WO2016095437A1 - Thermosetting resin composition and application thereof - Google Patents

Abstract

The present invention provides a thermosetting resin composition, comprising thermosetting resin with an unsaturated bond and an alkene compound. In the present invention, an alkene compound with two or more unsaturated bonds such as alkenyl and alkynyl is selected to match thermosetting resin with an unsaturated bond, to obtain a thermosetting resin composition with an excellent dielectric property. On the basis of ensuring the excellent dielectric property, the thermosetting resin composition also has excellent thermal resistance, production and processing properties, and a drilling processability. The thermosetting resin composition in the present invention can be used to prepare a resin sheet material, resin composite tinsel, prepreg, an laminated board, a metal foil-clad laminated board, and a printed wiring board, and can also be used to prepare adhesive and a coating material, and can be further used for the building, aviation, shipping, and automobile industries.

Description

Thermosetting resin composition and application thereof Technical field

The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition and its use in a resin sheet, a resin composite metal foil, a prepreg, a laminate, a metal foil-clad laminate, a printed wiring board, and the like. application.

Background technique

In recent years, with the rapid development of computers and information communication equipment, in order to transmit and process a large amount of information at high speed, the operation signals tend to be high-frequency. At the same time, in order to meet the trend of use and development of various electronic products, the circuit boards are oriented toward high layers. The development of high-density interconnects requires that the substrate material not only have low dielectric constant and low dielectric loss tangent to meet the high-frequency transmission of signals, but also have good heat resistance, processability and superior reliability. Among the materials currently used for printed circuit board substrates, epoxy-based adhesives are widely used. The circuit board made of such epoxy has a high dielectric constant (about 4.4) and a dielectric loss tangent (about 0.02), which cannot meet the requirements of high frequency signal.

In view of the fact that the high dielectric constant and dielectric loss tangent of ordinary epoxy resins cannot meet the requirements of high frequency, people are also looking for materials with lower dielectric constant and dielectric loss tangent, such as thermoplastic fluorine-containing resins ( Polytetrafluoroethylene), but since fluororesin generally has a high melting temperature and a high melt viscosity, press molding must be carried out under high temperature and high pressure, and processability, dimensional stability and pore metal are produced in the production of high-layer printed circuit boards. Shortcomings such as insufficientization.

In view of the deficiencies of fluororesins, research work in place of fluororesins has become a research hotspot. Polyphenylene ether has excellent dielectric constant and dielectric loss performance, but it also has high melting temperature and high melt viscosity. It is difficult to ensure all electrical properties and mechanical properties (high copper foil stripping) while ensuring excellent dielectric properties. Strength and dimensional stability, etc.). In addition, the processability in manufacturing and processing is poor, and it is easy to cause scrapping. The pass rate is low.

In order to obtain circuit substrate materials that meet the high frequency requirements of signals, many attempts have been made by those skilled in the art, and it is expected that other processing properties and reliability are optimized on the basis of satisfying excellent dielectric properties, but ultimately It is difficult to achieve, or to maintain excellent dielectric properties, but insufficient heat resistance, or excellent heat resistance but poor processability.

U.S. Patent No. 5,932,682 discloses the use of a double epoxy resin containing a ketal or an acetal chain, but it is essentially a difunctional epoxy resin at both ends of the molecular chain, which is an epoxy resin and is difficult to meet the requirements of high frequency signal. Such ketals or acetal chains have not been modified so that their compounds contain at least two or more unsaturated bonds such as alkenyl and alkynyl groups as curing agents or polymerized monomers to satisfy electronic device products. Report on high frequency requirements.

Summary of the invention

In view of the problems of the prior art, one of the objects of the present invention is to provide a thermosetting resin composition for solving the problems of insufficient dielectric properties, poor processability, and poor reliability of a thermosetting polymer in the prior art, and obtaining excellent dielectric properties. At the same time of performance, it also has excellent heat resistance, processability and drilling performance.

