2, wherein: the structural formula of the ruthenium carbene catalyst is shown as a formula I:

wherein L is¹、L²、L³Is an independently selected electron donating group;

n is 0 or 1;

m is 0, 1 or 2;

k is 0 or 1;

X¹and X²Are independently selected anionic ligands;

R¹and R²Are respectively selected from H atom, hydrocarbon group and heteroatom-containing hydrocarbon group;

preferably, the first and second electrodes are formed of a metal,

the structural formula of the ruthenium carbene catalyst is shown in the specification

8. The insulating substrate according to claim 1 or 2, wherein: the inorganic filler is one or more of calcium carbonate, aluminum oxide, magnesium oxide, boron nitride, silica glass beads and silica hollow glass beads;

the thermosetting resin is one or more of epoxy resin, benzoxazine resin, cyanate ester resin, bismaleimide resin, polyphenyl ether resin and phenolic resin;

the organic filler is one or more of polystyrene, styrene-butadiene-styrene block copolymer, acrylonitrile-butadiene-styrene plastic, styrene-ethylene-butylene-styrene block copolymer, light stabilizer, antioxidant and flame retardant;

the organic solvent is toluene, methyl ethyl ketone, butanone, tetrahydrofuran or N, N-dimethylformamide;

preferably, the first and second electrodes are formed of a metal,

the inorganic filler is composed of alumina and silica glass beads, and the mass ratio of the alumina to the silica glass beads is (1-5): (1-5);

the light stabilizer is one or more of bis (1,2,2,6, 6-pentamethylpiperidinol) sebacate, succinic acid, 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol polymer, 3- [3- (2-H-benzotriazole-2-yl) -4-hydroxy-5-tert-butylphenyl ] -propionic acid-polyethylene glycol ester, bis (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate and 1-methyl-8- (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate;

the antioxidant is antioxidant TPP, antioxidant 164, antioxidant 1010, antioxidant BHT or antioxidant CA;

one or more of ammonium polyphosphate, red phosphorus, decabromodiphenylethane, hexabromocyclododecane, DOPO, DiDOPO and triphenyl phosphate serving as a flame retardant;

the organic solvent is toluene or butanone;

more preferably still, the first and second liquid crystal compositions are,

the mass ratio of the alumina to the silica glass beads is 3: 2.

9. the insulating substrate according to claim 1 or 2, wherein: the preparation method of the resin composition comprises the following steps: mixing the raw materials in the weight ratio to obtain the product.

10. The insulating substrate according to claim 1 or 2, wherein: the reinforced material is glass fiber cloth.

11. A method for producing an insulating substrate according to any one of claims 1 to 10, characterized in that: it comprises the following steps: coating or impregnating the reinforcing material with the resin composition, and heating and curing to obtain the composite material;

preferably, the temperature for heating and curing is 60-180 ℃ and the time is 1-20 minutes;

more preferably, the temperature for heating and curing is 60-100 ℃ and the time is 5-10 minutes.

12. Use of the insulating substrate according to any one of claims 1 to 10 for the preparation of a copper clad laminate; preferably, the copper clad laminate is a high-frequency high-speed copper clad laminate; more preferably, the copper clad laminate is a 5G communication high-frequency high-speed copper clad laminate.

13. A copper clad laminate characterized in that: the insulating substrate is obtained by attaching a copper foil to the insulating substrate according to any one of claims 1 to 10.

14. A method for producing the copper clad laminate as claimed in claim 13, characterized in that: it comprises the following steps: pasting a copper foil on the surface of the insulating substrate, and carrying out hot pressing to obtain the copper foil; the copper foil is adhered to one side or two sides of the insulating substrate.

15. The method of claim 14, wherein: coating an adhesive on the surface of the insulating substrate or the surface of the copper foil during copper foil pasting;

preferably, the adhesive is one or more of epoxy resin, phenolic resin, polyphenyl ether resin and cyanate resin;

and/or the hot pressing is vacuum hot pressing or composite roller hot pressing.

