CN112662131B - Liquid crystal modified resin composition, composite resin, prepreg and printed wiring board - Google Patents
Liquid crystal modified resin composition, composite resin, prepreg and printed wiring board Download PDFInfo
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- CN112662131B CN112662131B CN202011525179.4A CN202011525179A CN112662131B CN 112662131 B CN112662131 B CN 112662131B CN 202011525179 A CN202011525179 A CN 202011525179A CN 112662131 B CN112662131 B CN 112662131B
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Abstract
The application provides a liquid crystal modified resin composition, composite resin, prepreg and a printed wiring board; the preparation raw materials of the liquid crystal modified resin composition comprise: 30 to 70 parts of matrix resin, 10 to 40 parts of thermotropic liquid crystal polymer modified epoxy resin, 20 to 50 parts of phenoxy resin, 2 to 15 parts of curing agent, 20 to 60 parts of filler and 0 to 2 parts of curing accelerator; the liquid crystal modified resin composition has excellent adhesive property, heat resistance and higher glass transition temperature, and can be applied to the preparation of high-density and multi-performance Printed Circuit Boards (PCBs) with high temperature resistance, aging resistance, integrated circuit packaging, high frequency, high speed and the like, thereby promoting the development of high-end integrated circuits.
Description
Technical Field
The application relates to the technical field of composite resins, in particular to a liquid crystal modified resin composition, a composite resin, a prepreg and a printed wiring board.
Background
With the rapid development of the electronic industry, electronic products are being developed toward miniaturization, multifunction and high security, and high density and multi-performance of Printed Circuit Boards (PCBs) are required, while simultaneously satisfying the requirements of three-dimensional installation of electronic products. There is an increasing concern about the use of rigid-flex technology, i.e., technology that employs rigid circuit boards to be bonded to flexible circuit boards by bonding materials to produce printed wiring boards.
In the prior art, a common FR-4 bonding sheet is often used as a bonding material, and in recent years, a non-gumming prepreg (No flow prepreg) is increasingly considered to replace the traditional FR-4 bonding sheet, and compared with the FR-4 bonding sheet, when the non-gumming prepreg (No flow prepreg) is positioned in a B-stage resin section which is not cured by hot pressing, the non-gumming prepreg is non-gumming or extremely little gumming at high temperature and high pressure, and meanwhile, has good bonding performance, is very suitable for being used as a bonding material between a rigid circuit board and a flexible circuit board, and is widely used for manufacturing rigid-flexible Printed Circuit Boards (PCB). The traditional nonfluent prepregs mostly adopt rubber toughened and modified epoxy resin as a main matrix material, and although the nonfluent prepregs or prepregs with little gummosis can be obtained, the addition of the rubber component can obviously reduce the glass transition temperature of the resin material, thereby affecting the adhesive property and the heat resistance of the material.
Therefore, how to obtain a resin having excellent adhesion properties, heat resistance and a high glass transition temperature has been a difficult problem for those skilled in the art to overcome.
Disclosure of Invention
Based on this, the present application provides a liquid crystal modified resin composition having excellent adhesion property, heat resistance and higher glass transition temperature, and further provides a composite resin, a prepreg and a printed wiring board comprising the same.
The technical scheme of the application is as follows.
The application provides a liquid crystal modified resin composition, which comprises the following preparation raw materials in parts by mass:
in some of these embodiments, the liquid crystal modified resin composition is prepared from the following raw materials:
in some of these embodiments, the phenoxy resin is represented by formula (1):
wherein n is selected from any integer of 20 to 120, R 1 、R 2 、R 3 And R is 4 Each independently selected from a H atom, a halogen atom, or a phosphorus-containing group.
In some of these embodiments, the matrix resin is selected from epoxy resins.
In some embodiments, the curing accelerator is selected from at least one of imidazole-based curing accelerators, peroxide-based curing accelerators, azo-based curing accelerators, tertiary amine-based curing accelerators, phenolic curing accelerators, organometallic salt curing accelerators, and inorganic metal salt curing accelerators.
In some embodiments, the curing agent is selected from at least one of cyanate ester curing agents, aliphatic polyamine curing agents, alicyclic polyamine curing agents, aromatic amine curing agents, polyamide curing agents, latent curing agents, lewis acid-amine complex curing agents, and organic anhydride curing agents.
In some of these embodiments, the filler is selected from inorganic fillers.