In order to achieve the above object, the present invention adopts the following technical solutions:

A thermosetting resin composition comprising a thermosetting resin containing an unsaturated bond and an olefin compound having the following molecular structural formula:

Wherein R ₁ and R _{2 are} independently a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an alkylalkyl group, an alkynyl group. Any one of an alkylene group, an alkylene hydrocarbon group, an alkenylene group, an alkylene heteroalkenylene group, an alkynylene group or an alkylene alkynylene group; and R ₁ and R ₂ may be the same or different;

R ₃ and R _{4 are} independently an alkylene group, an alkylene hydrocarbon group, an alkenylene group, an alkylene alkenylene group, an alkylene heteroalkenylene group, an alkynylene group, a cycloalkylene group, an alkylene cycloalkylene group. An alkylenecycloalkylene group, an eneene naphthene group, an eneene naphthene alkenylene group, an alkylene cycloalkenylene alkenylene group, an alkyncycloalkylene group, an alkyncycloalkanylene group, Heterocycloalkylene, alkylene heterocycloalkylene, alkylene heterocycloalkylene, alkylene heteroalkylene, alkylene heteroalkenylene, alkylene heterocycloalkenylene, alkyne Heterocycloalkylene, alkyne heteroalkenylene alkynylene, cycloalkenylene, alkylene cycloalkenylene, alkylene cycloalkenylene, eneene cycloalkenyl, eneeneene alkenylene , alkylene cycloalkenylene alkenylene, alkynylene cycloalkenylene, alkynylene cycloalkynylene, heterocycloalkylene, alkylene heterocycloalkenylene, alkylene heterocycloalkylene, alkene Heterocyclic olefinic group, alkylene heteroalkenylene group, alkylene heteroalkenylene alkenylene group, alkyne heterocycloalkenylene group, alkyne heteroalkenylene alkynylene group, aromatic group, alkylene aromatic group , an alkylene aromatic alkylene group, an alkylene aromatic group, an alkylene aromatic alkenylene group, Hydrocarbon aromatic alkenylene, alkyne aromatic group, alkyne aromatic alkynylene group, heteroaromatic group, alkylene heteroaryl group, alkylene heteroalkylene group, alkylene aromatic group, alkylene Any of a heteroaromatic alkenylene group, an alkylene heteroalkenylene group, an alkyne heteroaryl group, an alkyne heteroalkenylene group, a 1,4-alkyl substituted piperazine, a carbonyl group or a thiocarbonyl group. One; R3 and R4 may be the same or different;

Of the four groups of R ₁ , R ₂ , R ₃ and R ₄ , two or more groups contain an unsaturated bond.

Of the four groups R ₁ , R ₂ , R ₃ and R ₄ , two or more groups contain an unsaturated bond, which is a carbon-carbon double bond, a carbon-carbon triple bond, or a carbon nitrogen Double bond, carbon-nitrogen triple bond, nitrogen-nitrogen double bond or nitrogen-nitrogen triple bond.

R ₁ and R ₂ may be in the same ring structure as the co-adjacent carbon atoms.

Preferably, R ₁ and R _{2 are} independently hydrogen, alkyl, cycloalkyl, heterocyclyl, heterocycloalkyl, aryl, heteroaryl, alkanealkyl, alkylene or alkylene hydrocarbon. Any of them.

Preferably, R ₃ and R _{4 are} independently alkenylene, alkenylene, alkenylene, alkenylene, alkynylene, alkenylene, enecycloalkenylene, sub a hydrocarbon cycloalkylene alkenylene group, an alkynylene cycloalkenylene group, an alkynylene naphthylene alkynylene group, an eneene heteroalkylene group, an alkylene heteroalkenylene group, an alkylene heterocycloalkanylene group, Alkyne heterocycloalkylene, alkyne heteroalkenylene alkynylene, cycloalkenylene, alkylene cycloalkenylene, alkylene cycloalkenylene, eneeneene, enelenene Alkenyl, alkylene cycloalkenylene, alkenylene cycloalkenylene, alkynylene cycloalkenylene, heterocycloalkenylene, alkylene heterocycloalkenylene, alkylene heterocycloalkylene, Alkene heterocycloalkylene, alkylene heteroalkenylene, alkylene heteroalkenylene, alkyne heterocycloalkenylene, alkyne heteroalkenylene alkynylene, alkylene aromatic group, sub Aromatic aromatic alkenylene, alkylene aromatic alkenylene, alkyne aromatic group, alkyne aromatic alkynylene group, alkylene aromatic group, alkylene aromatic alkenylene group, alkylene heteroaromatic Alkenylene, alkyne heteroaromatic, alkyne heteroalkenylene, 1, 4-alkyl-substituted piperazine, carbonyl or thiocarbonyl.

