CN102206397B - Resin composition and prepreg, laminate and circuit board containing same - Google Patents

Abstract

The present invention relates to a resin composition, which mainly comprises an epoxy resin, a hardening accelerator, a crosslinking agent and a phosphorus-containing resin, wherein the phosphorus-containing resin is a bisphenol-formaldehyde resin substituted by 9,10-dihydro-9-oxa-10-phosphophananthrene-10-oxide or a derivative thereof, and the resin composition can be applied to a semi-cured film or a circuit substrate insulating layer. In addition, the present invention also relates to a semi-cured film, a laminate and a circuit board containing the resin composition.

Description

Resin composition and prepreg, laminate and circuit board containing same

technical field

The present invention relates to a kind of resin composition, especially a kind of thermosetting resin composition that can be applied to semi-cured film (prepreg) or circuit substrate insulating layer, and it mainly comprises epoxy resin, hardening accelerator, crosslinking agent and by Phosphorous resin.

Background technique

DOPO is a commonly used additive in the resin composition, and its main purpose is to improve the flame retardancy of the resin composition, so that the resin composition can still maintain stability when it is applied in a high temperature environment.

However, due to the poor reactivity of DOPO with epoxy resins and cross-linking agents, the flame retardancy it can achieve is still unsatisfactory. Therefore, it has been proposed in the prior art to bond 1,4-bishydroxyphenol to DOPO , to form DOPO-HQ (HQ stands for hydroquinone, that is, hydroquinone), and improve its reactivity through the introduction of hydroxyl groups.

Taiwan Patent Publication No. I239973 discloses a flame retardant resin composition modified by phosphorus and polysilane, which is obtained by reacting DOPO-HQ modified epoxy resin with polysilane.

Taiwan Patent Announcement No. I299352 discloses an adhesive containing a halogen-free epoxy resin substituted by DOPO, which has high flexibility, moisture resistance and flame retardancy, and has good adhesion to metal and plastic substrates. Then intensity.

In addition, Taiwan Patent Publication No. 593526 discloses a phosphorus-containing compound, which has a DOPO or DOPO-HQ substituent, and can be used to form a flame-retardant epoxy resin cured product for packaging materials and printed circuit boards.

Contents of the invention

The main object of the present invention is to provide a kind of resin composition, and it mainly comprises epoxy resin, hardening accelerator, crosslinking agent and phosphorus-containing resin, and phosphorus-containing resin is bisphenol novolac substituted by DOPO or its derivatives (bisphenol novolac, BPN) resin or phenolic (phenol novolac, PN) resin. In terms of its characteristics, the resin composition provided by the present invention generally has characteristics such as high glass transition temperature (Tg), high heat resistance, flame retardancy, and high storage life, and can be applied to prepregs, metal foil layers, etc. Plywood and circuit boards, etc.

In the resin composition of the present invention, the phosphorus-containing resin preferably has a structure of formula (I), formula (II) or formula (III):

Formula (I)

Formula (II)

式(III)

Formula (III)

Among them, both Ph ₁ and Ph ₂ are phenyl groups, and the hydroxyl group (-OH) on them is connected in a para position relative to W, at least one of Ph ₁ and Ph ₂ includes more than one X, and Ph ₁ and Ph ₂ Each independently and selectively includes more than one Z; X is 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide or its derivatives; Y is selected from covalent bonds, aliphatic functional and aromatic functional groups; Z is selected from hydrogen, aliphatic functional groups and aromatic functional groups; W is selected from the following groups:

; n is an integer greater than or equal to 1.

In particular, the phosphorus-containing resin is preferably a resin containing DOPO functional groups, such as DOPO-PN (formula 1) or DOPO-BPN, and wherein DOPO-BPN can be DOPO-BPAN (DOPO-bisphenol Anovolac, formula 2,3) , DOPO-BPFN (DOPO-bisphenol F novolac, formula 4, 5), DOPO-BPSN (DOPO-bisphenol S novolac, formula 6, 7) and other bisphenol novolac compounds, respectively as shown in the following formula:

式(1)

Formula 1)

式(2)

Formula (2)

式(3)

Formula (3)

式(4)

Formula (4)

式(5)

Formula (5)

式(6)

Formula (6)

式(7)

Formula (7)

Wherein, n is an integer greater than or equal to 1; X is a DOPO functional group; Y is a covalent bond, an aliphatic functional group or an aromatic functional group; Z is hydrogen, an aliphatic functional group or an aromatic functional group. In addition, X and Z can be linked to any substituent position on the benzene ring structure, and each benzene ring is not limited to only one X or Z substituent; for example, there can be two or more X on the benzene ring structure Substituents, or two or more Z substituents. In addition, not every benzene ring structure needs to have X and Z substituents, and some benzene ring structures may have X and Z substituents respectively or both X and Z substituents, while some benzene ring structures do not have X and Z substituents.

