An unsaturated bond-containing halogen-free flame-retardant resin composition and its application

Abstract

The present invention relates to the technical field of electronic materials, and in particular to an unsaturated bond-containing halogen-free flame retardant resin composition and an application thereof. The resin composition comprises the following components, by weight: 5-50 parts of a thermosetting phosphorus-containing flame retardant compound, 5-100 parts of an unsaturated bond-containing resin, 0-50 parts of an epoxy resin, 0-40 parts of a curing agent, 0.01-10 parts of an initiator, 0-10 parts of a accelerator and 0-200 parts of an inorganic filler, and has the advantages of good flame retardancy, high glass transition temperature, lower dielectric constant and dielectric loss tangent value.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic materials, and particularly relates to a halogen-free flame-retardant resin composition containing unsaturated bonds and its application. Background Art

[0002] Copper clad laminate is the base material of electronic circuits and is the basic material for supporting electronic components and realizing circuit and information transmission. With the development of electronic products towards being light, thin and small, and the characteristics of large-capacity and low-latency information transmission, higher requirements are also put forward for the performance of copper clad laminate materials. This requires that the copper clad laminate materials have higher heat resistance, higher glass transition temperature, lower thermal expansion rate, lower dielectric constant and dielectric loss, etc.

[0003] Most of the resin materials in copper clad laminates are flammable materials and are prone to catching fire and then causing fires in the case of electrical short circuits. Therefore, flame retardants are usually introduced into the resin formula, such as halogen flame retardants, phosphorus-containing flame retardants, nitrogen-containing flame retardants, metal hydrates, etc.

[0004] Although halogen flame retardants show good flame retardant effects, the gases such as hydrogen halide released by them cause harm to the human body, and most halogen flame retardants are not friendly to the environment and have been gradually restricted from use.

[0005] Phosphorus-containing flame retardants also show good flame retardant effects, but common additive flame retardants often show problems such as poor compatibility, easy agglomeration, sedimentation, etc. Due to the large addition amount, it will also cause a decline in the mechanical properties, mechanical properties, etc. of the materials.

[0006] Although common phosphorus-containing epoxy resins and nitrogen-containing phenolic resins meet most of the requirements for halogen-free flame retardancy of FR-4 copper clad laminates, there are still some deficiencies. For example, to meet the UL94-V0 flame retardant requirement of the product, the proportion of phosphorus (phosphorus content 3±0.05%) must be guaranteed, and such products have defects such as large water absorption rate, poor heat resistance, easy moisture absorption and poor heat resistance during tin dipping. For common phosphorus-containing epoxy resin series, there are defects such as large water absorption rate, poor heat resistance, easy moisture absorption and poor heat resistance during tin dipping. Currently, the common method is to introduce benzoxazine resin. After the benzoxazine resin ring opens, it can generate a structure similar to phenolic resin, which can effectively reduce the water absorption rate of the cured system and improve chemical resistance, but the cured substrate has defects such as poor flexibility, high brittleness, insufficient heat resistance during tin dipping and poor processing performance. At the same time, due to the generation of hydroxyl groups after the ring opening of general structural benzoxazine resins, the tangent of the dielectric loss angle of the substrate is relatively large, and it is still difficult to meet the performance requirements of high-performance copper clad laminates.

[0007] Chinese Patent Application CN1484674A discloses a composition with a dihydrobenzoxazine resin as the main resin, epoxy compounds, phenols, compounds with a triazine ring, and aldehyde polymers as curing agents. The halogen-free substrate made therefrom has excellent properties in all aspects; Chinese Patent Application CN101643570A discloses a resin composition with a dihydrobenzoxazine resin as the main resin, epoxy compounds, phenolic aldehyde as the curing agent, and phenoxyphosphazene as the flame retardant. The composition has excellent properties in all aspects; Chinese Patent Application CN103013046A discloses a halogen-free flame-retardant resin composition with a dihydrobenzoxazine resin as the main resin. The substrate produced therefrom has excellent comprehensive properties.