Another aspect of the present application provides a composite resin produced using a raw material comprising the liquid crystal modified resin composition as described above.
The application also provides a prepreg, which comprises a reinforcing material and a resin material loaded on the surface of the reinforcing material, wherein the resin material is the composite resin.
The application further provides a printed wiring board, and the preparation raw materials of the printed wiring board comprise the prepreg.
Advantageous effects
In the liquid crystal modified resin composition provided by the application, the base resin is modified by adopting the synergistic cooperation of the phenoxy resin with the thermotropic liquid crystal polymer modified epoxy resin (TLCP modified epoxy resin) in a specific proportion, wherein the TLCP modified epoxy resin contains a large number of rigid mesogens and a certain number of flexible chain ends, so that the flexibility of the base resin can be obviously improved, the adhesive property of the resin is improved, and the glass transition temperature of a cured resin system cannot be reduced by using the TLCP modified epoxy resin in the specific proportion. The resin prepared by the composition ratio of the specific raw materials is not easy to generate molecular chain movement at high temperature and high pressure, so that the purpose that the pressing plate does not flow glue is achieved, and the resin can be applied to the preparation of high-density and multi-performance Printed Circuit Boards (PCBs) with high temperature resistance, ageing resistance, integrated circuit packaging, high frequency, high speed and the like, thereby promoting the development of high-end integrated circuits.
The present application also provides a composite resin prepared from the raw materials comprising the thermosetting resin composition as described above, which has excellent adhesive properties, heat resistance and a high glass transition temperature.
The application also comprises a prepreg which comprises a reinforcing material and a resin material loaded on the surface of the reinforcing material, wherein the resin material is the composite resin. The prepreg has excellent adhesive property, heat resistance and higher glass transition temperature, is not easy to generate molecular chain movement at high temperature and high pressure, achieves no or little gummosis at high temperature and high pressure, and can be applied to the preparation of high-density and multi-performance Printed Circuit Boards (PCBs) with high temperature resistance, ageing resistance, integrated circuit encapsulation, high frequency, high speed and the like, thereby promoting the development of high-end integrated circuits.
Detailed Description
The present application will be described more fully hereinafter in order to facilitate an understanding of the present application, and preferred embodiments of the present application are set forth. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the conventional Printed Circuit Board (PCB) technology field, a technology of preparing a printed circuit board by bonding a rigid circuit board and a flexible circuit board through a bonding material is increasingly adopted, so as to obtain a multifunctional printed circuit board. In recent years, non-gumming prepregs (No flow prepregs) have been widely used as bonding materials between rigid circuit boards and flexible circuit boards instead of conventional FR-4 bonding sheets. However, most of traditional non-gummosis prepregs adopt rubber toughening modified epoxy resin as a main matrix material, and although the non-gummosis or very little gummosis prepregs can be obtained, the addition of the rubber component can obviously reduce the glass transition temperature of the resin material, thereby affecting the adhesive property and heat resistance of the material.
Based on the research experience of the field of printed circuit boards for many years, the person skilled in the art finds that: the technical scheme of the application is obtained by adopting the synergistic cooperation of the phenoxy resin with the thermotropic liquid crystal polymer modified epoxy resin (TLCP modified epoxy resin) in a specific proportion to modify the matrix resin, wherein the TLCP modified epoxy resin can obviously improve the flexibility of the matrix resin so as to improve the adhesive property of the resin, and the glass transition temperature of a cured resin system cannot be reduced by using the TLCP modified epoxy resin in the specific proportion, and further through a large number of experimental researches.
The embodiment of the application provides a liquid crystal modified resin composition, which comprises the following preparation raw materials in parts by mass:
in the liquid crystal modified resin composition, a specific proportion of phenoxy resin and a thermotropic liquid crystal polymer modified epoxy resin (TLCP modified epoxy resin) are adopted to cooperatively match to modify the matrix resin, wherein the TLCP modified epoxy resin can obviously improve the flexibility of the matrix resin, so that the adhesive property of the resin is improved, and the glass transition temperature of a cured resin system cannot be reduced by using the TLCP modified epoxy resin with the specific proportion. The resin prepared by the composition ratio of the specific raw materials is not easy to generate molecular chain movement at high temperature and high pressure, so that the purpose that the pressing plate does not flow glue is achieved, and the resin can be applied to the preparation of high-density and multi-performance Printed Circuit Boards (PCBs) with high temperature resistance, ageing resistance, integrated circuit packaging, high frequency, high speed and the like, thereby promoting the development of high-end integrated circuits.