16. The method of claim 15, wherein: the temperature of the vacuum hot pressing is 60-150 ℃, and the time is 5-10 minutes;

and/or, the hot pressing of the composite roller is carried out after the normal temperature composite roller is hot pressed, and then curing is carried out;

preferably, hot pressing is carried out on the compound roller after 3-5 minutes of normal temperature compound, and the hot pressing of the compound roller is carried out for 2-5 minutes at the temperature of 60-100 ℃; the curing is carried out at 150-200 ℃ for 2-5 minutes.

17. Use of the copper clad laminate of claim 13 in the preparation of a printed circuit board.

Technical Field

The invention belongs to the field of electronic materials, and particularly relates to an insulating substrate, and a preparation method and application thereof.

Background

In many electronic products, a Printed Circuit Board (PCB) functions as a circuit interconnection and is an indispensable main part of the electronic products. Printed Circuit Boards (PCBs) are manufactured by etching a copper clad laminate (CCL, copper clad laminate for short) to obtain the associated circuitry. A Copper Clad Laminate (CCL) is a plate-like material formed by impregnating a reinforcing material with a resin, coating one or both surfaces with a copper foil, and performing hot pressing, and is a basic material for manufacturing a Printed Circuit Board (PCB).

In the production of a conventional single-sided or double-sided PCB, a series of operations (e.g., etching, plating, drilling, etc.) are performed on the copper-clad plate to form the desired conductive pattern circuit. In the process of manufacturing the multilayer printed circuit board, the unprocessed copper clad laminate is used as a base material to be manufactured into a conductive pattern circuit, and is directly pressed and molded by a hot press after being alternately pressed with a Bonding sheet (Bonding sheet) to be bonded together, so that more than three pattern circuit layers, namely the multilayer printed circuit board, are manufactured.

The aforementioned copper clad laminate for single-sided or double-sided PCB, as well as the copper clad laminate for multi-layer PCB and prepreg (insulating substrate) are all PCB-based materials, and are all the fields of copper clad laminate manufacturing industry technology. In the current production of Printed Circuit Boards (PCB), a copper clad laminate prepared from a glass fiber epoxy prepreg is mainly applied, thermosetting resin such as epoxy resin is dissolved in organic solvent such as toluene or butanone to form glue solution, then glass fiber cloth is immersed in the glue solution, and the solvent in the glue solution is volatilized through high-temperature heating to obtain the prepreg; and (3) pressing the prepreg and the copper foil together through a high-pressure high-temperature pressing machine, and finally obtaining the copper-clad plate through the complicated and high-energy-consumption process steps.

According to the traditional technology for preparing the copper-clad plate by using the solvent method, a large amount of organic solvent is consumed, the environmental pollution is caused, meanwhile, a large amount of heat is consumed in the solvent volatilization and solidification processes, the process is high in energy consumption, the performances such as dip-soldering resistance, peeling strength and the like are influenced due to the fact that the solvent cannot be completely volatilized, meanwhile, the epoxy resin material has the defects of high dielectric constant, high dielectric loss and the like, and the requirements of the high-frequency high-speed copper-clad plate in the current 5G communication cannot be met.

Patent CN107417864 discloses a polyphenylene ether prepolymer and a preparation method thereof, and also discloses a composition containing the polyphenylene ether prepolymer, and the resin composition is made into a prepreg, a laminated board or a printed circuit board. The polyphenyl ether prepolymer is obtained by reacting dicyclopentadiene monomer and vinyl-containing polyphenyl ether under a ruthenium catalyst. The prepolymer preparation process is relatively complicated and also requires the use of large amounts of organic solvents.

Disclosure of Invention

The invention aims to provide an insulating substrate and a preparation method and application thereof.

The invention provides an insulating substrate, which is obtained by coating or impregnating a reinforcing material with a resin composition; the resin composition is prepared from the following raw materials in parts by weight: 9000-10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 0.1-10 parts of ruthenium carbene catalyst.

Further, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-6 parts of ruthenium carbene catalysts;

preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-4 parts of ruthenium carbene catalysts;

more preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 2 parts of ruthenium carbene catalyst.

