CN114292607B - Adhesive and preparation method and application thereof - Google Patents
Adhesive and preparation method and application thereof Download PDFInfo
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- CN114292607B CN114292607B CN202210012395.1A CN202210012395A CN114292607B CN 114292607 B CN114292607 B CN 114292607B CN 202210012395 A CN202210012395 A CN 202210012395A CN 114292607 B CN114292607 B CN 114292607B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an adhesive, a preparation method and application thereof, wherein the adhesive comprises the following raw materials: a modified polyolefin resin, ethylene propylene diene monomer, polyphenylene oxide and an epoxy resin, the modified polyolefin resin comprising at least one of a polybutadiene-styrene copolymer modified with maleic anhydride, polybutadiene, a butadiene-styrene copolymer and polybutadiene; the ethylene propylene diene monomer main chain is saturated hydrocarbon; the polyphenyl ether is double-end hydroxyl polyphenyl ether; the modified polyolefin resin added by the epoxy resin which is the epoxy polybutadiene with the hydroxyl groups has extremely low dielectric constant, higher reactivity and compatibility, less polar groups of the epoxy resin and smaller dielectric property, and can effectively reduce Dk and Df in a glue system and improve the crosslinking density of the epoxy resin, so that the pure adhesive film has low dielectric constant and low dielectric loss.
Description
Technical Field
The invention belongs to the technical field of electronic circuit boards, and particularly relates to an adhesive and a preparation method and application thereof.
Background
The 21 st century is a highly informative society. An important technical basis for the development of informatization is high-speed, high-frequency and high-capacity signal transmission. Current advances in information and communication technology have led electronic information products to move into the gigahertz (GHz) era. Among the most prominent are digital video products, which enable the integrated transmission of synchronous transmission of voice, video signals and data. On the other hand, the widespread networking has advanced the development of increasing the capacity of information.
In a high frequency line, the relation between the signal transmission speed V and the dielectric constant er (Dk) of the material is: v=k×c/(er) 1/2; the relation between the signal transmission attenuation α and the material dielectric loss tangent tan δ (Df) is: α=k (f/C) ×tan δ (er) 1/2, where K is a constant, C is the speed of light, and f is the signal transmission frequency. It can be seen that the lower the dielectric constant (Dk) of the material, the faster the signal transmission speed; the smaller the dielectric constant (Dk) and dielectric loss tangent (Df) of the material, the less distortion the signal transmission will be. In recent years, with rapid development of electronic industry, information processing and information transmission are accelerated, requirements on high-frequency characteristics of materials are higher and higher, and with continuous development of 5G technology, requirements on dielectric constants and dielectric losses of materials inside circuit boards are lower and lower, so that requirements on low dielectric constants and low losses are also provided for materials inside circuit boards.
In view of the above, it is an urgent need to provide a plastic film with low dielectric constant and low dielectric loss.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the adhesive provided by the invention can effectively reduce Dk and Df of a glue system and improve the crosslinking density through the combination of the components, so that the pure adhesive film prepared from the adhesive has low dielectric constant and low dielectric loss.
The invention also provides a preparation method of the adhesive.
The invention also provides a pure adhesive film prepared from the adhesive.
The invention also provides a preparation method of the pure adhesive film.
The invention also provides application of the pure adhesive film in preparing a circuit board material.
The first aspect of the invention provides an adhesive, which is prepared from the following raw materials: modified polyolefin resin, ethylene propylene diene monomer, polyphenyl ether and epoxy resin;
the modified polyolefin resin includes at least one of a maleic anhydride modified polybutadiene-styrene copolymer, a polybutadiene, a butadiene-styrene copolymer, and a polybutadiene;
the ethylene propylene diene monomer main chain is saturated hydrocarbon;
the polyphenyl ether is double-end hydroxyl polyphenyl ether;
the epoxy resin is an epoxidized polybutadiene having a terminal hydroxyl group.
The adhesive provided by the invention has at least the following beneficial effects:
1. the polybutadiene chain segment in the modified polyolefin resin is nonpolar and has poor compatibility with polar solvents, and the compatibility of the polybutadiene chain segment grafted with polar group maleic anhydride can be improved; and maleic anhydride participates in the reaction to form a three-dimensional reticular structure; meanwhile, the maleic anhydride modified polyolefin resin is selected to have extremely low dielectric constant, the dielectric constant is related to polarity, the more polar groups are, the larger dielectric constant is, the smaller the dielectric constant is, the maleic anhydride reacts with hydroxyl in polyphenyl ether and epoxy groups in epoxy resin to form a three-dimensional network polymer, and meanwhile, double bonds on a polyolefin chain segment in the modified polyolefin resin and double bonds in ethylene propylene diene monomer rubber can also form the three-dimensional network polymer, so that the performances of heat resistance, strength, glass transition temperature and the like of the modified polyolefin resin can be improved.