In the curing agent of the present invention, one side of R ₃ (or R ₄ ) is bonded to an oxygen atom, and the other side is bonded to an end group of the molecule, and the terminal group may have an unsaturated bond, and the unsaturated bond is carbon. Carbon double bond, carbon-carbon triple bond, carbon-nitrogen double bond, carbon-nitrogen triple bond, nitrogen-nitrogen double bond or nitrogen-nitrogen triple bond. The end group may also be free of unsaturated bonds. For the purpose of the invention

Indicates the terminal group of the molecular chain of the curing agent.

Preferably, the olefin compound accounts for 5 to 95%, preferably 35 to 70%, such as 35%, 40%, 45%, 50%, 55%, 60%, 65%, of the total mass of the thermosetting resin composition. 70%.

Preferably, the unsaturated bond in the thermosetting resin containing an unsaturated bond is a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-nitrogen double bond, a carbon-nitrogen triple bond, a nitrogen-nitrogen double bond, or a nitrogen-nitrogen triple bond.

Preferably, the thermosetting resin containing an unsaturated bond is selected from the group consisting of a polyphenylene ether resin, a cyanate resin, a bismaleimide-triazine resin, a 1,2-polybutadiene resin, a styrene-butadiene resin or a double Any one or a mixture of at least two of maleimides.

Preferably, the unsaturated bond contains 5 to 95%, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, based on the total weight of the thermosetting resin composition. 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%, preferably 30-65%.

Preferably, the polyphenylene ether resin is a polyphenylene ether resin having an unsaturated group in a molecular structure, and the unsaturated group is a vinyl group, an allyl group, a styryl group, an acrylate group or an alkynyl group.

Preferably, the thermosetting resin composition further contains an organic additive type flame retardant which is a phosphorus-based flame retardant and/or a halogen-based flame retardant.

Preferably, the phosphorus flame retardant is a phosphazene flame retardant, a phosphate ester FRX series flame retardant, tris(2,6-dimethylphenyl)phosphine, resorcinol double [2 (6, 6) - dimethylphenyl)phosphate], resorcinol tetraphenyl diphosphate, triphenyl phosphate or bisphenol A (diphenyl phosphate), or a mixture of at least two.

Preferably, the halogen-based flame retardant is any of decabromodiphenyl ether, brominated styrene, brominated polycarbonate, decabromodiphenylethane or ethylene bis-tetrabromophthalimide. One or a mixture of at least two.

Preferably, the organic additive type flame retardant accounts for 1 to 50%, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45% of the total weight of the thermosetting resin composition. %, preferably 10% to 30%.

Preferably, the thermosetting resin composition further comprises a filler and/or a curing initiator.

Preferably, the filler comprises from 5 to 80%, such as 10%, 20%, 30%, 40%, 50%, 60% or 70%, preferably 10% to 30%, based on the total weight of the thermosetting resin composition.

Preferably, the filler is crystalline silicon micropowder, molten silicon micropowder, spherical silicon micropowder, aluminum hydroxide, magnesium hydroxide, kaolin, talc, calcium silicate, metal oxide, nitride, silicon carbide, titanium dioxide, Moray Stone, hollow glass microbead, potassium titanate fiber, silicon carbide single crystal fiber, boron nitride fiber, alumina single crystal fiber, glass short fiber, polytetrafluoroethylene powder, polyphenylene sulfide powder, polystyrene powder Or any one of styrene-butadiene rubber powders or a mixture of at least two.

