CN112048155A - Glue solution for halogen-free medium-Tg loss copper-clad plate and preparation method and application thereof - Google Patents
Glue solution for halogen-free medium-Tg loss copper-clad plate and preparation method and application thereof Download PDFInfo
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- CN112048155A CN112048155A CN202010983666.9A CN202010983666A CN112048155A CN 112048155 A CN112048155 A CN 112048155A CN 202010983666 A CN202010983666 A CN 202010983666A CN 112048155 A CN112048155 A CN 112048155A
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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Abstract
The invention provides glue solution for a halogen-free middle-Tg loss copper-clad plate, and a preparation method and application thereof. The glue solution for the halogen-free middle-Tg loss copper-clad plate comprises the following components in parts by weight: 25-35 parts of biphenyl epoxy resin, 15-25 parts of isocyanate epoxy resin, 10-30 parts of o-cresol formaldehyde epoxy resin, 10-20 parts of phenolic resin, 1-5 parts of phosphorus-containing phenolic resin, 5-15 parts of benzoxazine resin, 0.2-0.5 part of curing accelerator, 50-70 parts of inorganic filler, 0.1-0.3 part of interface bonding agent and 150 parts of solvent 120-. The halogen-free middle-Tg loss copper clad laminate prepared by using the glue solution has good flame retardance and heat resistance, low water absorption and excellent dielectric property.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to glue solution for a halogen-free medium-Tg loss copper-clad plate, and a preparation method and application thereof.
Background
Since 2 months in 2003, European regulations on the waste of electrical and electronic equipment and regulations on the use of harmful substances in electrical and electronic equipment stipulate that halogen-containing flame retardants such as polybrominated biphenyls (PBB) and polybrominated diphenyl ethers (PBDE) are limited, and the development of halogen-free copper-clad plates is promoted. In month 1 of 2008, the Intel corporation proposed a seating meeting with the theme of "pushing non-halogenated electronic products", promises to implement non-halogenation of products of the Intel corporation within a few years, and pushed the development of halogen-free copper-clad plates again.
Due to the environmental protection requirement, the global electronics industry has entered the lead-free soldering era since 2006, month 7 and day 1. Since the soldering temperature in the lead-free soldering process is higher than that in the past by more than 20 ℃, higher requirements are put on the comprehensive properties of the printed circuit board and the base material, such as: flame retardancy, low water absorption, heat resistance, etc. However, the halogen-free copper clad laminate always faces the defects of large brittleness, large water absorption, low heat resistance, high cost and the like when starting to develop from the beginning.
Meanwhile, with the development of technology, the amount of information to be processed by electronic devices has increased significantly, and packaging technologies such as high integration of semiconductor devices mounted thereon, high density of wiring, and multilayering have rapidly developed, and it is required to apply an insulating material having a low dielectric constant and low dielectric loss to a printed wiring board in order to increase the transmission rate of signals, reduce the loss during signal transmission, and increase the amount of information to be processed by the corresponding electronic devices. Therefore, it is very important to improve the defects of halogen-free substrates and develop corresponding resin compositions to meet the market demand.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide glue solution for a halogen-free middle-Tg loss copper-clad plate, and a preparation method and application thereof.
The invention provides a glue solution for a halogen-free middle-Tg loss copper-clad plate, which comprises the following raw materials in parts by weight: 25-35 parts of biphenyl epoxy resin, 15-25 parts of isocyanate epoxy resin, 10-30 parts of o-cresol formaldehyde epoxy resin, 10-20 parts of phenolic resin, 1-5 parts of phosphorus-containing phenolic resin, 5-15 parts of benzoxazine resin, 0.2-0.5 part of curing accelerator, 50-70 parts of inorganic filler, 0.1-0.3 part of interface bonding agent and 150 parts of solvent 120-.