2. The ethylene propylene diene monomer mainly plays a role in toughening, the main chains of the ethylene propylene diene monomer are all saturated bonds, only unsaturated double bonds possibly exist on side chains, and the ethylene propylene diene monomer has excellent ageing resistance such as ozone resistance, heat resistance and weather resistance. While the unsaturated double bonds on the side chains can be ring-opened crosslinked.
3. The polyphenyl ether has a relatively symmetrical structure, fewer polar groups and very low dielectric loss and dielectric constant, and hydroxyl groups in the polyphenyl ether can react with maleic anhydride in the modified polyolefin resin to form a polymer.
4. Conventional epoxy resins carry, in addition to the epoxide groups, other polar groups, e.g. -CH 3 The epoxy hydroxyl-terminated polybutadiene selected by the invention has no other polar groups except epoxy groups and hydroxyl groups at two ends, so that the dielectric properties of the epoxy-terminated polybutadiene are smaller, dk and Df in a glue system can be effectively reduced, and the crosslinking density of the epoxy-terminated polybutadiene is improved.
In some embodiments of the present invention, the modified polyolefin resin is 20 to 50 parts by weight, the ethylene propylene diene monomer is 20 to 40 parts by weight, the polyphenylene ether is 5 to 20 parts by weight, and the epoxy resin is 5 to 20 parts by weight.
In some embodiments of the invention, the preparation of the feedstock further comprises: a filler and an initiator.
In some embodiments of the invention, the filler is 10 to 40 parts by weight and the initiator is 1 to 10 parts by weight.
In some embodiments of the invention, the filler comprises silica.
In some embodiments of the invention, the initiator comprises at least one of dibenzoyl peroxide and azobisisobutyronitrile.
In some embodiments of the present invention, the adhesive is prepared from the following raw materials in parts by weight: 20-50 parts of modified polyolefin resin, 20-40 parts of ethylene propylene diene monomer rubber, 5-20 parts of polyphenyl ether, 5-20 parts of epoxy resin and 10-40 parts of filler.
In some embodiments of the present invention, adjuvants such as silane coupling agents, flame retardants, accelerators, antioxidants, and the like may be added as needed.
The second aspect of the invention provides a preparation method of an adhesive, comprising the following steps:
a1: dispersing and mixing the polyphenyl ether and the ethylene propylene diene monomer to obtain mother liquor;
a2: and C, dispersing the mother solution obtained in the step A1, and mixing the modified polyolefin resin and the epoxy resin to obtain the modified polyolefin resin.
In some preferred embodiments of the present invention, a method for preparing an adhesive includes the steps of:
a1: sequentially adding and mixing polyphenyl ether resin, ethylene propylene diene monomer, filler and solvent to obtain mother solution;
a2: and (C) mixing the mother liquor obtained in the step (A1), the modified polyolefin resin, the epoxidized polyolefin and the initiator to obtain the modified polyolefin resin.
In some embodiments of the invention, in step A1, the solvent comprises at least one of toluene and xylene.
In some embodiments of the present invention, in step A1, the polyphenylene ether resin, the ethylene propylene diene monomer, the filler and the solvent are sequentially added into a stirring kettle, mixed and stirred, and then sanded with a sand mill for 2-3 times to prepare a mother solution.
In some embodiments of the invention, the mother liquor has a particle size of no more than 10 μm.
In some embodiments of the invention, in step A2, the mixing is for a period of 2 to 4 hours.
The third aspect of the invention provides an adhesive pure film, wherein the preparation raw materials of the pure film comprise the adhesive.
The fourth aspect of the invention provides a method for preparing the pure film, comprising the following steps:
b1: and coating the adhesive on the release film, and drying to obtain the compound.
B2: and B1, pressing the compound obtained in the step B1 with the release paper to prepare a pure adhesive film.
In some embodiments of the invention, the drying time is 100 to 150 seconds.
In some embodiments of the invention, the drying temperature is 120 to 180 ℃.
In some embodiments of the invention, the temperature of the press-fit is 50-100 ℃.