Preferably, the metal oxide is any one of alumina, magnesia, cerium oxide, boron oxide or cerium oxide or a mixture of at least two.

Preferably, the nitride is boron nitride or/and silicon nitride.

Preferably, the curing initiator accounts for 1 to 10%, such as 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, preferably 2 to 5, based on the total weight of the thermosetting resin composition. %.

Preferably, the curing initiator is benzoyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, di-(tert-butylperoxyisopropyl)benzene, 2,5-di ( 2-ethylhexanoylperoxy)-2,5-dimethylhexane or 2,5-di(2-ethylhexanoylperoxy)-2,5-dimethyl-3-hexyne, etc. Any one or a mixture of at least two.

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 thermosetting resin composition. In addition, the "include" of the present invention may also be replaced by a closed "for" or "consisting of".

For example, the 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, a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds.

Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing the thermosetting resin composition as described above in a solvent.

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, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone. Above dissolution The agents may be used singly or in combination of two or more. Preferred are aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, methyl ethyl ketone, methyl ethyl ketone, and methyl isobutyl group. A ketone flux such as a ketone or a cyclohexanone is used in combination.

A third object of the present invention is to provide a prepreg comprising a reinforcing material and a thermosetting resin composition as described above adhered to the reinforcing material by impregnation and drying.

A fourth object of the present invention is to provide a laminate comprising at least one prepreg as described above.

A fifth object of the present invention is to provide a copper clad laminate comprising at least one laminated prepreg as described above and laminated on one side of the laminated prepreg Or copper foil on both sides.

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

The present invention obtains a thermosetting resin composition having excellent dielectric properties by blending an olefin compound containing two or more unsaturated bonds such as an alkenyl group and an alkynyl group with a thermosetting resin. The thermosetting resin composition has excellent heat resistance, production processability, and drilling processability while ensuring excellent dielectric properties.

The thermosetting resin composition of the present invention can be used for preparing an adhesive in addition to a resin sheet, a resin composite metal foil, a prepreg, a laminate, a metal foil-clad laminate, and a printed wiring board. , coatings, can also be used in the construction, aerospace, marine and automotive industries.

detailed description

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

Example 1

Using 55 parts of SA9000 polyphenylene ether, 8 parts of olefin compound (A), 3 parts of dicumyl peroxide, 13 parts of BT93 (ethylene bis-tetrabromophthalimide), 20 parts of SC2050MB, using toluene Above The compound is dissolved and prepared into a suitable viscosity. This type of glue was used to wet the 2116 type electronic grade glass cloth, and the solvent was removed in an oven at 115 ° C to obtain a B-stage prepreg sample having a resin content of 54%. The sum of the SA9000, the olefin compound (A), dicumyl peroxide, BT93 (ethylene bistetrabromophthalimide) and SC2050MB parts by weight is 100 parts.

Eight sheets of the prepreg prepared above and two sheets of one ounce of electrolytic copper foil were laminated together and laminated by a hot press to obtain a double-sided copper clad laminate. The lamination conditions are as follows: 1. When the feed temperature is between 80 ° C and 120 ° C, the heating rate is controlled at 0.5 ° C to 4.0 ° C / min; 2, the pressure is designed to be 20 kg / cm ² ; 3, the curing temperature is 190 ° C, and maintained at 90 minute. The obtained double-sided copper clad laminates were tested for performance, and the corresponding properties are shown in Table 1.

CH ₂ =CH-O-CH ₂ -O-CH=CH ₂

(A)

Example 2

Using 52 parts of SA9000 polyphenylene ether, 10 parts of olefin compound (B), 3 parts of benzoyl peroxide, 15 parts of SPB-100 (phosphazene), 20 parts of SC2050MB, the above compound was dissolved using toluene, and prepared to a suitable viscosity. Glue. This type of glue was used to wet the 2116 type electronic grade glass cloth, and the solvent was removed in an oven at 115 ° C to obtain a B-stage prepreg sample having a resin content of 54%. The sum of the SA9000, the olefin compound (B), dicumyl peroxide, SPB-100 (phosphazene) and SC2050MB parts by weight is 100 parts.