[0008] However, in the above several solutions, bisphenol F is used as a raw material to synthesize dihydrobenzoxazine resin or commercially available bisphenol F benzoxazine resin is used. And when the content of bisphenol F type benzoxazine resin in the resin system exceeds 50% of the organic solids, the fluidity of the resin system decreases, thus seriously affecting the manufacturing processes of the substrate and the downstream PCB.

[0009] Chinese Patent Application CN1558920A discloses (1) an epoxy resin composition, including tetramethyl bisphenol F type epoxy resin, a curing agent, a filler, and a silane coupling agent including a silane coupling agent with a primary amino group; (2) an epoxy resin composition, including tetramethyl bisphenol F type epoxy resin, a curing agent including a specific phenol compound, and a filler; and (3) an epoxy resin composition, including tetramethyl bisphenol F type epoxy resin, a curing agent, and a specific filler. The said epoxy resin composition exhibits excellent reliability, such as peel resistance and anti-swelling property during reflow, and can be conveniently used for sealing circuit components. However, this invention cannot solve the problem of poor glue filling in the laminate, nor can it ensure achieving a low dielectric constant and dielectric loss.

[0010] The above technical solutions mainly focus on modifying the resin or optimizing the resin type. While reactive flame retardants participate in the reaction and bind chemical bonds in the polymer structure, thus not precipitating, and can achieve a long-lasting flame retardant effect. At the same time, selecting flame retardants with different structures can endow the curing system with different properties, such as improving heat resistance, etc.

[0011] Therefore, it is very necessary to develop an unsaturated bond-containing halogen-free flame-retardant resin composition that can solve the above technical problems. Summary of the Invention

[0012] The object of the present invention is to overcome the deficiencies of the prior art and provide a halogen-free flame retardant resin composition containing unsaturated bonds having good flame retardant properties, a high glass transition temperature, a relatively low dielectric constant and a dielectric loss tangent value. The present invention also provides a prepreg or a laminated board prepared using the resin composition. The present invention also provides the use of the resin composition, the prepreg or the laminated board in the preparation of a printed circuit board.

[0013] The present invention is achieved through the following technical solutions:

[0014] A halogen-free flame-retardant resin composition containing unsaturated bonds comprises the following components by weight: 5-50 parts of a thermosetting phosphorus-containing flame-retardant compound, 5-100 parts of an unsaturated bond-containing resin, 0-50 parts of an epoxy resin, 0-40 parts of a curing agent, 0.01-10 parts of an initiator, 0-10 parts of a accelerator and 0-200 parts of an inorganic filler.

[0015] Preferably, the inorganic filler is 30-80 parts.

[0016] More preferably, the resin composition comprises the following components by weight: 20-40 parts of thermosetting phosphorus-containing flame retardant compound, 60-100 parts of unsaturated bond-containing resin, 0-50 parts of epoxy resin, 0-40 parts of curing agent, 3-5 parts of initiator, 0.05-10 parts of accelerator and 30-80 parts of inorganic filler.

[0017] More preferably, the resin composition comprises the following components by weight: 20-40 parts of a thermosetting phosphorus-containing flame retardant compound, 60-100 parts of an unsaturated bond-containing resin, 0-20 parts of an epoxy resin, 0-20 parts of a curing agent, 3-5 parts of an initiator, 0-0.05 parts of an accelerator and 30-80 parts of an inorganic filler.

[0018] More preferably, the resin composition comprises the following components by weight: 20-40 parts of a thermosetting phosphorus-containing flame retardant compound, 60-100 parts of an unsaturated bond-containing resin, 0-10 parts of an epoxy resin, 0-10 parts of a curing agent, 3-5 parts of an initiator, 0-0.05 parts of an accelerator and 30-80 parts of an inorganic filler.

[0019] Preferably, the thermosetting phosphorus-containing flame retardant compound is selected from at least one of the compounds represented by formula (1) to formula (8). The specific compounds represented by formula (1) to formula (8) are as follows:

[0020]

[0021]

[0022] Preferably, the unsaturated bond-containing resin includes one or more of a double bond-modified polyphenylene ether resin, an allyl bisphenol A resin, a double bond-modified benzoxazine resin, a bismaleimide resin, triallyl isocyanurate, a styrene-butadiene copolymer, a styrene-butadiene-divinylbenzene copolymer, dicyclopentadiene, norbornene, and dicycloheptadiene.