The fifth aspect of the invention provides an application of the pure adhesive film in preparing a circuit board material.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a molecular formula of a modified polyolefin resin;
FIG. 2 is a schematic representation of ethylene propylene diene monomer molecular formula;
FIG. 3 is a molecular formula of polyphenylene ether;
FIG. 4 is a molecular formula of an epoxy resin;
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment prepares an adhesive, which comprises the following specific processes:
a1: 10 parts of polyphenyl ether (the molecular formula of the polyphenyl ether is shown as figure 3), 30 parts of ethylene propylene diene monomer (the molecular formula of the ethylene propylene diene monomer is shown as figure 2), 25 parts of silicon dioxide and a solvent are sequentially added into a stirring kettle, mixed and stirred at 25 ℃ at 300r/min, and then a sand mill is used for sand milling for 3 times to prepare mother liquor.
A2: 25 parts of mother solution and modified polyolefin resin (the molecular formula of the modified polyolefin resin is shown in figure 1, wherein the values of x, y and z are 10-30); 10 parts of epoxy resin (the molecular formula of the epoxy resin is shown in figure 4); adding into a stirring kettle, continuously stirring, and stirring for 3 hours to mix uniformly to prepare the adhesive.
Example 2
The embodiment prepares an adhesive, which comprises the following specific processes:
a1: 7 parts of polyphenyl ether, 50 parts of ethylene propylene diene monomer and 18 parts of silicon dioxide as well as solvent are sequentially added into a stirring kettle, mixed and stirred at 25 ℃ for 300r/min, and then sand ground for 3 times by a sand mill to prepare mother liquor.
A2: adding 18 parts of mother solution, 18 parts of modified polyolefin resin and 7 parts of epoxy resin into a stirring kettle, continuously stirring, and stirring for 3 hours to uniformly mix to prepare the adhesive.
Example 3
The embodiment prepares a pure adhesive film, which comprises the following specific processes:
b1: and coating the adhesive on the release film, and drying at 150 ℃ for 300 seconds to obtain the compound.
B2: and (3) pressing the compound obtained in the step (B1) and the release paper at the temperature of 75 ℃ to prepare a pure adhesive film.
Comparative example 1
The adhesive is prepared according to the comparative example, and ethylene propylene diene monomer is not added in the comparative example, and the specific process is as follows:
a1: 14 parts of polyphenyl ether, 36 parts of silicon dioxide and a solvent are sequentially added into a stirring kettle, mixed and stirred at 25 ℃ for 300r/min, and then sanded for 3 times by a sand mill to prepare mother liquor.
A2: and adding 36 parts of mother solution, 36 parts of modified polyolefin resin and 14 parts of epoxy resin into a stirring kettle, continuously stirring, and stirring for 3 hours to uniformly mix to prepare the adhesive.
Comparative example 2
The comparative example is an adhesive which is different from the example 1 in that ethylene propylene diene monomer rubber is replaced by nitrile rubber with the same toughening effect, and the specific process is as follows:
a1: 10 parts of polyphenyl ether, 30 parts of nitrile rubber and 25 parts of silicon dioxide are sequentially added into a stirring kettle, mixed and stirred at 25 ℃ for 300r/min, and then sanded for 3 times by a sand mill to prepare mother liquor.
A2: adding 25 parts of mother solution, 25 parts of modified polyolefin resin and 10 parts of epoxy resin into a stirring kettle, continuously stirring, and stirring for 3 hours to uniformly mix to prepare the adhesive.
Comparative example 3
The adhesive prepared in this example is different from that in example 1 in that ethylene propylene diene monomer is changed into polyimide solution, and the specific process is as follows:
a1: 10 parts of polyphenyl ether, 30 parts of polyimide solution and 25 parts of silicon dioxide are sequentially added into a stirring kettle, mixed and stirred at 25 ℃ for 300r/min, and then sanded for 3 times by a sand mill to prepare mother liquor.
A2: adding 25 parts of mother solution, 25 parts of modified polyolefin resin and 10 parts of epoxy resin into a stirring kettle, continuously stirring, and stirring for 3 hours to uniformly mix to prepare the adhesive.
Comparative example 4
This example produced an adhesive differing from example 2 in the specific procedure of adding a polyolefin resin containing no maleic anhydride:
a1: 7 parts of polyphenyl ether, 50 parts of ethylene propylene diene monomer and 18 parts of silicon dioxide as well as solvent are sequentially added into a stirring kettle, mixed and stirred at 25 ℃ for 300r/min, and then sand ground for 3 times by a sand mill to prepare mother liquor.
A2: adding 18 parts of mother solution, 18 parts of polybutadiene resin and 7 parts of epoxy resin into a stirring kettle, continuously stirring, and stirring for 3 hours to uniformly mix to prepare the adhesive.