Eight sheets of the prepreg prepared above and two sheets of one ounce of electrolytic copper foil were laminated together and laminated by a hot press to obtain a double-sided copper clad laminate. The lamination conditions are as follows: 1. When the feed temperature is between 80 ° C and 120 ° C, the heating rate is controlled at 0.5 ° C to 4.0 ° C / min; 2, the pressure is designed to be 20 kg / cm ² ; 3, the curing temperature is 190 ° C, and maintained at 90 minute. The obtained double-sided copper clad laminates were tested for performance, and the corresponding properties are shown in Table 1.

Examples 3 to 6

A double-sided copper-clad laminate was prepared in the same manner as in Example 1, and the specific formulation and performance test results are shown in Table 1.

Comparative example 1

33 parts of SA9000 polyphenylene ether, 12 parts of styrene-butadiene block polymer, 22 parts of TAIC (triallyl isocyanurate), 3 parts of dicumyl peroxide, 13 parts of BT93 (B Bis-tetrabromophthalimide), 20 parts of SC2050MB, the above compound was dissolved using toluene, and prepared into a suitable viscosity. This type of glue was used to wet the 2116 type electronic grade glass cloth, and the solvent was removed in an oven at 115 ° C to obtain a B-stage prepreg sample having a resin content of 54%. The SA9000, styrene-butadiene block polymer, TAIC (triallyl isocyanurate), dicumyl peroxide, BT93 (ethylene bis-tetrabromophthalimide) The sum of the parts by weight of SC2050MB is 100 parts.

Eight sheets of the prepreg prepared above and two sheets of one ounce of electrolytic copper foil were laminated together and laminated by a hot press to obtain a double-sided copper clad laminate. The lamination conditions are as follows: 1. When the feed temperature is between 80 ° C and 120 ° C, the heating rate is controlled at 0.5 ° C to 4.0 ° C / min; 2, the pressure is designed to be 20 kg / cm ² ; 3, the curing temperature is 190 ° C, and maintained at 90 minute. The obtained double-sided copper-clad laminates were tested for performance, and the corresponding properties are shown in Table 1.

Comparative example 2

Use 32 parts of SA9000 polyphenylene ether, 12 parts of thermoplastic polyphenylene ether, 20 parts of TAIC (triallyl isocyanurate), 3 parts of dicumyl peroxide, 13 parts of SPB-100 (phosphazene), 20 SC2050MB, The above compound was dissolved using toluene and prepared into a gum of a suitable viscosity. This type of glue was used to wet the 2116 type electronic grade glass cloth, and the solvent was removed in an oven at 115 ° C to obtain a B-stage prepreg sample having a resin content of 54%. The sum of the SA9000, thermoplastic polyphenylene ether, TAIC (triallyl isocyanurate), dicumyl peroxide, SPB-100 (phosphazene) and SC2050MB parts by weight is 100 parts.

Eight sheets of the prepreg prepared above and two sheets of one ounce of electrolytic copper foil were laminated together and laminated by a hot press to obtain a double-sided copper clad laminate. The lamination conditions are as follows: 1. When the feed temperature is between 80 ° C and 120 ° C, the heating rate is controlled at 0.5 ° C to 4.0 ° C / min; 2, the pressure is designed to be 20 kg / cm ² ; 3, the curing temperature is 190 ° C, and maintained at 90 minute. The obtained double-sided copper-clad laminates were tested for performance, and the corresponding properties are shown in Table 1.

Comparative example 3

Use 42 parts of SA9000 polyphenylene ether, 12 parts of 1,2-polybutadiene, 10 parts of BMI (bismaleimide), 3 parts of benzoyl peroxide, 13 parts of decabromodiphenylethane, 20 parts SC2050MB, the above compound was dissolved using toluene and prepared into a suitable viscosity. This type of glue was used to wet the 2116 type electronic grade glass cloth, and the solvent was removed in an oven at 115 ° C to obtain a B-stage prepreg sample having a resin content of 54%. The sum of the parts by weight of the SA9000, 1,2-polybutadiene, BMI (bismaleimide), benzoyl peroxide, decabromodiphenylethane and SC2050MB was 100 parts.

