WO2018098908A1

WO2018098908A1 - Thermosetting resin composition

Info

Publication number: WO2018098908A1
Application number: PCT/CN2017/074298
Authority: WO
Inventors: 罗成; 唐国坊; 许永静
Original assignee: 广东生益科技股份有限公司
Priority date: 2016-11-30
Filing date: 2017-02-21
Publication date: 2018-06-07
Also published as: CN108117634B; CN108117634A

Abstract

Provided is a thermosetting resin composition comprising a phosphorus-containing active ester, the thermosetting resin composition has the advantages of good thermal stability, moisture and heat resistance, a low dielectric constant and a dielectric loss tangent, a low water absorption, a halogen-free flame retardant effect, etc., and it has excellent processability. Also provided is a use of the thermosetting resin composition in a resin sheet, a resin composite metal foil, a prepreg, a laminate, a metal foil laminate and a printed wiring board.

Description

Thermosetting resin composition

Technical field

The present invention relates to the field of polymer materials, and in particular to a thermosetting resin composition and a prepreg and printed circuit board using the same.

Background technique

Conventional printed circuit laminates usually use brominated flame retardants to achieve flame retardancy, especially with tetrabromobisphenol A epoxy resin, which has good flame retardancy, but it Hydrogen bromide gas is produced during combustion. Further, in recent years, carcinogens such as dioxins and dibenzofurans have been detected in combustion products of electrical and electronic equipment wastes containing halogens such as bromine and chlorine, and thus the application of brominated epoxy resins is limited. On July 1, 2006, the EU's two environmental protection directives, the Waste Electrical and Electronic Equipment Directive and the Directive on the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment, were officially implemented. Halogen-free flame-retardant copper clad laminates. Development has become a hot spot in the industry, and various copper foil laminate manufacturers have launched their own halogen-free flame-retardant copper clad laminates.

The introduction of a phosphorus-containing compound into the resin matrix of the copper clad laminate is the main technical route for the halogen-free flame retardant of the copper clad laminate. At present, phosphorus-based flame retardants widely used in the field of copper clad laminates are mainly classified into two types: reactive type and additive type. The reaction type is mainly a DOPO compound, and the phosphorus-containing epoxy resin and the phosphorus-containing phenolic resin are mainly used, and the phosphorus content is between 2% and 10%. However, in practical applications, it has been found that DOPO-based compounds have a large water absorption rate and poor dielectric properties, and the sheet has poor heat and humidity resistance. The addition type is mainly a phosphazene and a phosphonate compound, and the added flame retardant has a low flame retardancy efficiency, and it is necessary to add more amount to achieve the flame retardant requirement. At the same time, due to its lower melting point (generally lower than 150 ° C), it is easy to migrate to the surface of the sheet during the processing of the laminate, which affects the performance of the sheet.

In addition, for copper clad substrate materials, in order to meet PCB processing performance and terminal electronics The performance requirements of the product must have good dielectric properties, heat resistance and mechanical properties. At the same time, it should have good processing characteristics, high peel strength and excellent heat and humidity resistance.

The dicarboxyarylhydrocarbylphosphine oxide is a reactive phosphorus-containing curing agent capable of curing with an epoxy resin, but since its reactive group is a carboxyl group, it reacts with the epoxy resin to form a second polarity. Hydroxyl groups result in poor dielectric properties of the cured product. And the carboxyl group has strong reaction activity, and the process control is too difficult. In CN103384674A, a polyphosphonate or/and a phosphonate-carbonate copolymer having a hydroxyl group and an epoxy composition are used, the active group of which is a phenolic hydroxyl group, and the problem of poor dielectric properties is also present. CN103694642A discloses the use of epoxy resins, cyanate ester compounds or/and cyanate ester prepolymers, polyphosphonates or/and phosphonate-carbonate copolymers to prepare dielectric properties and good heat and humidity resistance. Halogen UL94 V-0 is flame retardant, but its peel strength, interlayer adhesion and bending strength are low.

Summary of the invention

The inventors have found that a phosphorus-containing active ester, that is, an esterified modified dicarboxyarylhydrocarbylphosphine oxide, is used as a curing agent for an epoxy resin, and does not generate a secondary hydroxyl group having a large polarity when reacted with an epoxy resin. The dielectric property of the system is better, and at the same time, it is a phosphorus-containing active ester curing agent, and has the effect of halogen-free flame retardant while being used as a curing agent, and has high flame retardant efficiency, and requires little or no addition. Adding other flame retardants can achieve a UL94 V-0 halogen-free flame retardant effect.