According to the invention, the resin system consisting of the biphenyl epoxy resin, the isocyanate epoxy resin and the o-cresol formaldehyde epoxy resin is adopted, so that the glass transition temperature is increased, the excellent flame retardant property is ensured, and the halogen-free requirement can be well met; meanwhile, the resin system also reduces Dk and Df, reduces hygroscopicity, and improves the characteristics of electrical insulation, mechanical strength and the like, thereby being capable of well improving the defects of the existing halogen-free substrate. In the resin system of the present invention, the mass ratio of the biphenyl epoxy resin, the isocyanate epoxy resin and the o-cresol novolac epoxy resin may be 30: 20: (10-30).
In addition, the curing agent system consisting of the phenolic resin, the phosphorus-containing phenolic resin and the benzoxazine resin is matched with the specific resin, so that the halogen-free product with the Tg of more than 150 ℃ can be prepared, the halogen-free product has good chemical stability, heat resistance and corrosion resistance, and has the advantages of low shrinkage, strong cohesiveness, high mechanical strength and the like, the substrate is ensured to have excellent reliability, the dielectric constant and dielectric loss of the substrate are remarkably reduced, the market requirements of high transmission and low loss are met, and the halogen-free product is suitable for the lead-free process of the PCB. In the curing agent system of the present invention, the mass ratio of the phenolic resin, the phosphorus-containing phenolic resin, and the benzoxazine resin may be 15: 2: (5-15).
In the present invention, the curing accelerator may include 2-phenylimidazole 0.1 to 0.3 parts and 2-ethyl-4-methylimidazole 0.1 to 0.2 parts; further, the mass ratio of 2-phenylimidazole to 2-ethyl-4-methylimidazole in the curing accelerator may be 2: 1.
in the present invention, the inorganic filler may include 45 to 55 parts of fine active fused silica powder and 5 to 15 parts of talc powder. Further, the mass ratio of the active fused silica powder to the talc powder in the inorganic filler may be 5: 1.
the invention does not impose strict restrictions on the interface binder; specifically, the interface bonding agent may be a silane coupling agent.
In the invention, the solvent can comprise 55-65 parts of butanone, 25-35 parts of propylene glycol methyl ether and 40-50 parts of cyclohexanone; further, the mass ratio of butanone, propylene glycol methyl ether and cyclohexanone in the solvent can be 6: 3: 4.
the invention also provides a preparation method of the glue solution for the halogen-free middle-Tg loss copper-clad plate, which comprises the following steps:
A) stirring and mixing a solvent, an interface bonding agent, phenolic resin, phosphorus-containing phenolic resin and benzoxazine resin according to parts by weight to obtain a first mixture;
B) and adding the rest components into the first mixture according to the parts by weight, and stirring to obtain the glue solution for the halogen-free middle-Tg loss copper-clad plate.
Specifically, in step B), the stirring may include: stirring at 800-.
The invention also provides application of the glue solution for the halogen-free middle-Tg loss copper-clad plate in preparation of the halogen-free middle-Tg loss copper-clad plate.
The invention also provides a preparation method of the halogen-free middle-Tg loss copper-clad plate, which comprises the following steps:
preparing the glue solution for the halogen-free middle-Tg loss copper-clad plate into a prepreg;
and (3) laminating the prepreg and the copper foil, and then carrying out hot pressing to obtain the halogen-free middle-Tg loss copper clad laminate.
Specifically, when the prepreg is prepared, the gel content is controlled to be 40-50%, the fluidity is controlled to be 15-50%, and the gelling time is controlled to be 120-180 s.
The invention also provides a halogen-free middle-Tg loss copper-clad plate which is prepared according to the preparation method. The halogen-free middle-Tg loss copper-clad plate does not contain halogen, belongs to an environment-friendly material, does not use the traditional curing agent dicyandiamide, and adopts phenolic resin as the curing agent, so that the heat resistance of the copper-clad plate is improved, and the lead-free process requirement is met; meanwhile, the substrate has lower dielectric property and meets the requirement of electronic informatization rapid processing.