Further, the resin composition also comprises the following raw materials in parts by weight: 0-5000 parts of organic filler, 0-10000 parts of inorganic filler, 0-10000 parts of thermosetting resin and 0-10000 parts of organic solvent;

preferably, the resin composition further comprises the following raw materials in parts by weight: 0-1000 parts of organic filler, 0-5000 parts of inorganic filler, 0-10000 parts of thermosetting resin and 0-10000 parts of organic solvent.

Further, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-6 parts of ruthenium carbene catalysts;

preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cycloolefin compounds containing one or two double bonds and at least one bridged ring, and 1-4 parts of ruthenium carbene catalysts;

more preferably, the resin composition is prepared from the following raw materials in parts by weight: 10000 parts of cyclic olefin compound containing one or two double bonds and at least one bridged ring, and 2 parts of ruthenium carbene catalyst.

Further, the cyclic olefin compound containing one or two double bonds and at least one bridged ring is one or a composition of more of dicyclopentadiene, cyclopentadiene trimer, cyclopentadiene tetramer and norbornene; the content of the dicyclopentadiene is 30-100%.

Further, the cyclic olefin compound containing one or two double bonds and at least one bridged ring is dicyclopentadiene;

or the cyclic olefin compound containing one or two double bonds and at least one bridge ring consists of dicyclopentadiene and norbornene; the mass ratio of dicyclopentadiene to norbornene is (5-10): 1;

preferably, the dicyclopentadiene and norbornene contain one or two functional groups; the functional group is one or more of methyl, methoxy, hydroxyl, carboxylic acid group, acrylate group and methacrylate group;

more preferably, the mass ratio of dicyclopentadiene to norbornene is 9: 1.

further, the structural formula of the ruthenium carbene catalyst is shown as formula I:

wherein L is¹、L²、L³Is an independently selected electron donating group;

n is 0 or 1;

m is 0, 1 or 2;

k is 0 or 1;

X¹and X²Are independently selected anionic ligands;

R¹and R²Are respectively selected from H atom, hydrocarbon group and heteroatom-containing hydrocarbon group;

preferably, the first and second electrodes are formed of a metal,

the structural formula of the ruthenium carbene catalyst is shown in the specification

Further, the inorganic filler is one or more of calcium carbonate, aluminum oxide, magnesium oxide, boron nitride, silica glass beads and silica hollow glass beads;

the thermosetting resin is one or more of epoxy resin, benzoxazine resin, cyanate ester resin, bismaleimide resin, polyphenyl ether resin and phenolic resin;

the organic filler is one or more of polystyrene, styrene-butadiene-styrene block copolymer, acrylonitrile-butadiene-styrene plastic, styrene-ethylene-butylene-styrene block copolymer, light stabilizer, antioxidant and flame retardant;

the organic solvent is toluene, methyl ethyl ketone, butanone, tetrahydrofuran or N, N-dimethylformamide;

preferably, the first and second electrodes are formed of a metal,

the inorganic filler is composed of alumina and silica glass beads, and the mass ratio of the alumina to the silica glass beads is (1-5): (1-5);

the light stabilizer is one or more of bis (1,2,2,6, 6-pentamethylpiperidinol) sebacate, succinic acid, 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol polymer, 3- [3- (2-H-benzotriazole-2-yl) -4-hydroxy-5-tert-butylphenyl ] -propionic acid-polyethylene glycol ester, bis (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate and 1-methyl-8- (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate;

the antioxidant is antioxidant TPP, antioxidant 164, antioxidant 1010, antioxidant BHT or antioxidant CA;

one or more of ammonium polyphosphate, red phosphorus, decabromodiphenylethane, hexabromocyclododecane, DOPO, DiDOPO and triphenyl phosphate serving as a flame retardant;

the organic solvent is toluene or butanone;

more preferably still, the first and second liquid crystal compositions are,

the mass ratio of the alumina to the silica glass beads is 3: 2.

further, the preparation method of the resin composition comprises the following steps: mixing the raw materials in the weight ratio to obtain the product.