Based on this, one of the objects of the present invention is to provide a thermosetting resin composition, and a prepreg and a laminate for printed circuit board using the same. The printed circuit board laminate produced by using the resin composition has high glass transition temperature, excellent dielectric properties, high heat resistance and moist heat resistance, and good processability, and can realize halogen-free flame retardant. UL94 V-0.

The present inventors conducted intensive studies to achieve the above object, and as a result, found that a composition obtained by appropriately mixing a halogen-free epoxy resin, an esterified modified dicarboxyarylhydrocarbylphosphine oxide, and optionally other curing agents, The above purpose can be achieved.

That is, the present invention employs the following technical solution: a thermosetting resin composition comprising an epoxy resin and an epoxy resin curing agent, wherein the curing agent contains at least one esterified modified dicarboxyarylhydrocarbylphosphine oxide.

The thermosetting resin composition of the present invention contains a phosphorus-containing active ester, that is, an esterified modified dicarboxyarylhydrocarbylphosphine oxide as a curing agent for an epoxy resin. The active ester group as a reactive group has a high content, and can be cured with an epoxy resin to obtain a cured product having a high crosslinking density, and a material having high heat resistance and high Tg can be obtained; and the esterified modified dicarboxy aromatic group can be obtained. The hydrocarbyl phosphine oxide structure has high symmetry, and the reactive ester unit in the molecule does not generate a secondary hydroxyl group having a large polarity after reacting with the epoxy resin, and the dielectric property of the secondary hydroxyl group having a large polarity can be eliminated. Disadvantages, excellent dielectric properties; the esterified modified dicarboxyarylhydrocarbylphosphine oxide is an active ester, and the ester bond formed by the reaction with the epoxy resin has a low water absorption rate, which improves the wet heat resistance of the phosphorus-containing compound Shortcomings. In addition, the esterified modified dicarboxyarylhydrocarbylphosphine oxide can have a halogen-free flame retardant effect, and has high flame retardant efficiency, and can achieve UL94 V-0 flame retardant with little or no additional flame retardant.

The present invention utilizes an active ester group of a highly symmetric esterified modified dicarboxyarylhydrocarbylphosphine oxide to significantly increase the glass transition temperature of a prepreg prepared using the resin composition and a laminate for a printed circuit. Heat resistance, and it has excellent dielectric properties, low water absorption, good heat and humidity resistance, and good processability, and achieves halogen-free flame retardant, reaching UL94 V-0. Each component will be described in detail below.

According to the present invention, the esterified modified dicarboxyarylhydrocarbylphosphine oxide has a structural formula of the formula (I):

Wherein n ₁ is an integer of 1 to 20, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20;

Wherein R ₁ is any _one of a phenyl group, a naphthyl group, and a linear or branched alkyl group having 1 to 4 carbon atoms; and a linear or branched alkyl group having 1 to 4 carbon atoms may be, for example, a Any one of a group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a t-butyl group;

Wherein, Ar ₁ and Ar ₂ are each independently selected from any one of the following groups:

Wherein X is selected from any of the following groups:

Wherein n ₂ is an integer from 0 to 5, such as 0, 1, ₂ , 3, 4 or 5; n ₃ is an integer from 0 to 7, such as 0, 1, 2, 3, 4, 5, 6 or 7;

Wherein R ₂ is any one of an allyl group and a linear or branched alkyl group having 1 to 4 carbon atoms; and a linear or branched alkyl group having 1 to 4 carbon atoms may be, for example, a methyl group. Either ethyl, propyl, butyl, isopropyl, isobutyl or tert-butyl.

The esterification-modified dicarboxyarylhydrocarbylphosphine oxide in the present invention may have the following structural formula:

According to the present invention, the esterification-modified dicarboxyarylhydrocarbylphosphine oxide accounts for 20% to 50%, for example, 20%, 22%, 24% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. , 25%, 26%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48% or 50%, and the specific value between the above values, limited by space and For the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the scope.

According to the present invention, the epoxy resin accounts for 30% to 60%, for example, 30%, 32%, 34%, 35%, 36%, 38% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. , 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58% or 60%, and the specific point value between the above values, limited by space and for the sake of concise consideration, the present invention does not The specific point values included in the range are exhausted.