[0023] Preferably, the epoxy resin includes one or more of a phenol novolac epoxy resin, a bisphenol A novolac epoxy resin, a DCPD epoxy resin, a biphenyl epoxy resin, a tetraphenylethane epoxy resin, a triphenylmethane epoxy resin, an alicyclic epoxy, an aliphatic epoxy, a hydantoin-based epoxy, and an epoxy soybean oil resin.

[0024] More preferably, the epoxy resin has an epoxy equivalent of 100-500 g / eq.

[0025] Preferably, the curing agent includes one or more of dicyandiamide, 4,4-diaminodiphenyl sulfone, a phenolic resin, a benzoxazine resin, a cyanate ester resin, an acid anhydride, and a styrene maleic anhydride copolymer.

[0026] Preferably, the initiator includes at least one of an azo initiator and a peroxide initiator.

[0027] More preferably, the initiator includes at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, dimethylbenzoyl peroxide, diisopropylbenzene peroxide, tert-butyl hydroperoxide, dilauroyl peroxide, and potassium persulfate.

[0028] Preferably, the accelerator includes one or more of imidazole, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and a substituted urea.

[0029] Preferably, the inorganic filler includes one or more of silica, aluminum hydroxide, magnesium hydroxide, alumina, titanium oxide, barium sulfate, aluminum borate, and calcium carbonate.

[0030] Preferably, the resin composition further contains an organic solvent.

[0031] More preferably, the organic solvent is selected from one or more of toluene, xylene, mesitylene, acetone, butanone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butanol, N,N'-dimethylformamide, N,N'-dimethylacetamide, ethyl acetate, and butyl acetate.

[0032] The present invention also relates to a prepreg mainly prepared from the above resin composition.

[0033] During the preparation of the prepreg, the resin composition is first formulated into a resin solution, and then impregnated on the reinforcing material and dried.

[0034] The resin solid content in the resin solution formulated from the resin composition can be appropriately adjusted according to the type and process of the reinforcing material impregnated with the solution. For example, the solid content of the resin solution is 40% to 80%, such as 40%, 45%, 50%, 52%, 55%, 58%, 60%, 63%, 65%, 70%, 75% or 80%. Preferably, it is 45% to 70%. The resin solution with the solid content in this range can improve the impregnation of the reinforcing material and obtain a prepreg with a highly uniform resin layer thickness.

[0035] Preferably, the prepreg includes a reinforcing material and the resin composition attached to the reinforcing material after impregnation and drying.

[0036] More preferably, the reinforcing material includes one of glass fiber cloth, wood pulp paper and cotton pulp paper.

[0037] The present invention also relates to a laminate comprising at least one prepreg as described above.

[0038] The present invention also relates to the use of the above-mentioned resin composition, or the above-mentioned prepreg, or the above-mentioned laminate in the preparation of printed circuit boards.

[0039] The beneficial effects of the present invention are:

[0040] By using a thermosetting phosphorus-containing flame retardant compound, the present invention solves the problems of poor compatibility and low glass transition temperature of additive flame retardants, and achieves high heat resistance. At the same time, by using free radical curing, the system has low polarity, and the copper clad laminate has low dielectric constant and dielectric loss, which can meet the requirements of high-frequency and high-speed fields, especially equipment such as 5G communication. Specific Embodiments

[0041] The present invention will be further described below in conjunction with specific embodiments, and the advantages and features of the present invention will become clearer as the description proceeds. However, these embodiments are exemplary only and do not constitute any limitation to the scope of the present invention. Those skilled in the art should understand that the details and forms of the technical solutions of the present invention can be modified or replaced without departing from the spirit and scope of the present invention, but these modifications and replacements all fall within the protection scope of the present invention.