In the thermotropic liquid crystal polymer modified epoxy resin (TLCP modified epoxy resin), the liquid crystal molecular structure contains a large number of rigid mesogens and a certain amount of flexible chain ends, when the thermotropic liquid crystal polymer modified epoxy resin is used for modifying the matrix resin by the synergistic effect of the thermotropic liquid crystal polymer modified epoxy resin and the phenoxy resin, the property of the continuous phase of the matrix resin can be obviously improved, the shearing sliding band and microcracks of the resin are facilitated to be generated under the stress effect, and the stress concentration of the relaxation crack ends is caused, so that the crack expansion is hindered, and the purpose of toughening is achieved. And the addition of TLCP increases the flexibility of the system and reduces the crosslinking density of the resin, thereby greatly improving the compatibility with matrix resin, and simultaneously, the network structure after the resin is solidified is more compact and ordered due to the self-alignment effect of the liquid crystal element of the TLCP modified epoxy resin, thereby overcoming the defects that the heat resistance and the adhesive property of the resin are reduced due to the addition of the rubber component when the rubber toughened modified epoxy resin is adopted in the traditional technology.
In some embodiments, the preparation raw materials of the liquid crystal modified resin composition comprise 25-40 parts of thermotropic liquid crystal polymer modified epoxy resin according to parts by weight.
In some embodiments, the preparation raw materials of the liquid crystal modified resin composition comprise 4-15 parts of curing agent according to parts by weight.
In some embodiments, the liquid crystal modified resin composition comprises 30-60 parts of filler according to parts by weight.
In some embodiments, the preparation raw materials of the liquid crystal modified resin composition comprise 0.5-2 parts of a curing accelerator according to parts by weight.
Preferably, the preparation raw materials of the liquid crystal modified resin composition comprise the following components in parts by mass:
in some embodiments, the phenoxy resin is represented by formula (1):
wherein n is selected from any integer of 20 to 120, R 1 、R 2 、R 3 And R is 4 Each independently selected from a H atom, a halogen atom, or a phosphorus-containing group.
In some embodiments, the halogen is selected from bromine; in this case, the phenoxy resin is brominated phenoxy resin.
In some of these embodiments, the above-described phosphorus-containing groups are selected from phosphorus groups, in particular, at least one selected from phosphorus groups, primary phosphorus groups, and tertiary phosphorus groups.
In some of these embodiments, R 1 、R 2 、R 3 And R is 4 Are all selected from H atoms.
The phenoxy resin and the cooperative TLCP modified epoxy resin act cooperatively, so that the resin is not easy to produce molecular chain movement at high temperature and high pressure when the matrix resin is modified, and the purpose of no gummosis of the pressing plate is realized. Meanwhile, the phenoxy resin is also resin with good flexibility, and can toughen the matrix resin by coordinating with the TLCP modified epoxy resin, so that the glass transition temperature of a resin curing system can not be reduced while the adhesive force of the resin composition is improved.
In some of these embodiments, the matrix resin is selected from epoxy resins; specifically, the matrix resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type, biphenyl type epoxy resin, benzoxazine resin, alicyclic type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, linear novolac type epoxy resin, resorcinol type epoxy resin, tetrafunctional epoxy resin, isocyanate modified epoxy resin and diglycidyl amine type epoxy resin.
The TLCP modified epoxy resin can further increase the flexibility of the epoxy resin and reduce the crosslinking density of the resin, thereby greatly improving the compatibility with matrix resin and being beneficial to improving the heat resistance and the adhesive property of the resin composition.
In the liquid crystal modified resin composition of the present application, the kind of the thermotropic liquid crystal polymer-modified epoxy resin is not particularly limited.
In some embodiments, the thermotropic mesogens in the thermotropic liquid crystalline polymer-modified epoxy resin are selected from at least one of esters, biphenyls, methyl styrenes, and methylenes; further, in the thermotropic liquid crystal polymer-modified epoxy resin, the mass ratio of the thermotropic liquid crystal polymer is 2-20wt%.
In some of these embodiments, the filler is selected from inorganic fillers. Further, the filler is at least one selected from the group consisting of titanium dioxide, silicon dioxide, magnesium oxide, magnesium hydroxide, talc, mica powder, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, and barium sulfate.