The present invention preferably employs a halogen-free epoxy resin, which is an epoxy resin having two or more epoxy groups in one molecule, and may be specifically selected from glycidyl ethers and shrinkage. Glycerides, glycidylamines, cycloaliphatic epoxy resins, epoxidized olefins, hydantoin or amide Any one or a mixture of at least two of the amine epoxy resins, wherein the typical but non-limiting mixtures are: glycidyl ethers and glycidyl esters, alicyclic epoxy resins and epoxidized olefins, shrinkage Glyceramines and hydantoin epoxy resins.

Preferably, the glycidyl ethers include bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, and trisphenol novolac epoxy resin. Any one or a mixture of at least two of a dicyclopentadiene novolac epoxy resin, a biphenyl type novolac epoxy resin, an alkylbenzene type novolac epoxy resin or a naphthol type novolac epoxy resin.

Further preferably, the glycidyl ether is selected from the group consisting of epoxy resins having the following structure:

Wherein Z ₁ , Z ₂ and Z ₃ are each independently selected from

R _{3 is} selected from the group consisting of a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group; for example, it may be a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group. Any one of a benzyl group, an isopropyl group, an isobutyl group, a t-butyl group or an isopentyl group;

Wherein Y ₁ and Y ₂ are each independently selected from -CH ₂ -,

Any one of R _{4 is} selected from a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group; for example, it may be a methyl group, an ethyl group or a C group. Any one of a butyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a t-butyl group or an isopentyl group;

Wherein n ₄ is any integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

Preferably, the glycidylamine is selected from the group consisting of triglycidyl-p-aminophenol, triglycidyl trimer isocyanate, tetraglycidyldiaminodimethylenebenzene, tetraglycidyl-4, 4' -diaminodiphenylmethane, tetraglycidyl-3,4'-diaminodiphenyl ether, tetraglycidyl-4,4'-diaminodiphenyl ether or tetraglycidyl-1,3- Any one or a mixture of at least two of diaminomethylcyclohexane.

The halogen-free thermosetting resin composition of the present invention employs the halogen-free epoxy resin having the specific molecular structure described above, which has high functionality and good dielectric properties, and has a high Tg of cured product and low water absorption.

According to the present invention, the curing agent may further comprise a cyanate resin and/or a bismaleimide-triazine resin; wherein the cyanate resin has the following structure:

Wherein R ₅ is -CH ₂ -,

Any one or a mixture of at least two; R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ are each independently selected from a hydrogen atom, a substituted or unsubstituted carbonaceous Any one of a linear alkyl group or a branched alkyl group having 1 to 4 may be, for example, any one of a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a t-butyl group. Kind.

Preferably, the cyanate resin is selected from the group consisting of 2,2-bis(4-cyanooxyphenyl)propane, bis(4-cyanooxyphenyl)ethane, bis(3,5-dimethyl- 4-cyanooxyphenyl)methane, 2,2-bis(4-cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'-bis(4- Cyanooxyphenyl)-m-isopropylbenzene, cyclopentadiene cyanate, phenol novolac cyanate, cresol novolac cyanate, 2,2-bis(4-cyanooxybenzene) Propane pre Polymer, bis(4-cyanooxyphenyl)ethane prepolymer, bis(3,5-dimethyl-4-cyanooxyphenyl)methane prepolymer, 2,2-bis(4- Cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropane prepolymer, α,α'-bis(4-cyanooxyphenyl)-m-isopropylbenzene prepolymer Any one or a mixture of at least two of a dicyclopentadiene type cyanate prepolymer, a phenol novolac type cyanate prepolymer or a cresol novolac type cyanate prepolymer, preferably 2, 2-bis(4-cyanooxyphenyl)propane, α,α'-bis(4-cyanooxyphenyl)-m-isopropylbenzene, bis(3,5-dimethyl-4-cyanide Oxyphenyl)methane, 2,2-bis(4-cyanooxyphenyl)propane prepolymer, α,α'-bis(4-cyanooxyphenyl)-m-isopropylbenzene prepolymer Or a mixture of any one or at least two of bis(3,5-dimethyl-4-cyanooxyphenyl)methane prepolymers.

According to the present invention, the cyanate resin and/or bismaleimide-triazine resin accounts for 0% to 50%, for example 0%, of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. 2%, 4%, 5%, 8%, 10%, 12%, 14%, 15%, 17%, 20%, 22%, 25%, 30%, 32%, 35%, 37%, 39% 40%, 42%, 45%, 48%, or 50%, and the specific point values between the above values are limited to the length and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range.

