Patent Grant
10544255
This application is a U.S. national stage filing, under 35 U.S.C. § 371(c), of International Application No. PCT/CN2016/077730, filed on Mar. 29, 2016, which claims priority to Chinese Patent Application No. 201511019388.0, filed on Dec. 28, 2015. The entire contents of each of the aforementioned applications are incorporated herein by reference.
The present invention belongs to the technical field of the copper-clad laminate, specifically relates to an epoxy resin composition, prepreg, laminate and printed circuit board prepared therefrom.
Along with the development of information communication equipments in the direction of high performance, high functionalization and networking, the operation signals tend to high frequency in recent years for high-speed transmission and processing of large-capacity information. Meanwhile, circuit boards are developed in the direction of high multilayer and high wiring density in order to meet the requirements on the development trends of various electronic products, which requires that the substrate materials have not only a relatively low and stable dielectric constant and dielectric loss factor to meet the requirements on high frequency transmission of signals, but also better heat resistance to meet the requirements on reliability of multilayer printed circuit boards.
CN101815734A disclosed a process for synthesizing isocyanate-modified epoxy by reacting multifunctional epoxy resin with diisocyanate compound, wherein such resin had a high softening point required by powder coatings. CN102666633A disclosed an epoxy oxazolidinone resin composition comprising divinylarene dioxide and reaction products of excessive polyisocyanate, and a curable epoxy resin composition, comprising the epoxy oxazolidinone resin composition of divinylarene dioxide derived from divinylbenzene dioxide, and polyisocyanate, at least a curing agent, and/or a catalyst. The composition had the features of low viscosity and high heat resistance.
CN1333791A disclosed a binder composition prepared from polyepoxide, polycyanate and chain extender, wherein such composition was advantageous to enhance the adhesiveness between copper foil and laminate.
CN101695880A disclosed a process for preparing polyoxazolidinone laminates, comprising reacting diisocynate with epoxy in the presence of imidazole catalyst to produce polyoxazolidinone, then preparing laminates by using the resultant polyoxazolidinone, wherein the prepared laminates had better mechanical strength and heat resistance.
JP2003-252958 disclosed obtaining cured products having a reduced dielectric loss factor by using biphenyl epoxy resin and active ester curing agent. Since the epoxy resin used therein was bifunctional, it had a low crosslinking density with active ester curing agent, and the condensate thereof had a low glass transition temperature.
Although the aforesaid patents disclosed that isocyanate-modified epoxy or polyoxazolidinone itself and the composition thereof had better adhesiveness, heat resistance and tenacity, but they had the defects such as worse moisture and heat resistance, lower reliability, and relatively higher dielectric loss factor, so as to limit the application in high-speed materials.
As for the problems in the prior art, the object of the present invention lies in providing an epoxy resin composition, as well as a prepreg and laminate prepared therefrom. The laminate prepared from such resin composition has a low dielectric loss factor, a low water absorption, excellent moisture and heat resistance and meets the performance requirements for printed circuit boards in the high-frequency high-speed era.
The inventor of the present invention found, by research, that the composition obtained by appropriately mixing an epoxy resin containing oxazolidinone structure, an active ester curing agent, and a curing accelerator, and other optional components can achieve the aforesaid object.
An epoxy resin composition comprises the following components:
(A) an epoxy resin containing oxazolidinone structure having the structure of the formula (1)
wherein m and n are each independently selected from the group consisting of 0, 1 and 2;
X is anyone independently selected from the group consisting of
R and R′ each is independently selected from any organic group;
(B) an active ester curing agent; and
(C) a curing accelerator
The epoxy resin containing oxazolidinone structure in the present invention comprises 5-membered heterocyclic oxazolidinone structure of C, N and O in the main chain. The molecular chain thereof has a great rigidity, a low coefficient of thermal expansion, but a high water absorption. While reducing the formation of secondary hydroxyl group and the water absorption thereof, the introduction of active ester will ensure the composition play its feature of lower dielectric loss factor of the oxazolidinone structure during the curing process. By the synergistic effect of the epoxy resin containing oxazolidinone structure and active ester, the epoxy resin composition provided by the present invention ensures the epoxy resin composition have a lower water absorption and a lower dielectric loss factor compared to the composition containing isocyanate or active ester alone, which ensure that the composition has a higher reliability.
By using the interaction and mutual synergistic effects of the aforesaid three necessary components, the present invention obtains the aforesaid epoxy resin composition. The prepreg and laminate prepared by using such epoxy resin composition have a low coefficient of thermal expansion of thermal expansion, a low dielectric loss factor, a low water absorption and excellent moisture and heat resistance.