The implementation of the invention has at least the following advantages:
1. the invention adopts a specific resin system, improves the glass transition temperature, ensures excellent flame retardant property, reduces Dk and Df, reduces hygroscopicity, improves the characteristics of electrical insulation, mechanical strength and the like, and can well improve the defects of the existing halogen-free substrate;
2. according to the invention, a specific curing agent system is matched with the specific resin, so that a halogen-free product with the Tg of more than 150 ℃ can be prepared, the halogen-free product has good chemical stability, heat resistance and corrosion resistance, and has the advantages of low shrinkage, strong cohesiveness, high mechanical strength and the like, the substrate is ensured to have excellent reliability, the dielectric constant and dielectric loss of the substrate are remarkably reduced, the market requirements of high transmission and low loss are met, and the halogen-free product is suitable for a lead-free process of a PCB.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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.
Example 1
Firstly, preparing glue solution
The glue solution of the embodiment comprises the following components in parts by weight:
the preparation steps of the glue solution are as follows:
cleaning a glue mixing tank by using acetone, adding the solvent 1, the solvent 2 and the interface bonding agent according to the parts by weight, adding the curing agent, stirring for 2 hours at 1500r/min to completely dissolve the curing agent, then sequentially adding the rest components, stirring for 3 hours at the rotating speed of 1000r/min, stirring for 2 hours at the rotating speed of 500r/min, and testing the gelation time of the glue to be qualified to obtain the glue solution.
Secondly, preparing a prepreg
Preparing the prepared glue solution into a prepreg according to a conventional mode; wherein, the content of the glue is controlled to be 42 percent, the fluidity is controlled to be 38 percent, the gelling time is 150s, and the volatile matter is less than 0.5 percent.
Thirdly, preparing the halogen-free middle-Tg loss copper-clad plate
And taking 8 prepregs, covering a copper foil on each prepreg to form a combined stack, putting the combined stack into a hot press, and pressing for 3.5 hours under the conditions that the temperature is 210 ℃ and the pressure is 420psi to obtain the halogen-free middle-Tg loss copper-clad plate.
The method for detecting the loss copper-clad plate in Tg in the halogen-free process comprises the following steps:
glass transition temperature (Tg): measured by Differential Scanning Calorimetry (DSC) according to the DSC method defined by IPC-TM-6502.4.25;
thermal stratification time T-288: measured according to the IPC-TM-6502.4.24.1 method;
thermal cracking temperature (Td): measured according to the method specified in IPC-TM-6502.4.25.6;
flame retardancy: measured according to the UL94 vertical burning method;
PCT + wicking: and (3) steaming the PCT for 3h, and then placing the PCT into a tin furnace at 288 ℃ to test whether the substrate has white spots, delamination and blistering.
The performance results of the loss copper clad laminate in Tg in no halogen are shown in table 1.
Example 2
Firstly, preparing glue solution
The glue solution of the embodiment comprises the following components in parts by weight:
the preparation steps of the glue solution are as follows:
cleaning a glue mixing tank by using acetone, adding the solvent 1, the solvent 2 and the interface bonding agent according to the parts by weight, adding the curing agent, stirring for 2 hours at 1500r/min to completely dissolve the curing agent, then sequentially adding the rest components, stirring for 2 hours at the rotating speed of 1200r/min, stirring for 1 hour at the rotating speed of 600r/min, and testing the gelation time of the glue to be qualified to obtain the glue solution.
Secondly, preparing a prepreg
Preparing the prepared glue solution into a prepreg according to a conventional mode; wherein, the content of the glue is controlled to be 40 percent, the fluidity is controlled to be 40 percent, the gelling time is 120s, and the volatile matter is less than 0.5 percent.
Thirdly, preparing the halogen-free middle-Tg loss copper-clad plate
And taking 8 prepregs, covering a copper foil on each prepreg to form a combined stack, putting the combined stack into a hot press, and pressing for 3.5 hours under the conditions that the temperature is 210 ℃ and the pressure is 420psi to obtain the halogen-free middle-Tg loss copper-clad plate.
The method of example 1 is adopted to detect the halogen-free middle Tg loss copper clad laminate prepared in the above, and the results are shown in Table 1.