According to the present invention, the curing agent may further comprise an SMA resin; the SMA resin means a styrene-maleic anhydride resin which can be obtained by copolymerization of styrene and maleic anhydride in a ratio of from 1:1 to 8:1.

According to the present invention, the SMA resin accounts for 0% to 40%, for example, 0%, 2%, 4%, 5%, 8%, 10%, of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. 12%, 14%, 15%, 17%, 20%, 22%, 25%, 30%, 32%, 35%, 37%, 39% or 40%, and the specific value between the above values is limited For the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the scope.

According to the present invention, the curing agent may further comprise a phenolic resin; the phenolic resin is a phosphorus-containing or phosphorus-free phenolic resin, which is a phenolic resin well known in the art, and is not particularly limited in the present invention.

According to the present invention, the phenolic resin accounts for an epoxy resin and a curing agent in the thermosetting resin composition. 0% to 20% of the total weight, such as 0%, 2%, 4%, 5%, 8%, 10%, 12%, 14%, 15%, 17% or 20%, and the specific between the above values Point values, limited to length and for the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the ranges.

The thermosetting resin composition according to the present invention, the organic solid content is 100 parts by weight, and specifically comprises: esterified modified dicarboxyaryl hydrocarbon phosphine oxide: 20 to 50 parts by weight; halogen-free epoxy resin: 30 to 60 parts by weight; cyanate resin and/or bismaleimide-triazine resin: 0 to 50 parts by weight; SMA resin: 0 to 40 parts by weight; phenol resin: 0 to 20 parts by weight.

The "total weight of the epoxy resin and the curing agent in the thermosetting resin composition" referred to in the present invention means the total weight of the components participating in the crosslinking polymerization reaction, wherein the curing agent means curing the epoxy resin Functional esterified modified dicarboxyarylhydrocarbylphosphine oxide and optionally cyanate resin and/or bismaleimide-triazine resin, SMA resin or phenolic resin, which does not contain fillers, accelerators and Flame retardant and other components.

The thermosetting resin composition of the present invention may further comprise an organic halogen-free flame retardant, and the organic halogen-free flame retardant may specifically be selected from the group consisting of phosphorus-containing flame retardants.

According to the present invention, the phosphorus-containing flame retardant may be selected from the group consisting of tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa- Any one or a mixture of at least two of 10-phosphaphenanthrene-10-oxide, phenoxyphosphazene compound, phosphate, polyphosphate, polyphosphonate or phosphonate-carbonate copolymer.

In the present invention, the total amount of the epoxy resin and the curing agent in the thermosetting resin composition is 100 parts by weight, and the organic halogen-free flame retardant is added in an amount of 0 to 15 parts by weight, that is, modified according to esterification. The sum of the addition amount of the dicarboxylic acid-based hydrocarbon phosphine oxide, the epoxy resin and the possibly added cyanate resin, the SMA resin, and the phenol resin is 100 parts by weight, and the organic halogen-free flame retardant is added in an amount of 0 to 15 parts by weight, for example, 1 part by weight, 3 parts by weight, 5 parts by weight, 6 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 Part by weight, 12 parts by weight, 13 parts by weight or 15 parts by weight, and the specific point values between the above values are limited to the extent and for the sake of brevity, the present invention is not exhaustively enumerated.

The halogen-free thermosetting resin composition of the present invention may further comprise a curing accelerator.

Preferably, the curing accelerator comprises an organic metal salt and any one or at least two selected from the group consisting of an imidazole compound, a derivative of an imidazole compound, a piperidine compound, a pyridine compound, a Lewis acid or a triphenylphosphine. Kind of mixture.

Preferably, the organometallic salt in the curing accelerator comprises any one of a metal octoate, a metal isooctanoate, a metal acetylacetonate, a metal naphthenate, a metal salicylate or a metal stearate. Or a mixture of at least two, wherein the metal is selected from any one or a mixture of at least two of zinc, copper, iron, tin, cobalt or aluminum.

Preferably, the imidazole compound is any one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole or a mixture of at least two .

Preferably, the piperidine compound is 2,3-diaminopiperidine, 2,5-diaminopiperidine, 2,6-diaminopiperidine, 2-amino-3-methylpiperidine, 2- Any one of amino-4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine or 2-amino-4,4-dimethylpiperidine or a mixture of at least two.

Preferably, the pyridine compound is any one or a mixture of at least two of 4-dimethylaminopyridine, 2-aminopyridine, 3-aminopyridine or 4-aminopyridine.