Preferably, m=0, and n=0 in the structure of formula (1); the component (A) epoxy resin containing oxazolidinone structure has the structure of formula (2)
In the formula (2), R and R′ have the same scope as those in claim 1.
Preferably, R and R′ in the formulae (1) and (2) each are anyone independently selected from the group consisting of the following structures:
Preferably, R and R′ are the same.
Preferably, the component (A) epoxy resin containing oxazolidinone structure is an epoxy resin containing oxazolidinone structure and having bisphenol-A and/or tetrabromobisphenol-A structure.
Preferably, the component (A) epoxy resin containing oxazolidinone structure and the component (B) active ester curing agent have an epoxide equivalent/ester group equivalent ratio of 1:0.9-1.1, e.g. 1:0.92, 1:0.94, 1:0.96, 1:0.98, 1:1, 1:1.02, 1:1.04, 1:1.06 or 1:1.08.
Preferably, the component (B) active ester curing agent is obtained by reacting a phenolic compound linked via aliphatic cyclic hydrocarbon structure, a difunctional carboxylic aromatic compound or an acidic halide with a monohydroxy compound. Said difunctional carboxylic aromatic compound or acidic halide is in an amount of 1 mol; the phenolic compound linked via aliphatic cyclic hydrocarbon structure is in an amount of 0.05-0.75 mol; the monohydroxy compound is in an amount of 0.25-0.95 mol.
Preferably, the component (B) active ester curing agent comprises an active ester having the structure of formula (3):
wherein Y is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents that the repeating unit is 0.25-1.25.
Due to the special structure of the active ester curing agent, the rigid structures therein, such as phenyl, naphthyl, cyclopentadiene and the like, endow a high thermal resistance to the active ester. Meanwhile, the structural regularity thereof and no production of secondary hydroxyl group during the reaction with the epoxy resin endow with better electrical property and lower water absorption.
Preferably, the component (C) curing accelerator of the present invention is selected from the group consisting of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methyl-imidazole or 2-phenylimidazole, or a mixture of at least two selected therefrom.
The exemplary mixtures of the component (C) curing accelerator of the present invention may be a mixture of 4-dimethylaminopyridine and 2-methylimidazole, a mixture of 2-methylimidazole and 2-ethyl-4-methylimidazole or 2-phenylimidazole, or a mixture of 4-dimethylaminopyridine, 2-methylimidazole and 2-phenylimidazole.
Preferably, based on the sum of the addition amounts of the components (A) epoxy resin containing oxazolidinone structure and (B) active ester curing agent being 100 parts by weight, the component (C) curing accelerator is added in an amount of from 0.05 to 1 part by weight, e.g. 0.08 parts by weight, 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.5 parts by weight, 0.55 parts by weight, 0.60 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight, or 0.95 parts by weight, preferably from 0.5 to 0.8 parts by weight.
Preferably, the epoxy resin composition of the present invention further comprises a cyanate ester resin.
Cyanate ester resin can better increase the glass transition temperature and decrease the coefficient of thermal expansion of the composition.
Preferably, based on the sum of the addition amounts of the components (A) epoxy resin containing oxazolidinone structure, (B) active ester curing agent and (C) curing accelerator being 100 parts by weight, the cyanate ester resin is added in an amount of 50 parts by weight or less, e.g. 12 parts by weight, 15 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 38 parts by weight, 43 parts by weight, 48 parts by weight, preferably 40 parts by weight or less, further preferably from 20 to 30 parts by weight.
The epoxy resin composition further comprises a flame retardant.
Preferably, the flame retardant is a bromine-containing flame retardant or/and halogen-free flame retardant.
Preferably, the flame retardant is added in an amount of from 5 to 50 parts by weight, based on the sum of the addition amounts of the components (A) epoxy resin containing oxazolidinone structure, (B) active ester curing agent and (C) curing accelerator being 100 parts by weight, e.g. 5 parts by weight, 10 parts by weight, 15 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or 45 parts by weight.
Preferably, the bromine-containing flame retardant is anyone selected from the group consisting of decabromodiphenyl ethane, brominated polystyrene, ethylene bis-tetrabromo phthalimide or bromine-containing epoxy resin, or a mixture of at least two selected therefrom.
Preferably, the halogen-free flame retardant is anyone selected from the group consisting of
tri(2,6-dimethylphenyl)phosphine,
10-(2,5-dihydroxylphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
2,6-di(2,6-dimethylphenyl)-phosphinophenyl;
10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenoxy-phosphazene compound, zinc borate, nitrogen and phosphorus-based intumescent, organic polymer flame retardant, and copolymers of phosphorus-containing phenolic resin or phosphorus-containing bismaleimide, polyphosphonate, phosphonate and carbonate, or a mixture of at least two selected therefrom.