Example 3
Firstly, preparing glue solution
The glue solution of the embodiment comprises the following components in parts by weight:
the preparation steps of the glue solution are as follows:
cleaning a glue mixing tank by using acetone, adding the solvent 1, the solvent 2 and the interface bonding agent according to the parts by weight, adding the curing agent, stirring for 2 hours at 1500r/min to completely dissolve the curing agent, then sequentially adding the rest components, stirring for 4 hours at the rotating speed of 800r/min, stirring for 3 hours at the rotating speed of 400r/min, and testing the gelation time of the glue to be qualified to obtain the glue solution.
Secondly, preparing a prepreg
Preparing the prepared glue solution into a prepreg according to a conventional mode; wherein the content of the rubber is controlled to be 50%, the fluidity is controlled to be 30%, the gelling time is 180s, and the volatile matter is less than 0.5%.
Thirdly, preparing the halogen-free middle-Tg loss copper-clad plate
And taking 8 prepregs, covering a copper foil on each prepreg to form a combined stack, putting the combined stack into a hot press, and pressing for 3.5 hours under the conditions that the temperature is 210 ℃ and the pressure is 420psi to obtain the halogen-free middle-Tg loss copper-clad plate.
The method of example 1 is adopted to detect the halogen-free middle Tg loss copper clad laminate prepared in the above, and the results are shown in Table 1.
Comparative example 1
Substantially the same as in example 1 except that the resin composition was different; the resin composition of this comparative example is as follows:
resin 1: 10 parts of biphenyl epoxy resin
Resin 2: bisphenol A type epoxy resin 20 parts
Resin 3: naphthalene ring epoxy resin 10 parts
The method of example 1 is adopted to detect the halogen-free middle Tg loss copper clad laminate prepared in the above, and the results are shown in Table 1.
Comparative example 2
Substantially the same as in example 1 except that the resin composition was different; the resin composition of this comparative example is as follows:
resin 1: 30 parts of phosphorus-containing epoxy resin
Resin 2: isocyanate epoxy resin 20 parts
Resin 3: 10 parts of phenoxy resin
The method of example 1 is adopted to detect the halogen-free middle Tg loss copper clad laminate prepared in the above, and the results are shown in Table 1.
Comparative example 3
The same as example 1 except that the composition of the curing agent was different; the curing agent composition of this comparative example was as follows:
curing agent 1: 15 portions of phenolic resin
Curing agent 2: 2 parts of phosphorus-containing phenolic resin
Curing agent 3: 5 parts of dicyandiamide
The method of example 1 is adopted to detect the halogen-free middle Tg loss copper clad laminate prepared in the above, and the results are shown in Table 1.
Table 1 performance test results of each copper-clad plate
| Test items | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tg(DSC)/℃ | 160 | 162 | 165 | 147 | 147 | 145 |
| Thermal stratification time T288(TMA) | ＞60 | ＞60 | ＞60 | 47 | 50 | 51 |
| Thermal cracking temperature Td (TGA) | 383 | 383 | 386 | 357 | 352 | 354 |
| CTE(50～260℃) | 2.7 | 2.7 | 2.8 | 3.0 | 3.2 | 3.1 |
| Flame retardancy (UL94) | V-0 | V-0 | V-0 | V-1 | V-1 | V-1 |
| Peel strength (lb/in)1OZ | 6.6 | 6.5 | 6.2 | 4.7 | 4.9 | 4.4 |
| Solder heat resistance (288 ℃ C.) 10 s/time | ＞15 | ＞15 | ＞15 | 8 | 7 | 9 |
| Solder heat resistance (288 ℃ C.) 60 s/time | ＞5 | ＞5 | ＞5 | 3 | 4 | 4 |
| Dielectric constant (RC: 50%, Dk,10G) | 4.2 | 4.2 | 4.1 | 4.5 | 4.4 | 4.6 |
| Dielectric loss (RC: 50%, Df,10G) | 0.0012 | 0.0012 | 0.0011 | 0.0018 | 0.0020 | 0.0019 |
| PCT (PCT120 x 3h) + tin dipping (min) | ＞5 | ＞5 | ＞5 | 1 | 2 | 1 |
Table 1 the results show that:
compared with the resin system and the immobilization system of the comparative example, the resin system composed of the biphenyl epoxy resin, the isocyanate epoxy resin and the o-cresol formaldehyde epoxy resin is adopted in the embodiments 1-3 of the invention, and the curing agent system composed of the phenol formaldehyde resin, the phosphorus-containing phenol formaldehyde resin and the benzoxazine resin is matched, so that the glass transition temperature is increased, the excellent flame retardant property is ensured, the Dk and the Df are reduced, the moisture absorption is reduced, the electrical insulation property, the mechanical strength and other properties are improved, and the defects of the existing halogen-free substrate can be well improved.