Preferably, the curing accelerator is based on 100 parts by weight of the sum of the esterification-modified dicarboxyarylhydrocarbylphosphine oxide, epoxy resin, and possibly added cyanate resin, SMA resin, and phenol resin. The amount added is 0.01 to 1 part by weight, for example, 0.01 parts by weight, 0.025 parts by weight, 0.05 parts by weight, 0.07 parts by weight, 0.085 parts by weight, 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 0.9 parts by weight. Or 1 part by weight, preferably 0.025 to 0.85 parts by weight.

The halogen-free thermosetting resin composition of the present invention may further comprise a filler.

Preferably, the filler is selected from the group consisting of organic or inorganic fillers, preferably inorganic fillers, further preferably surface treated inorganic fillers, most preferably surface treated silica.

Preferably, the surface treated surface treatment agent is selected from any one or a mixture of at least two of a silane coupling agent, a silicone oligomer or a titanate coupling agent.

Preferably, the surface treatment agent is used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, more preferably 0.75 to 2 parts by weight, based on 100 parts by weight of the inorganic filler.

Preferably, the inorganic filler is selected from any one or a mixture of at least two of a non-metal oxide, a metal nitride, a non-metal nitride, an inorganic hydrate, an inorganic salt, a metal hydrate or an inorganic phosphorus, preferably molten. Silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, titanium Any one or a mixture of at least two of acid strontium, calcium carbonate, calcium silicate or mica.

Preferably, the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder.

Preferably, the filler has a median particle diameter of from 0.01 to 50 μm, preferably from 0.01 to 20 μm, further preferably from 0.1 to 10 μm.

Preferably, the addition of the filler is carried out in an amount of 100 parts by weight of the addition amount of the esterified modified dicarboxyarylhydrocarbylphosphine oxide, epoxy resin, and possibly added cyanate resin, SMA resin, and phenol resin. The amount is 5 to 300 parts by weight, preferably 5 to 200 parts by weight, and more preferably 5 to 150 parts by weight.

The term "comprising" as used in the present invention means that it may include other components in addition to the components, and these other components impart different characteristics to the halogen-free thermosetting resin composition. In addition, the "comprising" described in the present invention may also be replaced by a closed "for" or "consisting of".

For example, the halogen-free thermosetting resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, or a lubricant. Agents, etc. These additives may be used singly or in combination of two or more.

The preparation method of the halogen-free thermosetting resin composition of the present invention is a conventional technical means in the art, which is: firstly, the solid matter is put in, then the liquid solvent is added, and the mixture is stirred until the solid matter is completely dissolved, and then the liquid resin is added. Accelerator, continue to stir evenly.

The solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, and butyl. Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and ethoxyethyl acetate a nitrogen-containing solvent such as N,N-dimethylformamide or N,N-dimethylacetamide. The above solvents may be used singly or in combination of two or more. Preference is given to ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone and cyclohexanone. The amount of the solvent to be added is selected by those skilled in the art based on his own experience, so that the resin glue can reach a viscosity suitable for use.

The prepreg of the present invention comprises a reinforcing material and a halogen-free thermosetting resin composition as described above which is impregnated and adhered to the reinforcing material after drying, and the reinforcing material to be used is not particularly limited and may be an organic fiber, an inorganic fiber woven fabric or Non-woven fabric. The organic fiber may be selected from aramid nonwoven fabric, and the inorganic fiber woven fabric may be E-glass fabric, D-glass fabric, S-glass fabric, T-glass fabric, NE-glass fabric. Or quartz cloth. The thickness of the reinforcing material is not particularly limited, and the thickness of the woven fabric and the nonwoven fabric is preferably 0.01 to 0.2 mm, and preferably the fiber-opening treatment and the silane coupling agent are considered. The surface treatment, in order to provide good water resistance and heat resistance, the silane coupling agent is preferably any one or at least two of an epoxy silane coupling agent, an amino silane coupling agent or a vinyl silane coupling agent. Kind of mixture. The prepreg is obtained by impregnating the above-mentioned halogen-free thermosetting resin composition by baking at 100 to 250 ° C for 1 to 15 minutes.

The laminate for printed circuit of the present invention comprises a laminate prepared by bonding together one or two or more prepregs by heat and pressure, and a metal foil bonded to one or both sides of the laminate. . The laminate is obtained by curing in a hot press at a curing temperature of 150 to 250 ° C and a curing pressure of 10 to 60 kg/cm ² . The metal foil is copper foil, nickel foil, aluminum foil, SUS foil, etc., and the material thereof is not limited.