Take DOPO-BPAN resin as an example, where the DOPO functional group is bonded to the BPAN resin with long chains and provides flame retardancy, while the hydroxyl groups on the BPAN resin provide cross-linkability with other resins (such as epoxy resin). In addition to the long-chain structure of BPAN can provide multiple hydroxyl groups to cross-link with other resins, the DOPO functional groups attached to BPAN can be more evenly distributed on the resin structure.

In addition, the preparation of the aforementioned various DOPO derivatives can be obtained by substituting DOPO with bisphenol novolac resin or phenolic resin, and then making the phosphorus atom of DOPO bond with the carbon atom on the benzene ring.

In the present invention, phosphorus-containing resins have better flame retardancy than other types of phosphate compounds, and they have better cross-linking properties than DOPO compounds or DOPO-HQ resins, which can improve cross-linking properties. Density, reactivity and glass transition temperature, thereby forming a high Tg material and improving the heat resistance stability of the resin composition.

In the resin composition of the present invention, the epoxy resin preferably includes at least one bisphenol A (bisphenol A) epoxy resin, bisphenol F (bisphenol F) epoxy resin, bisphenol S (bisphenol S) epoxy resin, Phenol novolac epoxy resin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin ) epoxy resin, multifunctional epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus epoxy resin, p-xylene epoxy resin ), naphthalene epoxy resin, benzopyran epoxy resin, biphenyl novolac epoxy resin, phenol aralkyl novolac epoxy resin, or combination. In addition, the epoxy resin is preferably selected from trifunctional epoxy resins, tetrafunctional epoxy resins and multifunctional epoxy resins, which can effectively improve the crosslinkability of each resin in the resin composition, and can further improve the resin composition. Excellent heat resistance and mechanical strength after curing.

In the resin composition of the present invention, the hardening accelerator is preferably selected from imidazole (imidazole), boron trifluoride amine complex, ethyltriphenyl phosphonium chloride (ethyltriphenyl phosphonium chloride), 2-methylimidazole (2 -methylimidazole, 2MI), 2-phenylimidazole (2-phenyl-1H-imidazole, 2PZ), 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole, 2E4MZ), triphenylphosphine ( triphenylphosphine, TPP), 4-dimethylaminopyridine (4-dimethylaminopyridine, DMAP) and other one or more Lewis bases, or metal salt compounds selected from manganese, iron, cobalt, nickel, copper and zinc, etc. One or more Lewis acids.

In the resin composition of the present invention, the cross-linking agent preferably includes diaminodiphenyl sulfone (diaminodiphenyl sulfone, DDS), which has characteristics such as high glass transition temperature, high heat resistance and long storage life, and can effectively improve and The cross-linking and curing effect of epoxy resin; in addition, the resin composition can further comprise at least one cross-linking agent selected from the following group, its modification or its combination: cyanate resin, phenol resin, phenolic resin ( phenol novolac resin), styrene resin, polybutadiene resin, polyphenyl ether resin, anhydride compound, amino compound and benzoxazine resin.

Among them, the cyanate resin includes resins such as cyanate and isocyanate. The phenolic resin may be a hydroxyl-containing resin such as dicyclopentadiene (DCPD) type phenolic resin. The amine-based crosslinking agent can be amide, dicyandiamide (DICY), diamino diphenylmethane (DDM), bismaleimide (bismaleimide, BMI) and other compounds. The acid anhydride compound can be methyl tetrahydrophthalic anhydride (MTHPA), phthalic anhydride (PA), methyl dicycloheptenedicarboxylic anhydride (nadic methyl anhydride, NMA), styrene maleic acid Acid anhydride (styrene maleic anhydride, SMA) and other compounds.

In order to further improve the flame retardant properties of the resin composition, in a preferred situation, at least one specific flame retardant compound can be optionally added in the present invention. The selected flame retardant compound may be a flame retardant salt, such as a phosphate compound or a nitrogen-containing phosphate compound, but not limited thereto. More specifically, the flame retardant compound preferably includes at least one of the following compounds: bisphenol biphenyl phosphate (bisphenoldiphenyl phosphate), ammonium polyphosphate (ammonium poly phosphate), hydroquinone-bis-(biphenyl Phosphate) (hydroquinone bis-(diphenyl phosphate)), tri (2-carboxyethyl) phosphine (tri (2-carboxyethyl) phosphine, TCEP), tri (isopropyl chloride) phosphate, trimethyl phosphate ( Trimethyl phosphate, TMP), dimethyl-methyl phosphate (dimethyl methyl phosphate, DMMP), resorcinol dixylenyl phosphate (resorcinol dixylenylphosphate, RDXP (such as PX-200)), melamine polyphosphate (melamine polyphosphate), phosphorus nitrogen-based compounds (phosphazene, such as SPB-100), aphosphazene compounds and their derivatives or resins, but not limited thereto.