Preferably, the epoxy resin composition further comprises a filler which is an organic filler or/and an inorganic filler, if necessary, for adjusting some physical properties of the composition, e.g. reducing coefficient of thermal expansion (CTE) and water absorption and increasing thermal conductivity.
Preferably, based on the sum of the addition amounts of the components (A) epoxy resin containing oxazolidinone structure, (B) active ester curing agent, and (C) curing accelerator being 100 parts by weight, the filler is added in an amount of 100 parts by weight or less, preferably 50 parts by weight or less, e.g. 0.5 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 or 95 parts by weight, further preferably from 20 to 40 parts by weight.
Preferably, the inorganic filler is anyone selected from the group consisting of molten silica, crystal silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica or glass fiber powder, or a mixture of at least two selected therefrom. The mixture is selected from the group consisting of, e.g. a mixture of molten silica and crystal silica, a mixture of spherical silica and hollow silica, a mixture of aluminum hydroxide and alumina, a mixture of talc and aluminum nitride, a mixture of boron nitride and silicon carbide, a mixture of barium sulfate and barium titanate, a mixture of strontium titanate and calcium carbonate, a mixture of calcium silicate, mica and glass fiber powder, a mixture of molten silica, crystal silica and spherical silica, a mixture of hollow silica, aluminum hydroxide and alumina, a mixture of talc, aluminum nitride and boron nitride, a mixture of silicon carbide, barium sulfate and barium titanate, a mixture of strontium titanate, calcium carbonate, calcium silicate, mica and glass fiber powder.
Preferably, the organic filler is anyone selected from the group consisting of polytetrafluoroethylene powder, polyphenylene sulfide or polyether sulfone, or a mixture of at least two selected therefrom. The mixture is selected from the group consisting of, e.g. a mixture of polytetrafluoroethylene powder and polyphenylene sulfide, a mixture of polyether sulfone and polytetrafluoroethylene powder, a mixture of polyphenylene sulfide and polyether sulfone, a mixture of polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone.
Preferably, the filler is silica; the medium value of the particle size of the filler is from 1 to 15 μm, preferably from 1 to 10 μm.
The wording “comprise(s)/comprising” in the present invention means that there may comprise other components besides said components, which endow different properties to the epoxy resin composition. Besides, the wording “comprise(s)/comprising” in the present invention may be replaced with “is/are” or “consist(s)/consisting of”.
For example, the epoxy resin composition may further comprise various additives, e.g. antioxidant, thermal stabilizer, antistatic agent, ultraviolet light absorber, pigment, colorant, lubricant and the like. These various additives may be used alone, or in combination.
The conventional method for preparing the resin composition of the present invention comprises: taking a container, first putting in solid components, then adding liquid solvent, stirring till complete dissolution, adding liquid resin, filler, flame retardant, curing accelerator, continuing to homogeneously stirring, and finally adjusting with the solvent till the solid content of the liquid to be 60-80% to prepare a glue solution.
The second object of the present invention lies in providing a prepreg comprising a reinforcing material and the above epoxy resin composition attached thereon after impregnation and drying.
The exemplary reinforcing material is selected from non-woven fabrics or/and other fabrics, e.g. natural fibers, organic synthetic fibers and inorganic fibers.
The glue solution is used to impregnate the reinforcing material, e.g. fabrics such as glass cloth, or organic fabrics, and the impregnated reinforcing material is heated and dried in an oven at a temperature of 155° C. for 5-10 min to obtain a prepreg.
The third object of the present invention lies in providing a laminate comprising at least one sheet of the aforesaid prepreg.
The fourth object of the present invention lies in providing a printed circuit board which can reduce the Df value and water absorption, wherein the printed circuit board comprises at least one sheet of the laminate above.
As compared to the prior art, the present invention has the following beneficial effects.
The technical solution of the present invention is further explained by the following embodiments.
Those skilled in the art should know that the examples are only for understanding the present invention, and shall not be deemed as specific limits to the present invention.
An epoxy resin composition metal-clad laminate prepared thereby was tested for the glass transition temperature, thermal decomposition temperature, coefficient of thermal expansion, dielectric constant, dielectric loss factor, PCT and PCT water absorption, which were stated and described in detail in the following examples, wherein the mass part of organic resins is based on the mass part of the organic solid matter.
Epoxy resins having different structures according to claim 1 were synthesized by the method of preparing the epoxy resin containing oxazolidinone structure by conventionally reacting epoxy resins with polyisocyanate disclosed in U.S. Pat. No. 5,112,932.