Compared with the prior art, the present invention has at least the following beneficial effects:

The prepreg and the printed circuit board made of the thermosetting resin composition provided by the invention have a glass transition temperature of up to 245 ° C; excellent dielectric properties, and the water absorption rate is controlled within a range of 0.05 to 0.10%; It has high heat resistance, excellent heat and humidity resistance and good processability; excellent flame retardant efficiency, and the phosphorus content of 1.0% can achieve UL94 V-0 halogen-free flame retardant effect.

detailed description

The technical solution of the present invention will be further described below by way of specific embodiments.

The following is a specific embodiment of the embodiments of the present invention. It should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the embodiments of the present invention. And retouching is also considered to be the scope of protection of the embodiments of the present invention.

The embodiments of the present invention are further described below in various embodiments. The embodiments of the present invention are not limited to the specific embodiments below. Modifications can be made as appropriate without departing from the scope of the claims.

1. Synthesis of phosphine oxide active ester P-AE1

343 g of bis(4-formylchlorophenyl)methylphosphine oxide, 116 g of hydroquinone and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer while introducing nitrogen gas, and then heating up to The reaction was carried out at this temperature for 4 h at 30 °C. Then, 21 g of benzoyl chloride was further added to the reaction system, and the reaction was also carried out at this temperature for 2 hours. The product was cooled to room temperature and then a 5% sodium carbonate solution was added and stirred vigorously, filtered, washed with water and dried to give <RTIgt;

Where n ₁ = 20.

2. Synthesis of phosphine oxide active ester P-AE2

403 g of bis(3-formylchlorophenyl)phenylphosphine oxide, 192 g of 2,7-dihydroxynaphthalene and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer while introducing nitrogen gas. Then, the temperature was raised to 30 ° C, and the reaction was carried out at this temperature for 4 hours. Then, 62 g of p-methylbenzoyl chloride was further added to the reaction system, and the reaction was also carried out at this temperature for 2 hours. The product was cooled to room temperature and then a 5% sodium carbonate solution was added and stirred vigorously, filtered, washed with water and dried to give product 480 g, numbered P-AE2.

Where n ₁ =10.

3. Synthesis of phosphine oxide active ester P-AE3

453 g of bis(3-formylchlorophenyl)naphthylphosphine oxide, 242 g of 4,4-biphenoldiol and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer while being introduced. Nitrogen gas was then heated to 30 ° C and reacted at this temperature for 4 h. Then, 138 g of p-tert-butylbenzoyl chloride was further added to the reaction system, and the reaction was also carried out at this temperature for 2 hours. The product was cooled to room temperature and then a 5% sodium carbonate solution was added and stirred vigorously, filtered, washed with water and dried to give 530 g of product, numbered P-AE3.

Where n ₁ = 5.

4. Synthesis of phosphine oxide active ester P-AE4

525 g of bis(4-(4-benzoylchloro)phenoxy)methylphosphine oxide, 375 g of bisphenol S and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer. Nitrogen gas was introduced, and then the temperature was raised to 30 ° C, and the reaction was carried out at this temperature for 4 hours. Then, 155 g of benzoyl chloride was further added to the reaction system, and the reaction was also carried out at this temperature for 2 hours. The product was cooled to room temperature and then a 5% sodium carbonate solution was added and stirred vigorously, filtered, washed with water and dried to give <RTIgt;

Where n ₁ = 3.

5. Synthesis of phosphine oxide active ester P-AE5

403 g of bis(3-formylchlorophenyl)phenylphosphine oxide, 364 g of 2,3,5,6-tetrafluorohydroquinone and 1500 g of pyridine in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer While stirring, nitrogen gas was introduced at the same time, and then the temperature was raised to 30 ° C, and the reaction was carried out at this temperature for 4 hours. Then, 295 g of benzoyl chloride was further added to the reaction system, and the reaction was also carried out at this temperature for 2 hours. The product was cooled to room temperature and then a 5% sodium carbonate solution was added and stirred vigorously, filtered, washed with water and dried to give &lt

Where n ₁ =1.

The above phosphine oxide active ester, halogen-free epoxy resin, curing accelerator, halogen-free flame retardant, filler are uniformly mixed in a solvent in a certain ratio, and the solid content of the glue is controlled to be 65%, and the glue is impregnated with 2116 glass fiber cloth. Liquid, control the appropriate thickness, then bake in the oven at 115 ~ 175 ° C for 2 ~ 15min to make a prepreg, then stack several prepregs together, on both sides of the stack of 18μRTF copper foil, at the curing temperature The copper-clad laminate is prepared at a temperature of 170 to 250 ° C, a curing pressure of 25 to 60 kg/cm ² , and a curing time of 60 to 300 minutes.