[0042] In the following examples and comparative examples, the raw material source "Tongyu New Materials (Guangdong) Co., Ltd." is abbreviated as "Tongyu New Materials", "Sabic" is abbreviated as "Sabic", "Cray Valley" is abbreviated as "Cray Valley", "Hubei Jusheng Technology Co., Ltd." is abbreviated as "Hubei Jusheng", "Daiwa Kasei Co., Ltd. of Japan" is abbreviated as "Daiwa Kasei of Japan", "KAYAKU Co., Ltd. of Japan" is abbreviated as "KAYAKU of Japan", and "Daihachi Chemical Industry Co., Ltd. of Japan" is abbreviated as "Daihachi of Japan".

[0043] Example 1

[0044] Prepare a resin solution: By solid weight, take 20 parts of a phosphorus-containing flame retardant compound (structure of formula (1), Tongyu New Materials), 50 parts of a double-bond modified polyphenylene ether (SA9000, Sabic), 20 parts of a styrene-butadiene copolymer (Ricon100, Cray Valley), 10 parts of triallyl isocyanurate (Hubei Jusheng), 4 parts of dicumyl peroxide, and 80 parts of spherical silica, and dissolve them in a methyl ethyl ketone solvent. Under sufficient stirring, a resin solution with a solid content of 50% is prepared.

[0045] Impregnate a fiberglass cloth of model 2116 with the above resin solution and bake it at 150 °C for 3 minutes to make a prepreg. The resin content of the prepreg is 55 ± 5%.

[0046] Take 6 prepregs, stack them neatly, cover both sides with copper foil, place them between stainless steel plates, and then put them in a vacuum press. Heat press at 210 ± 3 °C and 35 kgf / cm 2 for 180 minutes to make a double-sided copper clad laminate.

[0047] Example 2

[0048] Prepare a resin solution: By solid weight, take 30 parts of a phosphorus-containing flame retardant compound (structure of formula (1), Tongyu New Materials), 60 parts of a double-bond modified polyphenylene ether (SA9000, Sabic), 15 parts of a bismaleimide resin (BMI5100, Daiwa Kasei of Japan), 10 parts of a styrene-butadiene copolymer (Ricon100, Cray Valley), 15 parts of triallyl isocyanurate (Hubei Jusheng), 2.5 parts of dicumyl peroxide, and 30 parts of spherical silica, and dissolve them in a methyl ethyl ketone solvent. Under sufficient stirring, a resin solution with a solid content of 50% is prepared.

[0049] Impregnate a fiberglass cloth of model 2116 with the above resin solution and bake it at 150 °C for 3 minutes to make a prepreg. The resin content of the prepreg is 55 ± 5%.

[0050] Take 6 prepregs, stack them neatly, cover both sides with copper foil, place them between stainless steel plates, and then put them in a vacuum press. At 210 ± 3 °C and 35 kgf / cm2 The double-sided copper clad laminate was produced by hot pressing for 180 minutes under the conditions.

[0051] Embodiment 3

[0052] Preparation of resin glue: Based on the solid weight, take 40 parts of phosphorus-containing flame retardant compound (structure of formula (1), Tongyu New Materials), 60 parts of double-bond modified polyphenylene ether (SA9000, Sabic), 20 parts of styrene-butadiene copolymer (Ricon100, Crayville), 5 parts of diisopropylbenzene peroxide, and 60 parts of spherical silica, dissolve them in butanone solvent, and prepare a resin solution with a solid content of 50% under sufficient stirring.

[0053] The resin solution was impregnated with 2116 fiberglass cloth and baked at 150°C for 3 minutes to form a prepreg. The prepreg had a glue content of 55±5%.

[0054] Take 6 prepregs, stack them neatly, cover both sides with copper foil, place them between stainless steel plates, and then put them in a vacuum press at 210±3℃ and 35kgf / cm 2 The double-sided copper clad laminate was produced by hot pressing for 180 minutes under the conditions.

[0055] Embodiment 4

[0056] Preparation of resin glue: by solid weight, take 20 parts of phosphorus-containing flame retardant compound (structure of formula (1), Tongyu New Materials), 40 parts of double bond modified benzoxazine resin (TBN8730K70, Tongyu New Materials), 20 parts of bismaleimide resin (BMI5100, Yamato Chemical), 10 parts of biphenyl epoxy resin (NC3000H, Nippon Kayaku), 10 parts of styrene-maleic anhydride copolymer (EF-30, Crayville), 4 parts of diisopropylbenzene peroxide, 0.05 parts of 2-methylimidazole, and 60 parts of spherical silica, dissolve them in butanone solvent, and prepare a resin solution with a solid content of 50% under sufficient stirring.