Eight sheets of the prepreg prepared above and two sheets of one ounce of electrolytic copper foil were laminated together and laminated by a hot press to obtain a double-sided copper clad laminate. The lamination conditions are as follows: 1. When the feed temperature is between 80 ° C and 120 ° C, the heating rate is controlled at 0.5 ° C to 4.0 ° C / min; 2, the pressure is designed to be 20 kg / cm ² ; 3, the curing temperature is 190 ° C, and maintained at 90 minute. The obtained double-sided copper-clad laminates were tested for performance, and the corresponding properties are shown in Table 1.

The obtained double-sided copper-clad laminates were tested for performance, and the corresponding properties are shown in Table 1.

Table 1 Performance test results of copper-clad laminate obtained from thermosetting resin composition

It can be seen from the test results of the above examples and comparative examples that the use of the olefin compound of the present invention has better dielectric properties (lower Dk value) and better heat resistance (dip resistance, PCT test) For a long time, it can not be stratified.) The prepreg volatiles are also at a lower level, which is easy for customers to store, process and have stable performance.

The above performance test methods are as follows:

Dielectric constant (Dk), dielectric loss (Df): The test uses the IPC-TM-650 2.5.5.9 method;

Tg: Measured according to the DSC test method specified in IPC-TM-650 2.4.25.

Td: The copper clad laminate was etched away from the copper foil, and the substrate was tested using a thermogravimetric analyzer (TGA), and the temperature was raised at 10/min in a nitrogen atmosphere when the thermal weight loss reached a weight loss of 5%.

PCT: The copper clad laminate is etched away from the copper foil, the substrate is placed in a steam pressure cooker, treated at 121 ° C, 2 atm for 2 hours, and then immersed in a tin furnace at a temperature of 288 ° C, when the substrate is blistering or Record the corresponding time when stratifying. The evaluation was terminated when the substrate did not show blistering or delamination in the tin furnace for more than 5 minutes.

Evaluation of the soldering resistance: The copper-clad laminate was immersed in a tin furnace at a temperature of 288 ° C for 20 seconds, and then taken out to room temperature, and then immersed in a tin furnace for 5 times, and the solder resistance was evaluated by observing the appearance.

Prepreg Volatile: The prepreg was placed in an oven at 163 ° C and baked for 30 minutes to test for volatiles.

Water absorption rate: test using IPC-TM-650 2.6.2.1;

The embodiments described above are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Therefore, equivalent changes in the structures, features, and principles described in the claims of the present invention. Or modifications are included in the scope of the present invention.

The Applicant declares that the present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must be implemented by the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims (12)

1. A thermosetting resin composition comprising a thermosetting resin containing an unsaturated bond and an olefin compound having the following molecular structural formula:

   

   Wherein R ₁ and R _{2 are} independently a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heteroaryl group, an alkylalkyl group, an alkynyl group. Any one of an alkylene group, an alkylene hydrocarbon group, an alkenylene group, an alkylene heteroalkenylene group, an alkynylene group or an alkylene alkynylene group;