Examples 1 to 10 and Comparative Examples 1 to 7 relate to materials and brand information as follows:

(A) phosphine oxide active ester P-AE

P-AE1: Homemade phosphine oxide active ester P-AE

Where n ₁ =20;

P-AE2: Homemade phosphine oxide active ester P-AE

Where n ₁ =10;

P-AE3: Homemade phosphine oxide active ester P-AE

Wherein n ₁ = 5;

P-AE4: Homemade phosphine oxide active ester P-AE

Where n ₁ = 3;

P-AE5: Homemade phosphine oxide active ester P-AE

Wherein n ₁ =1;

BCPPO: bis(4-carboxyphenyl)phenylphosphine oxide

FRX-3001:

(B) Cyanate ester

CY-40: Wuqiao resin factory, DCPD type cyanate resin

PT-60S: LONCZ, phenolic cyanate resin

CE01PS: Jiangsu Tianqi, bisphenol A type cyanate resin

CE01MO: Jiangsu Tianqi, bisphenol A type cyanate resin

(C) epoxy resin

HP-7200HHH: DIC, DCPD type epoxy resin, epoxy equivalent 288

HP-7200H-75M: DIC, DCPD type epoxy resin, epoxy equivalent 280

HP-6000: DIC, epoxy resin, epoxy equivalent 250

HP-9900: DIC, naphthol type epoxy resin, epoxy equivalent 274

NC-3000H: Nippon Chemical, Biphenyl Epoxy Resin, Epoxy Equivalent 294

SKE-1: Shankote, special epoxy resin, epoxy equivalent 120

SKE-3: Shankote, special epoxy resin, epoxy equivalent 120

(D) phenolic resin

DOW92741: Phosphorus-containing phenolic, Dow Chemical

2812: Linear phenolic resin, MOMENTIVE (Korea)

(E) phosphorus-containing flame retardant

SPB-100: Otsuka Chemical, phosphazene flame retardant, phosphorus content 13.4%

(F)SMA

EF60: SMA, Sartomer

(G) accelerator

2E4MZ: 2-ethyl-4-methylimidazole, the formation of four countries

DMAP: 4-dimethylaminopyridine, Guangrong Chemical

Fused silica (average particle size 1 to 10 μm, purity 99% or more)

Table 1 shows the formulation compositions and physical property data of Examples 1 to 10, Table 2 Comparative Examples 1 to 7.

Table 1

Table 2

Supplementary description of the PCT/6h performance icon: × is a layered burst board, and O is a layered burst board.

The test methods for the above characteristics are as follows:

(1) Glass transition temperature (Tg): Measured according to the DMA test method specified in IPC-TM-650 2.4.24 using a DMA test.

(2) Dielectric constant and dielectric loss factor: tested according to the SPDR method.

(3) Evaluation of heat and humidity resistance (PCT): After etching the copper foil on the surface of the copper clad laminate, the substrate was evaluated; the substrate was placed in a pressure cooker, treated at 120 ° C, 105 KPa for 6 hours, and then immersed in a tin furnace at 288 ° C. When the substrate is stratified, the corresponding time is recorded; when the substrate is in the tin furnace for more than 5 minutes, no blistering or delamination occurs, and the evaluation can be ended.

(4) T288: Determined by TMA instrument according to the T300 test method specified in IPC-TM-650 2.4.24.1.

(5) Water absorption: The measurement was carried out in accordance with the water absorption test method specified in IPC-TM-650 2.6.2.1.

(6) Flame retardancy: It was carried out in accordance with the UL 94 standard method.

From the comparison of the data in Table 1 and Table 2, it can be seen that:

Comparing Comparative Example 1 with Example 6, the copper clad laminate prepared by using BCPPO and the halogen-free epoxy resin in Comparative Example 1 has poor dielectric properties, poor heat resistance and moist heat resistance, and high water absorption; Comparative Example 2 and In Comparative Example 5, BCPPO cured cyanate ester and halogen-free epoxy resin were used in Comparative Example 2. Under the same conditions, since the hydrogen activity of BCPPO was too strong, the cyanate ester was rapidly solidified and was phase-separated from the epoxy system. Copper clad laminate; Comparative Example 3 and Example 6 were compared. In Comparative Example 3, FRX3001 was used to cure the halogen-free epoxy resin. Under the same conditions, the FRX3001 had poor reactivity and low OH-content, and it was impossible to form a copper clad laminate; Comparative Example 4 and Comparing Example 2, the copper clad laminate prepared by using FRX3001 and cyanate resin co-cured halogen-free epoxy resin in Comparative Example 4 has poor dielectric properties, low Tg, poor heat and humidity resistance, and poor flame retardancy; Comparative Example 5 and In Comparative Example 9, the epoxy resin co-cured using FRX-3001 and EF60 in Comparative Example 5 was inferior in heat resistance, moist heat resistance, and flame retardancy as in Example 9.