In some embodiments, the above-mentioned curing accelerator is selected from at least one of imidazole-based curing accelerators, peroxide-based curing accelerators, azo-based curing accelerators, tertiary amine-based curing accelerators, phenol-based curing accelerators, organometallic salt curing accelerators, and inorganic metal salt curing accelerators. For example, the curing accelerator may be selected from imidazole curing accelerators such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, and may be at least one of organometallic salt curing accelerators such as zinc octoate, zinc iso-octoate, stannous octoate, dibutyltin dilaurate, zinc naphthenate, cobalt naphthenate, aluminum acetylacetonate, cobalt acetylacetonate, copper acetylacetonate.
In some embodiments, the curing agent is at least one selected from the group consisting of cyanate curing agents, aliphatic polyamine curing agents, alicyclic polyamine curing agents, aromatic amine curing agents, polyamide curing agents, latent curing agents, lewis acid-amine complex curing agents, and organic acid anhydride curing agents.
For example, the above-mentioned curing agent is selected from aliphatic polyhydric curing agents, specifically, at least one selected from ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine and trimethylhexamethylene. Specifically, the curing agent is selected from dicyandiamide.
Further, the present application also provides a composite resin produced using a raw material comprising any one of the liquid crystal-modified resin compositions as described above.
The composite resin has excellent adhesive property, heat resistance and higher glass transition temperature. In particular, the bonding strength with polyimide which is a preparation material of the flexible PCB is high.
An embodiment of the present application also provides a prepreg, where the prepreg includes a reinforcing material and a resin material loaded on a surface of the reinforcing material, and the resin material is a composite resin as described above.
In some of these embodiments, the reinforcing material is selected from inorganic fibrous materials or organic fibrous materials.
The prepreg has excellent adhesive property, heat resistance and higher glass transition temperature, is not easy to generate molecular chain movement at high temperature and high pressure, achieves no or little gummosis at high temperature and high pressure, and can be applied to the preparation of high-density and multi-performance Printed Circuit Boards (PCBs) with high temperature resistance, ageing resistance, integrated circuit encapsulation, high frequency, high speed and the like, thereby promoting the development of high-end integrated circuits.
The inorganic fiber material includes, but is not limited to, glass fiber, carbon fiber, silicon carbide fiber, asbestos fiber, and the like. The machine fiber material includes, but is not limited to, nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber, cotton fiber, and the like.
Wherein the glass fibers comprise E, NE, D, S, T and other different types of glass fibers.
Further, the preparation of the prepreg includes the following steps S20 to S30.
Step S20, preparing the thermosetting resin composition into a resin glue solution.
In some of these embodiments, step S20 includes the following steps S21-S21.
Step S21, mixing the curing agent and the organic solvent to obtain a mixture.
In some embodiments, the organic solvent is selected from at least one of dimethylformamide and dimethylacetamide. Further, the organic solvent is selected from dimethylformamide.
Step S22, mixing the mixture, the thermotropic liquid crystal polymer modified epoxy resin, the phenoxy resin, the matrix resin, the filler and the curing accelerator to obtain uniform resin glue solution.
And step S30, placing the reinforcing material into the resin glue solution obtained in the step S20 for soaking, taking out and heating for curing to obtain the prepreg.
In some of these embodiments, in step S30, the conditions of the impregnation are: soaking at normal temperature for 10s.
In some of these embodiments, in step S30, the conditions for heat curing are: heating and curing for 2-10 min at 130-250 ℃.
Further, an embodiment of the application also provides a printed wiring board, and the preparation raw materials of the printed wiring board comprise the prepreg.
In some embodiments, the raw materials for preparing the printed circuit board further comprise a rigid circuit board and a flexible circuit board; further, the prepreg is used for preparing an adhesive layer between the rigid circuit board and the flexible circuit board.
The printed circuit board has the characteristics of high density and multiple performances, can meet the requirement of three-dimensional installation of electronic products, and can promote development of high-end integrated circuits.
The application will be described in connection with specific embodiments, but the application is not limited thereto, and it will be appreciated that the appended claims outline the scope of the application, and those skilled in the art, guided by the inventive concept, will appreciate that certain changes made to the embodiments of the application will be covered by the spirit and scope of the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
1) According to the parts by weight, adding 4 parts of dicyandiamide and 60 parts of dimethylformamide into a batching bottle, fully stirring and dissolving, sequentially adding 10 parts of TLCP modified epoxy resin, 20 parts of phenoxy resin and 70 parts of matrix resin into the batching bottle, adding 33 parts of silicon dioxide and 0.5 part of 2-methylimidazole under stirring, and continuously and uniformly stirring to prepare the glue solution.