Test examples
The performance of the adhesives prepared in the examples and comparative examples was tested in this test example. The results are recorded in table 1 below.
TABLE 1 Properties of the adhesive
The ethylene propylene diene monomer rubber is not included in the comparative example 1, the ethylene propylene diene monomer rubber is replaced by the nitrile rubber with the same toughening effect in the comparative example 2, the heat resistance NG is caused by the fact that the heat resistance of soldering tin is related to the crosslinking density, too low crosslinking density is caused by too many polar groups, dk and Df are increased due to the fact that the crosslinking density is too high, the flexibility is generally used for making the rubber not too brittle, and the currently used toughening agent is generally carboxyl-terminated nitrile rubber. The excessive carboxyl group thereof increases Dk, df, and the ethylene propylene diene monomer is converted into a polyimide solution in comparison with example 3, and the addition of the polyimide solution results in an increase in dielectric constant, and the polyolefin resin excluding maleic anhydride, which is a polar group capable of participating in the reaction, reacts with hydroxyl groups in polyphenylene ether and epoxy groups in epoxy resin to form a three-dimensional network polymer in comparison with example 1, thereby improving heat resistance and strength.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (9)
1. The adhesive is characterized by comprising the following preparation raw materials: modified polyolefin resin, ethylene propylene diene monomer, polyphenyl ether and epoxy resin;
the modified polyolefin resin includes at least one of a maleic anhydride modified polybutadiene-styrene copolymer, a polybutadiene, a butadiene-styrene copolymer, and a polybutadiene;
the ethylene propylene diene monomer main chain is saturated hydrocarbon;
the polyphenyl ether is double-end hydroxyl polyphenyl ether;
the epoxy resin is epoxidized polybutadiene with terminal hydroxyl groups;
20-50 parts of modified polyolefin resin, 20-40 parts of ethylene propylene diene monomer rubber, 5-20 parts of polyphenyl ether and 5-20 parts of epoxy resin.
2. The adhesive according to claim 1, wherein the adhesive is prepared from the following raw materials: a filler and an initiator.
3. The adhesive according to claim 2, wherein the filler is 10 to 40 parts by weight and the initiator is 1 to 10 parts by weight.
4. The adhesive of claim 3, wherein the filler comprises silica.
5. A method of preparing the adhesive of claim 1, comprising the steps of:
a1: dispersing and mixing the polyphenyl ether and the ethylene propylene diene monomer to obtain mother liquor;
a2: and C, dispersing and mixing the mother solution obtained in the step A1 and the modified polyolefin resin, thereby obtaining the epoxy resin.
6. A pellicle characterized in that the raw material for preparing the pellicle comprises the adhesive according to any one of claims 1 to 4.
7. A method for preparing a pellicle according to claim 6, comprising spreading, drying, and laminating the adhesive.
8. The method of claim 7, wherein the drying temperature is 120-180 ℃.
9. Use of a pure film prepared by the preparation method according to claim 7 or 8 for preparing a circuit board material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210012395.1A CN114292607B (en) | 2022-01-06 | 2022-01-06 | Adhesive and preparation method and application thereof |
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| CN202210012395.1A CN114292607B (en) | 2022-01-06 | 2022-01-06 | Adhesive and preparation method and application thereof |
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| CN114292607B true CN114292607B (en) | 2023-06-06 |
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| CN116162431A (en) * | 2022-12-30 | 2023-05-26 | 烟台德邦科技股份有限公司 | Hybrid curing damp-heat resistant adhesive and preparation method thereof |
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| KR102479228B1 (en) * | 2016-12-22 | 2022-12-21 | 도아고세이가부시키가이샤 | Adhesive composition and coverlay film, bonding sheet, copper-clad laminate and electromagnetic shielding material using the same |
| TWI637405B (en) * | 2017-03-15 | 2018-10-01 | 臻鼎科技股份有限公司 | Low dielectric resin composition, film and circuit board using the same |
| CN110317541B (en) * | 2019-06-19 | 2021-07-13 | 南亚新材料科技股份有限公司 | Bonding sheet and preparation method of high-speed copper-clad plate |
| CN111393724A (en) * | 2020-03-30 | 2020-07-10 | 广东生益科技股份有限公司 | Resin composition, and prepreg and circuit material using same |
| CN113234242B (en) * | 2021-06-29 | 2022-05-24 | 四川大学 | Double-bond-terminated polyphenyl ether and epoxidized polybutadiene resin co-crosslinked polymer capable of being used for 5G high-speed high-frequency communication and preparation method thereof |
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