[0057] The resin solution was impregnated with a 2116 fiberglass cloth and baked at 170°C for 4 minutes to form a prepreg. The prepreg had a glue content of 55±5%.

[0058] Take 6 prepregs, stack them neatly, cover both sides with copper foil, place them between stainless steel plates, and then put them in a vacuum press at 220±3℃ and 35kgf / cm 2 The double-sided copper clad laminate was produced by hot pressing for 180 minutes under the conditions.

[0059] Embodiment 5

[0060] Compared with Example 1, 20 parts of the phosphorus-containing flame retardant compound (structure of formula (1), Tongyu New Materials) were replaced with 20 parts of the phosphorus-containing flame retardant compound (structure of formula (2), Tongyu New Materials), and other materials and conditions remained unchanged.

[0061] Example 6

[0062] Compared with Example 1, 20 parts of the phosphorus-containing flame retardant compound (structure of formula (1), Tongyu New Materials) were replaced with 20 parts of the phosphorus-containing flame retardant compound (structure of formula (3), Tongyu New Materials), and other materials and conditions remained unchanged.

[0063] Example 7

[0064] Compared with Example 1, 20 parts of the phosphorus-containing flame retardant compound (structure of formula (1), Tongyu New Materials) were replaced with 20 parts of the phosphorus-containing flame retardant compound (structure of formula (8), Tongyu New Materials), and other materials and conditions remained unchanged.

[0065] Example 8

[0066] Compared with Example 1, 10 parts of triallyl isocyanurate were replaced with 10 parts of dicyclopentadiene, and other materials and conditions remained unchanged.

[0067] Example 9

[0068] Compared with Example 1, 20 parts of the phosphorus-containing flame retardant compound (structure of formula (1), Tongyu New Materials) were replaced with 40 parts, and other materials and conditions remained unchanged.

[0069] Example 10

[0070] Compared with Example 1, 4 parts of dicumyl peroxide were changed to 3 parts of azobisisobutyronitrile formamide, and other materials and conditions remained unchanged.

[0071] Comparative Example 1

[0072] Compared with Example 1, 20 parts of the phosphorus-containing flame retardant compound (structure of formula (1), Tongyu New Materials) were replaced with 20 g of a phosphate ester flame retardant (PX200, Daihachi, Japan), and other materials and conditions remained unchanged.

[0073] Comparative Example 2

[0074] Compared with Example 2, 30 parts of the phosphorus-containing flame retardant compound (structure of formula (1), Tongyu New Materials) were removed, and other materials and conditions remained unchanged.

[0075] Comparative Example 3

[0076] Compared with Example 4, 20 parts of the phosphorus-containing flame retardant compound (structure of formula (1), Tongyu New Materials) were replaced with a phosphorus-containing modified epoxy resin (TER530K75, DOPO-modified PNE epoxy resin, phosphorus content 3.0%, Tongyu New Materials), and other materials and conditions remained unchanged.

[0077] The double-sided copper clad laminates prepared in each of the examples and comparative examples were subjected to performance tests, and the results are shown in Table 1.

[0078] Table 1

[0079]

[0080] The resin composition of the present invention exhibits a relatively high Tg and a relatively low coefficient of thermal expansion.

[0081] For the parameters involved in Table 1, the detection methods are as follows:

[0082] Glass transition temperature (Tg): Measured using DMA, in accordance with the DMA test method specified in IPC-TM-650 2.4.24.4.

[0083] Coefficient of thermal expansion CET was tested according to the standard of IPC-TM-650 2.4.41.

[0084] T288 was tested according to the standard of IPC-TM-650 2.4.24.1

[0085] Dielectric constant and dielectric loss factor: Tested according to the method of IPC-TM-650 2.5.5.9, and the test frequency was 5 GHz.