Synthesis of epoxy resins containing bisphenol-A structure and diphenylmethane structure, having the following structure
wherein
R and R′ both are
Into a three-necked flask (1000 mL) equipped with a stirrer, a thermometer and a reflux condenser was added 400 g of bisphenol-A epoxy resin, which was heated to 145-150° C. under the protection of nitrogen gas. 2-phenylimidazole (0.175 g) was added and then heated to 160° C. At 160° C., 100 g of diphenylmethanediisocyanate (MDI) was dropwise added to the aforesaid mixed solution within 30 min. After MDI was added, thermostatic reaction was carried out at 160° C. under the protection of nitrogen gas, and stopped after 15 min. The reacted solution was slowly added into stirred distilled water, to separate out the polymer, filtrated, water-washed, dried, impregnated with methanol for 24 h, vacuum-dried to obtain the product.
Synthesis of epoxy resins containing tetrabromo-bisphenol-A structure and diphenylmethane structure, having the following structure
wherein
Into a three-necked flask (1000 mL) equipped with a stirrer, a thermometer and a reflux condenser was added 245 g of bisphenol-A epoxy resin and 185 g of tetrabromo-bisphenol-A epoxy resin, which was heated to 145-150° C. under the protection of nitrogen gas. 0.2 g of 2-phenylimidazole was added and then heated to 160° C. At 160° C., 90 g of diphenyl-methane-diisocyanate (MDI) was dropwise added to the aforesaid mixed solution within 30 min. After MDI was added, thermostatic reaction was carried out at 160° C. under the protection of nitrogen gas, and stopped after 15 min. The reacted solution was slowly added into stirred distilled water, to separate out the polymer, filtrated, water-washed, dried, impregnated with methanol for 24 h, vacuum-dried to obtain the product.
Synthesis of epoxy resins containing bisphenol-A structure and 2,4-toluene structure, having the following structure
wherein
R and R′ both are
Into a three-necked flask (1000 mL) equipped with a stirrer, a thermometer and a reflux condenser was added 400 g of bisphenol-A epoxy resin, which was heated to 135-140° C. under the protection of nitrogen gas. 0.175 g of 2-phenylimidazole was added and then heated to 160° C. At 160° C., 100 g of toluene-2,4-diisocyanate (TDI) was dropwise added to the aforesaid mixed solution within 30 min. After TDI was added, thermostatic reaction was carried out at 160° C. under the protection of nitrogen gas, and stopped after 15 min. The reacted solution was slowly added into stirred distilled water, to separate out the polymer, filtrated, water-washed, dried, impregnated with methanol for 24 h, vacuum-dried to obtain the product.
Synthesis of epoxy resins containing tetrabromo-bisphenol-A structure and 2,4-toluene structure, having the following structure
wherein
Into a three-necked flask (1000 mL) equipped with a stirrer, a thermometer and a reflux condenser was added 245 g of bisphenol-A epoxy resin and 185 g of tetrabromo-bisphenol-A epoxy resin, which was heated to 135-140° C. under the protection of nitrogen gas. 0.2 g of 2-phenylimidazole was added and then heated to 160° C. At 160° C., 90 g of toluene-2,4-diisocyanate (TDI) was dropwise added to the aforesaid mixed solution within 30 min. After TDI was added, thermostatic reaction was carried out at 160° C. under the protection of nitrogen gas, and stopped after 15 min. The reacted solution was slowly added into stirred distilled water, to separate out the polymer, filtrated, water-washed, dried, impregnated with methanol for 24 h, vacuum-dried to obtain the product.
Into a container was added 60 parts by weight of the product in Synthesis Example 1. A suitable amount of MEK was added and stirred till complete dissolution. Then an active ester and a curing accelerator DMAP dissolved in advance were added and homogeneously stirred. Finally a solvent was used to adjust the solid content of the liquid to 60-80% so as to obtain a glue solution. A glass fiber cloth was impregnated with the aforesaid glue solution, and to control the thickness thereof, and then dried to remove the solvent to obtain a prepreg. Several prepregs were overlapped with each other, coated with one sheet of RTF copper foil on each side thereof, placed into a thermocompressor and cured to obtain said epoxy resin copper-clad laminate. The formulation and physical properties thereof are shown in Table 1.
Into a container was added 65 parts by weight of the product in Synthesis Example 1. A suitable amount of MEK was added and stirred till complete dissolution. Then an active ester and a curing accelerator DMAP dissolved in advance were added and homogeneously stirred. Cyanate and zinc isoocatanoate dissolved in advance were added. Finally a solvent was used to adjust the solid content of the liquid to 60-80% so as to obtain a glue solution. A glass fiber cloth was impregnated with the aforesaid glue solution, and to control the thickness thereof, and then dried to remove the solvent to obtain a prepreg. Several prepregs were overlapped with each other, coated with one sheet of RTF copper foil on each side thereof, placed into a thermocompressor and cured to obtain said epoxy resin copper-clad laminate. The formulation and physical properties thereof are shown in Table 1.