2) 1078 glass fiber cloth (basis weight 47.5g/m 2 ) Soaking the mixture in the glue solution obtained in the step 1) at normal temperature for 10s, taking out the mixture, and baking the mixture in a hot air circulation oven at 180 ℃ for 3min to obtain the nonfluent prepreg with the resin content of (65+/-1) wt%.
Example 2
1) According to the parts by weight, adding 4 parts of dicyandiamide and 60 parts of dimethylformamide into a batching bottle, fully stirring and dissolving, sequentially adding 10 parts of TLCP modified epoxy resin, 50 parts of phenoxy resin and 70 parts of matrix resin into the batching bottle, adding 33 parts of silicon dioxide and 0.5 part of 2-methylimidazole under stirring, and continuously and uniformly stirring to prepare the glue solution.
2) 1078 glass fiber cloth (basis weight 47.5g/m 2 ) Soaking the mixture in the glue solution obtained in the step 1) at normal temperature for 10s, taking out the mixture, and baking the mixture in a hot air circulation oven at 180 ℃ for 3min to obtain the nonfluent prepreg with the resin content of (65+/-1) wt%.
Example 3
1) According to the parts by weight, 5.5 parts of dicyandiamide and 60 parts of dimethylformamide are added into a batching bottle, after fully stirring and dissolving, 40 parts of TLCP modified epoxy resin, 20 parts of phenoxy resin and 70 parts of matrix resin are sequentially added into the batching bottle, and 33 parts of silicon dioxide and 0.5 part of 2-methylimidazole are added under the stirring condition, and then the mixture is continuously and uniformly stirred to prepare the glue solution.
2) 1078 glass fiber cloth (basis weight 47.5g/m 2 ) Soaking the mixture in the glue solution obtained in the step 1) at normal temperature for 10s, taking out the mixture, and baking the mixture in a hot air circulation oven at 180 ℃ for 3min to obtain the nonfluent prepreg with the resin content of (65+/-1) wt%.
Example 4
1) According to the parts by weight, adding 5.5 parts of dicyandiamide and 60 parts of dimethylformamide into a batching bottle, fully stirring and dissolving, sequentially adding 40 parts of TLCP modified epoxy resin, 50 parts of phenoxy resin and 70 parts of matrix resin into the batching bottle, adding 33 parts of silicon dioxide and 0.5 part of 2-methylimidazole under the stirring condition, and continuously and uniformly stirring to prepare the glue solution.
2) 1078 glass fiber cloth (basis weight 47.5g/m 2 ) Soaking the mixture in the glue solution obtained in the step 1) at normal temperature for 10s, taking out the mixture, and baking the mixture in a hot air circulation oven at 180 ℃ for 3min to obtain the nonfluent prepreg with the resin content of (65+/-1) wt%.
Example 5
1) According to the parts by weight, adding 4.5 parts of dicyandiamide and 60 parts of dimethylformamide into a batching bottle, fully stirring and dissolving, sequentially adding 25 parts of TLCP modified epoxy resin, 20 parts of phenoxy resin and 70 parts of matrix resin into the batching bottle, adding 33 parts of silicon dioxide and 0.5 part of 2-methylimidazole under the stirring condition, and continuously and uniformly stirring to prepare the glue solution.
2) 1078 glass fiber cloth (basis weight 47.5g/m 2 ) Soaking the mixture in the glue solution obtained in the step 1) at normal temperature for 10s, taking out the mixture, and baking the mixture in a hot air circulation oven at 180 ℃ for 3min to obtain the nonfluent prepreg with the resin content of (65+/-1) wt%.
Example 6
1) According to the parts by weight, adding 4.5 parts of dicyandiamide and 60 parts of dimethylformamide into a batching bottle, fully stirring and dissolving, sequentially adding 25 parts of TLCP modified epoxy resin, 30 parts of phenoxy resin and 70 parts of matrix resin into the batching bottle, adding 33 parts of silicon dioxide and 0.5 part of 2-methylimidazole under the stirring condition, and continuously and uniformly stirring to prepare the glue solution.