In addition, the resin composition of the present invention may further optionally include additives such as inorganic fillers, surfactants, toughening agents or solvents.

The main function of adding inorganic fillers is to increase the thermal conductivity of the resin composition, improve its thermal expansion and mechanical strength, and the inorganic fillers are preferably evenly distributed in the resin composition; the main purpose of adding surfactants is to make the inorganic The filler can be uniformly dispersed in the resin composition; the main purpose of adding the toughening agent is to improve the toughness of the resin composition; and the main purpose of adding the solvent is to change the solid content of the resin composition and adjust the viscosity of the resin composition.

Among them, inorganic fillers may include silicon dioxide (melted or non-melted), aluminum oxide, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, boron nitride, aluminum hydroxide, aluminum carbide At least one of silicon, silicon carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconia, quartz, diamond powder, diamond-like powder, graphite or calcined kaolin, and the inorganic filler can be spherical or irregular, and can be selected Sexually via surfactant pretreatment. The inorganic filler can be a particle powder with a particle size of less than 100 μm, preferably a particle size of 1-20 μm, and most preferably a nano-sized particle powder with a particle size of less than 1 μm.

The surfactant may contain silane compounds, siloxane compounds, aminosilane compounds, or polymers of the above-mentioned compounds.

Tougheners may include rubber resins, polybutadiene, or core-shell polymers, among others.

Solvents can include methanol, ethanol, ethylene glycol monomethyl ether, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxy Solvents such as ethyl ethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, propylene glycol methyl ether or their mixed solvents.

In terms of the ratio of each main component of the resin composition, if the epoxy resin is 100 parts by weight, the preferred hardening accelerator is 0.001 to 1.0 parts by weight, the phosphorus-containing resin is 5 to 300 parts by weight, and the crosslinking agent 5 to 100 parts by weight.

Another object of the present invention is to provide a semi-cured film, which has good flame retardancy, heat resistance stability, high glass transition temperature, halogen-free and other characteristics, and can be applied to the insulation layer material of laminated boards and circuit boards .

The prepreg of the present invention includes the aforementioned resin composition, wherein the resin composition undergoes a mixing and stirring process to uniformly mix the components and then undergoes a heating process to form a semi-cured state. For example, the resin composition can be placed on a polyethylene terephthalate (PET) film and heated to form a prepreg.

Yet another object of the present invention is to provide a laminate comprising at least one metal foil laminate and at least one insulating layer. Among them, the metal foil laminate may include metals such as copper, aluminum, nickel, platinum, silver, gold or alloys thereof, and is preferably a copper foil laminate. By attaching the prepreg provided by the present invention to at least one piece of metal foil laminate, removing the PET film, and heating and curing the prepreg and the metal foil laminate under high temperature and pressure, a metal laminate can be formed. Foil laminates tightly bonded insulating layer.

Another object of the present invention is to provide a semi-cured film, which has the characteristics of high mechanical strength, good flame retardancy, heat resistance stability, high glass transition temperature and no halogen. Accordingly, the prepreg provided by the present invention may include a reinforcing material and the above-mentioned resin composition, wherein the resin composition is adhered to the reinforcing material after the components are uniformly mixed through a mixing and stirring process, and passed through Heating at high temperature forms a semi-cured state. Wherein, the reinforcing material can be fiber material, woven fabric and non-woven fabric, such as glass fiber fabric, which can increase the mechanical strength of the prepreg. In addition, the reinforcing material can optionally be pretreated with a silane coupling agent or a siloxane coupling agent, such as glass fiber cloth pretreated with a silane coupling agent.

The above-mentioned prepreg can be cured by heating at high temperature or under high temperature and high pressure to form a cured film or a solid insulating layer. If the resin composition contains a solvent, the solvent will be volatilized and removed during the high temperature heating process.

Another object of the present invention is to provide a laminate, which comprises two or more metal foil laminates and at least one insulating layer. Among them, the metal foil laminate may contain copper, aluminum, nickel, platinum, silver, gold and other metals or their alloys, and it is preferably a copper foil plate: the insulating layer is cured by the aforementioned prepreg under high temperature and high pressure. Alternatively, the aforementioned prepreg is laminated between two metal foil laminates and pressed under high temperature and high pressure.