Further, the reinforcing material is glass fiber cloth.

The invention also provides a preparation method of the insulating substrate, which comprises the following steps: coating or impregnating the reinforcing material with the resin composition, and heating and curing to obtain the composite material;

preferably, the temperature for heating and curing is 60-180 ℃ and the time is 1-20 minutes;

more preferably, the temperature for heating and curing is 60-100 ℃ and the time is 5-10 minutes.

The invention also provides the application of the insulating substrate in preparing the copper foil-clad laminated board; preferably, the copper clad laminate is a high-frequency high-speed copper clad laminate; more preferably, the copper clad laminate is a 5G communication high-frequency high-speed copper clad laminate.

The invention also provides a copper clad laminate which is obtained by pasting copper foil on the insulating substrate.

The invention also provides a preparation method of the copper clad laminate, which comprises the following steps: pasting a copper foil on the surface of the insulating substrate, and carrying out hot pressing to obtain the copper foil; the copper foil is adhered to one side or two sides of the insulating substrate.

Further, when the copper foil is pasted, an adhesive is coated on the surface of the insulating substrate or the surface of the copper foil;

preferably, the adhesive is one or more of epoxy resin, phenolic resin, polyphenyl ether resin and cyanate resin;

and/or the hot pressing is vacuum hot pressing or composite roller hot pressing.

Further, the temperature of the vacuum hot pressing is 60-150 ℃, and the time is 5-10 minutes;

and/or, the hot pressing of the composite roller is carried out after the normal temperature composite roller is hot pressed, and then curing is carried out;

preferably, hot pressing is carried out on the compound roller after 3-5 minutes of normal temperature compound, and the hot pressing of the compound roller is carried out for 2-5 minutes at the temperature of 60-100 ℃; the curing is carried out at 150-200 ℃ for 2-5 minutes.

The invention also provides application of the copper clad laminate in preparation of a printed circuit board.

In the invention, the normal temperature refers to room temperature, 25 +/-5 ℃; the overnight refers to 12. + -. 2 h.

The invention adopts the cycloolefine compounds containing one or two double bonds and at least one bridged ring as raw materials (such as dicyclopentadiene and norbornene) to obtain large-size materials (such as large-size polydicyclopentadiene) under the action of a specific ruthenium carbene catalyst. The material has no implosion bubbles, the mechanical property and the thermal stability are also obviously improved, the dielectric property is very excellent, and the material is suitable for manufacturing a high-frequency high-speed communication base material-Copper Clad Laminate (CCL) board and has very good application prospect.

The invention adopts the specific resin composition to prepare the insulating substrate and further prepare the copper-clad plate, thereby not only effectively improving the glass transition temperature of the copper-clad plate or the insulating substrate, but also obviously reducing the dielectric constant and the dielectric loss of the copper-clad plate or the insulating substrate compared with the prior art, effectively reducing the dielectric loss when in use, meeting the requirements of the current high-frequency high-speed communication application, in particular meeting the requirements of the high-frequency high-speed copper-clad plate such as 5G communication and the like. Meanwhile, the insulating substrate or the copper-clad plate prepared from the resin composition has good combustion resistance and dip soldering resistance, is not easy to absorb water, is more suitable for the technical field of electronics, and is further used for preparing printed circuit boards or other electronic materials. In addition, the preparation method does not need to use an organic solvent, reduces the pollution to operators and atmosphere to the minimum degree, and is safer and more environment-friendly; the cyclic olefin compound can be cured within minutes or even seconds by ring-opening shift polymerization, and compared with epoxy resin which requires several hours of curing time, the efficiency is improved, and the energy consumption is reduced. The resin composition is used for preparing the insulating substrate, and the prepared high-frequency high-speed copper-clad plate can be used for communication, particularly 5G communication, can realize the processing of a novel copper-clad plate with low dielectric constant and low dielectric loss and no solvent, and has good application prospect.

Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.

The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.

Detailed Description

The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.