2) 1078 glass fiber cloth (basis weight 47.5g/m 2 ) Is put in stepThe glue solution obtained in the step 1) is immersed for 10s at normal temperature, and is taken out and put into a hot air circulation oven for baking for 3min at 180 ℃ to obtain the nonfluent prepreg with the resin content of (65+/-1) wt%.
Comparative example 1
1) According to the parts by weight, 4.5 parts of dicyandiamide and 60 parts of dimethylformamide are added into a batching bottle, 15 parts of CTBN modified epoxy resin, 20 parts of phenoxy resin and 70 parts of matrix resin are added into the batching bottle in sequence after being fully stirred and dissolved, and 33 parts of silicon dioxide and 0.5 part of 2-methylimidazole are added under the stirring condition and then are continuously and uniformly stirred to prepare the glue solution.
2) 1078 glass fiber cloth (basis weight 47.5g/m 2 ) Soaking the mixture in the glue solution obtained in the step 1) at normal temperature for 10s, taking out the mixture, and baking the mixture in a hot air circulation oven at 180 ℃ for 3min to obtain the nonfluent prepreg with the resin content of (65+/-1) wt%.
Comparative example 2
1) According to the parts by weight, adding 6 parts of dicyandiamide and 60 parts of dimethylformamide into a batching bottle, fully stirring and dissolving, sequentially adding 50 parts of phenoxy resin and 70 parts of matrix resin into the batching bottle, adding 33 parts of silicon dioxide and 0.5 part of 2-methylimidazole under stirring, and continuously and uniformly stirring to prepare the glue solution.
2) 1078 glass fiber cloth (basis weight 47.5g/m 2 ) Soaking the mixture in the glue solution obtained in the step 1) at normal temperature for 10s, taking out the mixture, and baking the mixture in a hot air circulation oven at 180 ℃ for 3min to obtain the nonfluent prepreg with the resin content of (65+/-1) wt%.
Comparative example 3
1) According to the parts by weight, 5.5 parts of dicyandiamide and 60 parts of dimethylformamide are added into a batching bottle, after fully stirring and dissolving, 45 parts of TLCP modified epoxy resin, 15 parts of phenoxy resin and 70 parts of matrix resin are sequentially added into the batching bottle, and 33 parts of silicon dioxide and 0.5 part of 2-methylimidazole are added under the stirring condition, and then the mixture is continuously and uniformly stirred to prepare the glue solution.
2) 1078 glass fiber cloth (basis weight 47.5g/m 2 ) Soaking in the glue solution obtained in step 1) at normal temperature for 10s, taking out, and baking in a hot air circulation oven at 180deg.C for 3min to obtain non-gummosis semi-cured resin with a resin content of (65+ -1) wt%And (3) a sheet.
The above raw materials are all available from commercial products:
the TLCP modified epoxy resin was purchased from Jiaba electronic technologies Inc. of Guangzhou, model SE-500.
The phenoxy resin is purchased from Shandong Shengquan chemical industry and is model SQP-40AXM40.
The matrix resin was an epoxy resin, available from Kunshana under the model NPEB-450A80.
CTBN modified epoxy resin is available from Complex chemistry (Shanghai) Inc. under the model number EPC-240.
The raw materials in examples 1 to 6 and comparative examples 1 to 3 are shown in Table 1
TABLE 1
Example 7
Performance tests were performed on the non-gummosis prepregs produced in examples 1 to 6 and comparative examples 1 to 3, and the results are shown in table 2 below:
TABLE 2
The test method is as follows:
1) Peel strength: the test method was performed according to (IPC-TM-650.2.4.8); wherein the peel strength test was performed with polyimide material as the substrate.
2) Glass transition temperature (Tg): according to (IPC-TM-650.2.4.25);
3) Glue overflow amount: according to (IPC-TM-650.2.3.17.2);
4) Heat resistance: according to (IPC-TM-650.2.4.13.1).
As shown by the test results in Table 2, according to the technical scheme of the application, the prepared adhesive-free prepreg has excellent adhesive property, heat resistance and higher glass transition temperature, is not easy to generate molecular chain movement at high temperature and high pressure, and achieves no adhesive-free or little adhesive-free at high temperature and high pressure. In comparative examples 1 and 2, the conventional rubber modified epoxy resin (CTBN modified epoxy resin) and phenoxy resin were used to modify the matrix resin, and the adhesive property of the prepared non-gummosis prepreg was poor, and the peel strength (PI) and glass transition temperature were lower than those of the non-gummosis prepreg prepared by the technical scheme of the present application.