The laminated board of the present invention has at least one of the following advantages: excellent heat resistance and flame retardancy, heat resistance stability, high glass transition temperature, high mechanical strength and halogen-free environmental protection. The laminated board can be further processed into a circuit board after being processed such as making a circuit, and the circuit board can be operated in severe environments such as high temperature and high humidity without affecting its quality after being bonded with electronic components.

Another object of the present invention is to provide a circuit board, the insulation layer of which has the characteristics of heat resistance and flame retardancy, heat resistance stability, high glass transition temperature, high mechanical strength and halogen-free, which is suitable for high-speed and high-frequency signal transmission Applications. Wherein, the circuit board includes at least one laminated board mentioned above, and the circuit board can be made by known circuit board manufacturing process.

Detailed ways

In order to further describe the present invention so that those skilled in the art of the present invention can implement it, several examples are given below to further illustrate the present invention. However, it should be noted that the following examples are only used to further illustrate the present invention, and are not intended to limit the implementation scope of the present invention, and any person with ordinary knowledge in the technical field of the present invention can obtain it without departing from the spirit of the present invention. Modifications and changes achieved in this way all belong to the scope of the present invention.

Embodiment one

A resin composition comprising the following components:

(A) Novolac epoxy resin of 100 parts by weight

(B) 30 parts by weight of DDS

(C) DOPO-BPAN resin of 40 parts by weight

(D) Dimethylimidazole of 0.1 parts by weight

Embodiment two

A resin composition comprising the following components:

(A) 100 parts by weight of bisphenol A epoxy resin

(B) phenol novolac (phenolic novolac) resin of 40 weight parts

(C) 20 parts by weight of DDS

(D) DOPO-BPAN resin of 20 parts by weight

(E) dimethylimidazole of 0.1 weight part

Embodiment Three

A resin composition comprising the following components:

(A) 100 parts by weight of dicyclopentadiene epoxy resin

(B) 30 parts by weight of DDS

(C) DOPO-BPAN resin of 45 parts by weight

(D) fused silica of 50 parts by weight

(E) 1 part by weight of siloxane compound

(F) 50 parts by weight of methyl ethyl copper

(G) dimethylimidazole of 0.1 parts by weight

Embodiment four

A semi-cured film, which can be obtained by mixing the resin composition described in Example 2 uniformly in a stirring tank, coating it on a PET film, and heating and baking it into a semi-cured state.

Embodiment five

A prepreg, the resin composition described in Example 3 can be mixed evenly in a stirring tank and then placed in an impregnation tank, and then the glass fiber cloth is passed through the impregnation tank to make the resin composition adhere to the glass fiber cloth, and heated and baked into a semi-cured state.

Embodiment six

A laminated board comprising a semi-cured film, a copper foil and a circuit substrate, wherein the semi-cured film is as described in Embodiment 4, the plane of the semi-cured film not containing the PET film is combined with the circuit substrate, and then the PET film is removed remove, and bond the side of the prepreg that removes the PET film to a copper foil, and then press through high temperature and high pressure to solidify the prepreg to form an insulating layer between the copper foil and the circuit board.

Embodiment seven

A laminated board, comprising four prepregs and two copper foils described in Example 5, stacked in the order of copper foil, four prepregs, and copper foil, and then pressed together through a high temperature and high pressure process, The four prepregs are solidified to form an insulating layer between the two copper foils.

Embodiment eight

A circuit board, comprising a plurality of laminated boards and a plurality of prepregs, wherein the laminated boards are as described in Embodiment 7 and then undergo a lithography etching process to form a surface circuit, and the prepregs are as described in Embodiment 5, The multiple laminates and the multiple prepregs are interlaced and stacked between two copper foils. The above-mentioned laminated structure is then subjected to a high-temperature and high-pressure lamination process to form a circuit board substrate, and the circuit board substrate can be processed by a known circuit board. The manufacturing process forms a circuit board, so I won’t go into details here.

Embodiment nine

A circuit board, the main structure of which is as described in the eighth embodiment, the difference is that the laminated board undergoes a drilling process to form blind holes.

comparative example

In addition, in order to compare the influence of different phosphorus-containing compounds in the composition on the physicochemical properties of the composition, three different resin compositions were prepared according to the following table:

The above resin compositions A, B and C were prepared according to the steps described in Example 5 and Example 7 to form an insulating substrate, and the substrates containing resin compositions A, B and C were measured for solder dip heat resistance , flame resistance, water absorption, rigidity, glass transition temperature and heat resistance test (pressurecooking test) after water absorption, the test results show that compared with the insulating substrate formed by composition A containing DOPO-BPAN, the composition B and C formed All insulating substrates have a low glass transition temperature, and their water absorption, rigidity, flame resistance, heat resistance and heat resistance after water absorption are poor.