[0086] Flame retardancy: Determined according to the flammability test method specified in UL94.

[0087] The above detailed description is a specific description of one of the feasible embodiments of the present invention, and this embodiment is not intended to limit the patent scope of the present invention. Any equivalent implementation or modification without departing from the present invention should be included within the scope of the technical solution of the present invention.

Claims

1. A halogen-free flame-retardant resin composition containing unsaturated bonds, characterized in that, By weight parts, it comprises the following components: 5-50 parts of a thermosetting phosphorus-containing flame retardant compound, 5-100 parts of an unsaturated bond-containing resin, 0-50 parts of an epoxy resin, 0-40 parts of a curing agent, 0.01-10 parts of an initiator, 0-10 parts of an accelerator, and 0-200 parts of an inorganic filler; The thermosetting phosphorus-containing flame retardant compound is selected from at least one of the compounds shown in Formula (1) to Formula (8), and the compounds shown in Formula (1) to Formula (8) are specifically as follows:

2. The halogen-free flame retardant resin composition containing unsaturated bonds according to claim 1, wherein By weight parts, it comprises the following components: 20-40 parts of a thermosetting phosphorus-containing flame retardant compound, 60-100 parts of an unsaturated bond-containing resin, 0-10 parts of an epoxy resin, 0-10 parts of a curing agent, 3-5 parts of an initiator, 0-0.05 parts of an accelerator, and 30-80 parts of an inorganic filler.

3. The resin composition according to claim 1, characterized in that, The unsaturated bond-containing resin includes one or more of a double bond-modified polyphenylene ether resin, an allyl bisphenol A resin, a double bond-modified benzoxazine resin, a bismaleimide resin, triallyl isocyanurate, a styrene-butadiene copolymer, a styrene-butadiene-divinylbenzene copolymer, dicyclopentadiene, norbornene, and dicycloheptadiene.

4. The resin composition according to claim 1, characterized in that, The epoxy resin includes one or more of a phenol novolac epoxy resin, a bisphenol A novolac epoxy resin, a DCPD epoxy resin, a biphenyl epoxy resin, a tetraphenylethane epoxy resin, a triphenymethane epoxy resin, an alicyclic epoxy, an aliphatic epoxy, a hydantoin-based epoxy, and an epoxy soybean oil resin.

5. The resin composition according to claim 4, characterized in that, The epoxy equivalent of the epoxy resin is 100-500 g / eq.

6. The resin composition according to claim 1, wherein The curing agent includes one or more of dicyandiamide, 4,4-diaminodiphenyl sulfone, a phenolic resin, a benzoxazine resin, a cyanate ester resin, an acid anhydride, and a styrene maleic anhydride copolymer.

7. The resin composition according to claim 1, wherein The initiator includes at least one of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, dimethylbenzoyl peroxide, diisopropylbenzene peroxide, tert-butyl hydroperoxide, dilauroyl peroxide, and potassium persulfate.

8. The resin composition according to claim 1, wherein The accelerator includes one or more of imidazole, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, dicyclic amidine, and substituted urea.

9. The resin composition according to claim 1, characterized in that, The inorganic filler includes one or more of silica, aluminum hydroxide, magnesium hydroxide, alumina, titanium oxide, barium sulfate, aluminum borate, and calcium carbonate.

10. The resin composition according to claim 1, characterized in that, The resin composition further contains an organic solvent, and the organic solvent is selected from one or more of toluene, xylene, mesitylene, acetone, butanone, methyl isobutyl ketone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, butanol, N,N'-dimethylformamide, N,N'-dimethylacetamide, ethyl acetate, and butyl acetate.

11. A prepreg, characterized in that, It is mainly prepared from the resin composition according to any one of claims 1-10.

12. The prepreg according to claim 11, wherein, The prepreg includes a reinforcing material and the resin composition attached to the reinforcing material after impregnation and drying.

13. A laminate, characterized in that, It includes the prepreg according to any one of claims 11-12.

14. Use of the resin composition according to any one of claims 1-10, or the prepreg according to any one of claims 11-12, or the laminate according to claim 13 in the preparation of a printed circuit board.

Images