The preparation process was the same as Example 2. The formulation and physical properties thereof are shown in Table 1.
The preparation processes were the same as Example 1. The formulations and physical properties thereof are shown in Table 1.
Into a container was added 60 parts by weight of the product in Synthesis Example 1. A suitable amount of MEK was added and stirred till complete dissolution. Then an active ester and a curing accelerator DMAP dissolved in advance were added, and a suitable proportion of fillers were added and homogeneously stirred. Finally a solvent was used to adjust the solid content of the liquid to 60-80% so as to obtain a glue solution. A glass fiber cloth was impregnated with the aforesaid glue solution, and to control the thickness thereof, and then dried to remove the solvent to obtain a prepreg. Several prepregs were overlapped with each other, coated with one sheet of RTF copper foil on each side thereof, placed into a thermocompressor and cured to obtain said epoxy resin copper-clad laminate. The formulation and physical properties thereof are shown in Table 1.
The preparation process was the same as Example 9. The formulation and physical properties thereof are shown in Table 1.
Into a container was added 65 parts by weight of the product in Synthesis Example 1. A suitable amount of MEK was added and stirred till complete dissolution. Then an active ester and a curing accelerator DMAP dissolved in advance were added and homogeneously stirred. Cyanate and zinc isoocatanoate dissolved in advance were added, and a suitable proportion of fillers were added and homogeneously stirred. Finally a solvent was used to adjust the solid content of the liquid to 60-80% so as to obtain a glue solution. A glass fiber cloth was impregnated with the aforesaid glue solution, and to control the thickness thereof, and then dried to remove the solvent to obtain a prepreg. Several prepregs were overlapped with each other, coated with one sheet of RTF copper foil on each side thereof, placed into a thermocompressor and cured to obtain said epoxy resin copper-clad laminate. The formulation and physical properties thereof are shown in Table 1.
The preparation processes were the same as Example 11. The formulations and physical properties thereof are shown in Table 1.
The preparation processes were the same as Example 1. The formulations and physical properties thereof are shown in Table 2.
The preparation processes were the same as Example 2. The formulations and physical properties thereof are shown in Table 2.
The formulations and performance test results in Examples 1-8 are shown in Table 1; the formulations and performance test results in Examples 9-14 are shown in Table 2; the formulations and performance test results in Example 1 and Comparison Examples are shown in Table 3. Table 2
In Tables 1, 2 and 3, when the main resin components in the formulations are bi-component, the curing agent ratio is represented by the equivalent ratio of the epoxy resins. When the main resin components in the formulations are multi-component (beyond bi-component), the curing agent ratio is represented by the solid weight ratio of the epoxy components.
The materials in Tables 1 and 2 are listed as follows.
Epoxy resin 1: biphenyl novolac epoxy resin NC-3000H (Trade name from Nippon Kayaku).
Epoxy resin 2: dicyclopentadiene novolac epoxy resin HP-7200HHH (Trade name from DIC Japan)
Phenolic resin 1: novolac curing agent KPH-2002 (Trade name from KOLON)
Active ester: active ester crosslinking agent HPC-8000-65T (Trade name from DIC Japan)
Cyanate: biphenol A-cyanate resin CEO1PS (Trade name from Yangzhou Apocalypse)
DMAP: Curing accelerator, 4-dimethylaminopyridine (Trade name from Guangrong Chemical Company)
Zinc isoocatanoate: curing accelerator (Trade name from Alfa Aesar)
The aforesaid properties are tested by the following methods:
Physical Property Analyses
As stated above, the present invention has low coefficient of thermal expansion, low dielectric loss factor, low water absorption and excellent moisture and heat resistance as compared to general laminates.
The aforesaid examples are merely preferred examples. According to the technical solution and technical concept of the present invention, those ordinarily skilled in the art can make various changes and deformation, which all belong to the scope of the claims of the present invention.
The applicant declares that, the present invention detailedly discloses the process of the present invention by the aforesaid examples, but the present invention is not limited by the detailed process, i.e. it does not mean that the present invention cannot be fulfilled unless the aforesaid detailed process is used. Those skilled in the art shall know that, any amendment, equivalent change to the product materials of the present invention, addition of auxiliary ingredients, and selection of any specific modes all fall within the protection scope and disclosure scope of the present invention.
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