Claims (13)

1. resin combination comprises:

Epoxy resin;

Hardening accelerator;

Linking agent; And

Phosphorous resin, it is 9, the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-substituted bis-phenol resol of 10-oxide compound or derivatives thereof, it is characterized in that said phosphorous resin has the structure of formula (II) or formula (III):

formula (II)

formula (III)

Wherein, Ph ₁With Ph ₂Be phenyl, the hydroxyl on it connects with the contraposition mode with respect to W, Ph ₁With Ph ₂In at least one comprises more than one X, and Ph ₁With Ph ₂Independent separately and optionally comprise more than one Z; X is 9, and the 10-dihydro-9-oxy is mixed-10-phosphorus phenanthrene-10-oxide compound or derivatives thereof; Y is selected from covalent linkage, aliphatics functional group and aromatic series functional group; Z is selected from hydrogen, aliphatics functional group and aromatic series functional group; W is selected from following group:

N is the integer more than or equal to 1.

2. resin combination as claimed in claim 1; It is characterized in that said epoxy resin comprises at least a bisphenol A epoxide resin, bisphenol F epoxy resin, bisphenol-s epoxy resin, novolac epoxy, bisphenol-A phenolic epoxy resin, o-cresol epoxy resin, trifunctional basic ring epoxy resins, four functional group's epoxy resin, Dicyclopentadiene (DCPD) epoxy resin, phosphorous epoxy resin, p-Xylol epoxy resin, naphthalene type epoxy resin, benzo piperazine mutter type epoxy resin, xenol formaldehyde epoxy resin, phenolic group benzene alkyl phenolic epoxy resin or its combination.

3. resin combination as claimed in claim 1; It is characterized in that said hardening accelerator is selected from the metal salt compound of imidazoles, boron trifluoride amine compound, tonsilon triphenylphosphine, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 4-dimethyl amine yl pyridines and manganese, iron, cobalt, nickel, copper and zinc.

4. resin combination as claimed in claim 1 is characterized in that, said linking agent comprises two amido sulfobenzides.

5. resin combination as claimed in claim 4; It is characterized in that, more comprise at least a linking agent, its upgrading thing or its combination that is selected from following group: cyanate ester resin, phenolic resin, resol, styron, polybutadiene, polyphenylene oxide resin, anhydride compound, amino-complex and benzoxazine resin.

6. resin combination as claimed in claim 1; It is characterized in that, more comprise at least a fire-retardant compound or its combination that is selected from following group: bis-phenol biphenyl phosphoric acid salt, ammonium polyphosphate, Resorcinol-two-(diphenylphosphine hydrochlorate), three (2-propyloic) phosphine, three (isopropyl chloride) phosphoric acid salt, trimethylammonium phosphoric acid salt, dimethyl--methyl phosphate, Resorcinol bis-xylene based phosphates, polyphosphoric acid melamine, phosphonitryl compound and phosphazo compound.

7. resin combination as claimed in claim 1; It is characterized in that, more comprise at least a inorganic filler or its combination that is selected from following group: silicon-dioxide, aluminum oxide, Natural manganese dioxide, Marinco H, lime carbonate, talcum, clay, aluminium nitride AlN, SP 1, white lake, aluminum silicon carbide, silit, yellow soda ash, titanium oxide, zinc oxide, zirconium white, quartz, diamond, type diamond, graphite, calcined kaolin.

8. resin combination as claimed in claim 7 is characterized in that, more comprises at least a interface promoting agent, toughner, solvent or its combination.

9. the resin combination described in claim 1 is characterized in that, epoxy resin is 100 weight part meters, and hardening accelerator is that 0.001 to 1.0 weight part, phosphorous resin are that 5 to 300 weight parts, linking agent are 5 to 100 weight parts.

10. a semicure film comprises that wherein this resin combination forms the semicure attitude via heating like each described resin combination in the claim 1 to 9.

11. semicure film as claimed in claim 10 is characterized in that, more comprises the glasscloth that resin combination coated by the semicure attitude.

12. a laminated wood comprises at least one tinsel laminate and at least one insulation layer, this insulation layer is cured claim 10 or 11 described semicure films and forms.

13. a circuit card comprises at least a laminated wood as claimed in claim 12.