   R ₃ and R _{4 are} independently an alkylene group, an alkylene hydrocarbon group, an alkenylene group, an alkylene alkenylene group, an alkylene heteroalkenylene group, an alkynylene group, a cycloalkylene group, an alkylene cycloalkylene group. An alkylenecycloalkylene group, an eneene naphthene group, an eneene naphthene alkenylene group, an alkylene cycloalkenylene alkenylene group, an alkyncycloalkylene group, an alkyncycloalkanylene group, Heterocycloalkylene, alkylene heterocycloalkylene, alkylene heterocycloalkylene, alkylene heteroalkylene, alkylene heteroalkenylene, alkylene heterocycloalkenylene, alkyne Heterocycloalkylene, alkyne heteroalkenylene alkynylene, cycloalkenylene, alkylene cycloalkenylene, alkylene cycloalkenylene, eneene cycloalkenyl, eneeneene alkenylene , alkylene cycloalkenylene alkenylene, alkynylene cycloalkenylene, alkynylene cycloalkynylene, heterocycloalkylene, alkylene heterocycloalkenylene, alkylene heterocycloalkylene, alkene Heterocyclic olefinic group, alkylene heteroalkenylene group, alkylene heteroalkenylene alkenylene group, alkyne heterocycloalkenylene group, alkyne heteroalkenylene alkynylene group, aromatic group, alkylene aromatic group , an alkylene aromatic alkylene group, an alkylene aromatic group, an alkylene aromatic alkenylene group, Hydrocarbon aromatic alkenylene, alkyne aromatic group, alkyne aromatic alkynylene group, heteroaromatic group, alkylene heteroaryl group, alkylene heteroalkylene group, alkylene aromatic group, alkylene Any of a heteroaromatic alkenylene group, an alkylene heteroalkenylene group, an alkyne heteroaryl group, an alkyne heteroalkenylene group, a 1,4-alkyl substituted piperazine, a carbonyl group or a thiocarbonyl group. One type;

   Of the four groups of R ₁ , R ₂ , R ₃ and R ₄ , two or more groups contain an unsaturated bond.
2. The thermosetting resin composition according to claim 1, wherein two or more of the four groups of R ₁ , R ₂ , R ₃ and R ₄ contain an unsaturated bond, The unsaturated bond is a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-nitrogen double bond, a carbon-nitrogen triple bond, a nitrogen-nitrogen double bond, or a nitrogen-nitrogen triple bond.
3. The thermosetting resin composition according to claim 1 or 2, wherein R ₁ and R ₂ are in the same ring structure as the carbon atoms which are adjacent to each other.
4. The thermosetting resin composition according to any one of claims 1 to 3, wherein R ₁ and R _{2 are} independently a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, a heterocycloalkyl group, an aromatic group, Any one of a heteroaryl group, an alkylene group, an alkylene group or an alkylene hydrocarbon group.
5. The thermosetting resin composition according to any one of claims 1 to 4, wherein R ₃ and R _{4 are} independently an alkenylene group, an alkenylene group, an alkylene group, an alkynylene group, An alkenylenealkylene group, an eneene naphthene alkenylene group, an alkylene cycloalkenylene alkenylene group, an alkynylene cycloalkenylene group, an alkynylene naphthylene alkynylene group, an alkylene heterocycloalkylene group, a sub Olecycloalkenylene alkenylene, alkylene heterocycloalkenylene, alkyne heterocycloalkylene, alkyne heteroalkenylene alkynylene, cycloalkenylene, alkylene cycloalkenylene, alkylene cycloalkenyl A hydrocarbylene group, an eneene cycloalkenylene group, an enelenene alkenylene group, an alkylene cycloalkenylene group, an alkyne cycloalkenylene group, an alkyne cycloalkenylene group, a heterocycloalkenylene group , an alkylene heterocycloalkenylene, an alkylene heterocycloalkylene, an enelenene group, an alkene heteroalkenylene, an alkylene heteroalkenylene, an alkyne heterocycloalkenylene , alkyne heteroalkenylene alkynylene group, alkylene aromatic group, alkylene aromatic alkenylene group, alkylene aromatic alkenylene group, alkyne aromatic group, alkyne aromatic alkynylene group, alkylene aromatic Pillaring group, alkylene heteroalkenylene group, alkylene heteroaromatic Group, an alkynylene heteroaromatic alkylene group, an alkynylene heteroaromatic strut alkynylene, an alkyl-substituted 1,4-piperazine, any one or a carbonyl group a thiocarbonyl group.
6. The thermosetting resin composition according to any one of claims 1 to 5, wherein the olefin compound accounts for 5 to 95%, preferably 35 to 70%, based on the total mass of the thermosetting resin composition;