Further, when Comparative Example 6-7 was compared with Example 6, it was found that when the content of Comparative Example 6 was lower than that of the esterification-modified dicarboxyarylhydrocarbylphosphine oxide in Example 6, the curing agent was insufficient. When the sheet material was formed, and the content of the copper carboxylate prepared by using the esterification-modified dicarboxyaryl hydrocarbon phosphine oxide in Comparative Example 7 was higher than that in Comparative Example 7, the dielectric properties were poor, water absorption, heat resistance, and Poor heat and humidity resistance.

From the above results, it can be seen that by replacing BCPPO and FRX with the esterified modified dicarboxyarylhydrocarbylphosphine oxide of the present invention, it is a prepreg and a printed circuit layer made of a halogen-free epoxy resin or the like. The pressure plate has a glass transition temperature of up to 245 ° C; excellent dielectric properties, water absorption is controlled in the range of 0.05 to 0.10%; high heat resistance, excellent heat and humidity resistance and good processability; excellent resistance The fuel efficiency, phosphorus content of 1.0% can achieve UL94 V-0 halogen-free flame retardant effect.

In summary, the prepreg and the printed circuit board made of the halogen-free thermosetting resin composition provided by the present invention have high glass transition temperature and excellent dielectric properties as compared with a general laminate. Low water absorption, high heat resistance, excellent heat and humidity resistance and good processability, and can achieve halogen-free resistance Combustion, UL94 V-0 halogen-free flame retardant.

The above is only a preferred embodiment of the present invention, and various other changes and modifications can be made in accordance with the technical solutions and technical concept of the present invention, and all such changes and modifications will be made to those skilled in the art. Modifications are intended to fall within the scope of the claims of the present invention.

Claims

A thermosetting resin composition comprising an epoxy resin and a curing agent; wherein the curing agent comprises at least one phosphorus-containing active ester, and the structural formula is as shown in formula (I);

Wherein n 1 is an integer of 1-20;

Wherein R 1 is a phenyl group, a naphthyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms;

Wherein, Ar 1 and Ar 2 are each independently selected from any one of the following groups:

Wherein X is selected from any of the following groups:

Wherein n 2 is an integer of 0 to 5; and n 3 is an integer of 0 to 7;

Wherein R 2 is any one of an allyl group and a linear or branched alkyl group having 1 to 4 carbon atoms;

The phosphorus-containing active ester accounts for 20% to 50% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition;

The epoxy resin accounts for 30% to 60% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition.
The thermosetting resin composition according to claim 1, wherein the curing agent further comprises a cyanate resin and/or a bismaleimide-triazine resin;

Preferably, the cyanate resin and/or bismaleimide-triazine resin accounts for 0% to 50% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition.
The thermosetting resin composition according to claim 1 or 2, wherein the curing agent further comprises an SMA resin;

Preferably, the SMA resin accounts for 0% to 40% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition.
The thermosetting resin composition according to any one of claims 1 to 3, wherein the curing agent further comprises a phenol resin;

Preferably, the phenolic resin accounts for 0% to 20% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition.
The thermosetting resin composition according to any one of claims 1 to 4, wherein the thermosetting resin composition further comprises an organic halogen-free flame retardant;

Preferably, the organic halogen-free flame retardant is a phosphorus-containing flame retardant;

Preferably, the total amount of the epoxy resin and the curing agent in the thermosetting resin composition is from 0 to 15 parts by weight based on 100 parts by weight of the organic halogen-free flame retardant.
The thermosetting resin composition according to any one of claims 1 to 5, wherein the thermosetting resin composition further contains a filler and/or an accelerator.
Use of the thermosetting resin composition according to any one of claims 1 to 6 in a resin sheet, a resin composite metal foil, a prepreg, a laminate, a metal foil-clad laminate or a printed wiring board.