Compared with example 3, the TLCP modified epoxy beyond the proportion range of the application is adopted in comparative example 3, the proportion of the phenoxy resin is reduced, the total mass parts of the TLCP modified epoxy and the phenoxy resin are kept unchanged, the glue overflow amount of the non-gummosis prepreg prepared in comparative example 3 is increased, and the peel strength (PI) is reduced relative to example 3.
The foregoing examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (9)
1. The liquid crystal modified resin composition is characterized by comprising the following raw materials in parts by mass:
the phenoxy resin is shown as a formula (1):
wherein n is selected from 20 to ultra-high120, R 1 、R 2 、R 3 And R is 4 Each independently selected from a H atom, a halogen atom, or a phosphorus-containing group;
the matrix resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, alicyclic type epoxy resin, phenol novolac type epoxy resin, o-resol type epoxy resin, linear novolac type epoxy resin, resorcinol type epoxy resin, tetrafunctional epoxy resin, isocyanate modified epoxy resin and diglycidyl amine type epoxy resin.
2. The liquid crystal modified resin composition according to claim 1, wherein the liquid crystal modified resin composition is prepared from the following raw materials:
3. the liquid crystal modified resin composition according to claim 1 or 2, wherein the curing accelerator is at least one selected from the group consisting of imidazole-based curing accelerators, peroxide-based curing accelerators, azo-based curing accelerators, tertiary amine-based curing accelerators, phenol-based curing accelerators, organometallic salt curing accelerators and inorganic metallic salt curing accelerators.
4. The liquid crystal modified resin composition according to claim 1, wherein the curing agent is at least one selected from the group consisting of cyanate-based curing agents, aliphatic polyamine-based curing agents, alicyclic polyamine-based curing agents, aromatic amine-based curing agents, polyamide-based curing agents, latent-type curing agents and organic acid anhydride-based curing agents.
5. The liquid crystal modified resin composition according to claim 1, wherein the curing agent is selected from the group consisting of lewis acid-amine complex type curing agents.
6. The liquid crystal modified resin composition according to claim 1, wherein the filler is selected from inorganic fillers.
7. A composite resin prepared from the liquid crystal modified resin composition according to any one of claims 1 to 6.
8. A prepreg comprising a reinforcing material and a resin material supported on the surface of the reinforcing material, wherein the resin material is the composite resin according to claim 7.
9. A printed wiring board, wherein the raw material for preparing the printed wiring board comprises the prepreg according to claim 8.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009008455A1 (en) * | 2007-07-12 | 2009-01-15 | Agc Matex Co., Ltd. | Glass-integrated resin molding and method of molding therefor |
| CN104822768A (en) * | 2012-11-30 | 2015-08-05 | Lg伊诺特有限公司 | Epoxy resin composition, and printed circuit board comprising insulation layer using epoxy resin composition |
| CN108440903A (en) * | 2018-02-07 | 2018-08-24 | 浙江华正新材料股份有限公司 | A kind of halogen-free resin composition and its low fluidity prepreg |
| CN110066494A (en) * | 2019-05-07 | 2019-07-30 | 金安国纪科技（杭州）有限公司 | Composition epoxy resin and its preparation method and application, aluminum-based copper-clad plate |
| CN111087759A (en) * | 2019-11-27 | 2020-05-01 | 广东盈骅新材料科技有限公司 | Resin composition and use thereof |
-
2020
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009008455A1 (en) * | 2007-07-12 | 2009-01-15 | Agc Matex Co., Ltd. | Glass-integrated resin molding and method of molding therefor |
| CN104822768A (en) * | 2012-11-30 | 2015-08-05 | Lg伊诺特有限公司 | Epoxy resin composition, and printed circuit board comprising insulation layer using epoxy resin composition |
| CN108440903A (en) * | 2018-02-07 | 2018-08-24 | 浙江华正新材料股份有限公司 | A kind of halogen-free resin composition and its low fluidity prepreg |
| CN110066494A (en) * | 2019-05-07 | 2019-07-30 | 金安国纪科技（杭州）有限公司 | Composition epoxy resin and its preparation method and application, aluminum-based copper-clad plate |
| CN111087759A (en) * | 2019-11-27 | 2020-05-01 | 广东盈骅新材料科技有限公司 | Resin composition and use thereof |
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| CN112662131A (en) | 2021-04-16 |
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