   Preferably, the unsaturated bond in the thermosetting resin containing an unsaturated bond is a carbon-carbon double bond, carbon carbon a triple bond, a carbon-nitrogen double bond, a carbon-nitrogen triple bond, a nitrogen-nitrogen double bond or a nitrogen-nitrogen triple bond;

   Preferably, the thermosetting resin containing an unsaturated bond is selected from the group consisting of a polyphenylene ether resin, a cyanate resin, a bismaleimide-triazine resin, a 1,2-polybutadiene resin, a styrene-butadiene resin or a double Any one or a mixture of at least two of maleimides;

   Preferably, the thermosetting resin containing an unsaturated bond accounts for 5 to 95%, preferably 30 to 65%, based on the total weight of the thermosetting resin composition;

   Preferably, the polyphenylene ether resin is a polyphenylene ether resin having an unsaturated group in a molecular structure, and the unsaturated group is a vinyl group, an allyl group, a styryl group, an acrylate group or an alkynyl group.
7. The thermosetting resin composition according to any one of claims 1 to 6, wherein the thermosetting resin composition contains an organic additive type flame retardant, and the organic additive flame retardant is a phosphorus-based flame retardant and/or Halogen flame retardant;

   Preferably, the organic additive type flame retardant accounts for 1 to 50%, preferably 10% to 30%, based on the total weight of the thermosetting resin composition;

   Preferably, the phosphorus flame retardant is a phosphazene flame retardant, a phosphate ester FRX series flame retardant, tris(2,6-dimethylphenyl)phosphine, resorcinol double [2 (6, 6) - dimethylphenyl)phosphate], resorcinol tetraphenyl diphosphate, triphenyl phosphate or bisphenol A (diphenyl phosphate), or a mixture of at least two;

   Preferably, the halogen-based flame retardant is any of decabromodiphenyl ether, brominated styrene, brominated polycarbonate, decabromodiphenylethane or ethylene bis-tetrabromophthalimide. One or a mixture of at least two.
8. The thermosetting resin composition according to any one of claims 1 to 7, wherein the thermosetting resin composition comprises a filler and/or a curing initiator;

   Preferably, the filler accounts for 5 to 80%, preferably 10% to 30%, based on the total weight of the thermosetting resin composition;

   Preferably, the filler is crystalline silicon micropowder, molten silicon micropowder, spherical silicon micropowder, aluminum hydroxide, magnesium hydroxide, kaolin, talc, calcium silicate, metal oxide, nitride, silicon carbide, titanium dioxide, Moray Stone, hollow glass microbeads, potassium titanate fibers, silicon carbide single crystal fibers, boron nitride fibers, alumina single crystal fibers, glass short fibers, polytetrafluoroethylene powder, polyphenylene sulfide powder, polystyrene powder or Any one or a mixture of at least two of styrene-butadiene rubber powders;

   Preferably, the metal oxide is any one of alumina, magnesia, cerium oxide, boron oxide or cerium oxide or a mixture of at least two;

   Preferably, the nitride is boron nitride or/and silicon nitride;

   Preferably, the curing initiator accounts for 1 to 10%, preferably 2 to 5%, based on the total weight of the thermosetting resin composition;

   Preferably, the curing initiator is benzoyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, di-(tert-butylperoxyisopropyl)benzene, 2,5-di ( Of 2-ethylhexanoyl peroxy)-2,5-dimethylhexane or 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethyl-3-hexyne Any one or a mixture of at least two.
9. A resin glue obtained by dissolving or dispersing a thermosetting resin composition according to any one of claims 1 to 8 in a solvent.
10. A prepreg comprising a reinforcing material and a thermosetting resin composition according to any one of claims 1 to 8 adhered to the reinforcing material by impregnation and drying.
11. A laminate comprising at least one prepreg according to claim 10.
12. A copper clad laminate comprising at least one laminated prepreg according to claim 10 and copper laminated on one or both sides of the laminated prepreg Foil.