The glue solution for the halogen-free medium-Tg loss copper-clad plate can be used for preparing halogen-free products with Tg of more than 150 ℃, has good chemical stability, heat resistance and corrosion resistance, has the advantages of low shrinkage, strong cohesiveness, high mechanical strength and the like, ensures that the substrate has excellent reliability, remarkably reduces the dielectric constant and dielectric loss of the substrate, meets the market requirements of high transmission and low loss, and is suitable for the lead-free process of PCB.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The glue solution for the halogen-free middle-Tg loss copper-clad plate is characterized by comprising the following raw materials in parts by weight: 25-35 parts of biphenyl epoxy resin, 15-25 parts of isocyanate epoxy resin, 10-30 parts of o-cresol formaldehyde epoxy resin, 10-20 parts of phenolic resin, 1-5 parts of phosphorus-containing phenolic resin, 5-15 parts of benzoxazine resin, 0.2-0.5 part of curing accelerator, 50-70 parts of inorganic filler, 0.1-0.3 part of interface bonding agent and 150 parts of solvent 120-.
2. The glue solution for the halogen-free middle-Tg loss copper-clad plate according to claim 1, wherein the curing accelerator comprises 0.1-0.3 part of 2-phenylimidazole and 0.1-0.2 part of 2-ethyl-4-methylimidazole.
3. The glue solution for the halogen-free middle-Tg loss copper-clad plate according to claim 1, wherein the inorganic filler comprises 45-55 parts of active fused silica micropowder and 5-15 parts of talcum powder.
4. The glue solution for the halogen-free middle-Tg loss copper-clad plate according to claim 1, wherein the interface bonding agent is a silane coupling agent.
5. The glue solution for the halogen-free middle-Tg loss copper-clad plate according to claim 1, wherein the solvent comprises 55-65 parts of butanone, 25-35 parts of propylene glycol methyl ether and 40-50 parts of cyclohexanone.
6. The preparation method of the glue solution for the halogen-free middle-Tg loss copper-clad plate according to any one of claims 1 to 5, which is characterized by comprising the following steps:
A) stirring and mixing a solvent, an interface bonding agent, phenolic resin, phosphorus-containing phenolic resin and benzoxazine resin according to parts by weight to obtain a first mixture;
B) and adding the rest components into the first mixture according to the parts by weight, and stirring to obtain the glue solution for the halogen-free middle-Tg loss copper-clad plate.
7. The method according to claim 6, wherein the stirring in step B) comprises: stirring at 800-.
8. The application of the glue solution for the halogen-free middle-Tg loss copper-clad plate according to any one of claims 1 to 5 in preparation of the halogen-free middle-Tg loss copper-clad plate.
9. A preparation method of a halogen-free middle-Tg loss copper-clad plate is characterized by comprising the following steps:
preparing the glue solution for the halogen-free middle Tg loss copper clad laminate according to any one of claims 1-5 into a prepreg;
laminating the prepreg and the copper foil and then carrying out hot pressing to obtain a halogen-free middle-Tg loss copper clad laminate;
preferably, when the prepreg is prepared, the gel content is controlled to be 40-50%, the fluidity is controlled to be 15-50%, and the gelling time is controlled to be 120-180 s.
10. A halogen-free middle-Tg loss copper-clad plate is characterized by being prepared according to the preparation method of claim 9.
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