TW202126749A - Resin composition and prepreg sheet using same, and insulating plate - Google Patents

Abstract

The present invention relates to a resin composition and a prepreg sheet using same, and an insulating plate. The resin composition comprises a combination of a modified maleimide compound and a polymer containing an alkenyl group. The modified maleimide compound is prepared from compound (A) or an organometallic salt of an amino-containing silane, and compound (B) containing at least two maleimido groups. The resin composition provided by the present invention has a higher bonding strength, and can be used to prepare a laminate with a high peel strength, a low dielectric constant, a high heat resistance and a high flame retardancy, and the modified maleimide compound has a good compatibility with a resin and will not crystallize easily during processing.

Description

Resin composition, prepreg sheet and insulating board using the same

The present invention relates to the technical field of printed circuits, in particular to a resin composition and a prepreg sheet and insulating board using the resin composition.

With the progress of the electrical and electronic industry and the rapid development of terminal electronics, the development direction of electronic circuit substrates is light and thin, high performance, high reliability, and environmental protection. As a thermosetting polyimide resin, maleimide resin has outstanding performance in mechanical properties, electrical properties, heat resistance and solvent resistance. Among electronic circuit substrates, bismaleimide resin or polymaleimide resin has been widely used in the field of packaging substrates. However, one of the current problems is that the maleimide resin has been insufficient in adhesion. Therefore, it is generally used in combination with epoxy resins, phenolic resins and cyanate resins with better adhesion. When bismaleimide is combined with a lower polar resin, its adhesion performance is still very poor.

CN107109055A discloses a thermosetting resin composition, which contains a polyimide compound, a modified polybutadiene, and an inorganic filler. The polyimide compound has at least two N-substituted maleimide groups. The structural unit of the maleimide compound and the structural unit derived from the diamine compound. The thermosetting resin composition obtained by the invention has excellent heat resistance, a small dielectric loss tangent, and a smooth surface. However, the bonding performance of the composition is poor, and the use of it The peel strength of the prepared copper clad laminate is relatively low.

CN102115569B discloses a dielectric material composition comprising (a) 1 to 90 parts by weight of polybutadiene, its branch has maleic anhydride, its terminal has a carboxyl group, a hydroxyl group, or an epoxy group, and its weight is average The molecular weight is between 1200 and 15000; (b) 5 to 90 parts by weight of chain scission rearranged polyphenylene ether, and the weight average molecular weight is between 2000 and 8000; (c) 1 to 30 parts by weight of dima Leximine; and (d) 1 to 30 parts by weight of epoxy resin. The above-mentioned polybutadiene with excellent electrical properties can be modified polyphenylene ether, and bismaleimide is used to increase the cross-linking density of the resin, and the heat resistance and Tg are greatly improved. In addition, polybutene (PB) with different proportions /Polyphenylene ether (PPE)/BMI (BMI) can form a semi-interpenetrating structure, which can obtain a medium with higher Tg, low dielectric constant, low dissipation factor, and excellent solvent resistance and heat resistance. Electric materials. However, the adhesion of the dielectric material to materials such as copper foil and glass fiber cloth is poor, and it is difficult to obtain a laminate with high peel strength.

CN104177809B discloses a halogen-free resin composition comprising: (A) 100 parts by weight of polyphenylene ether resin; (B) 10 to 50 parts by weight of maleimide resin; (C) 5 to 100 parts by weight of poly Butadiene copolymer; (D) 5 to 30 parts by weight of cyanate ester resin; and (E) 15 to 150 parts by weight of phosphazene compound. The invention contains specific components and proportions to achieve high glass transition temperature, low thermal expansion coefficient, low dielectric properties, heat resistance, flame retardancy and halogen-free circuit board characteristics; it can be made into semi-cured Film or resin film can be applied to metal laminates and printed circuit boards. However, the bonding performance of the composition is poor, and the peel strength of the prepared laminate is low.

Therefore, there is an urgent need in the art to develop a resin composition with high bonding properties to prepare laminates with high peel strength, low dielectric loss, high heat resistance, and high flame retardancy at the same time.

One of the objectives of the present invention is to provide a resin composition, the aforementioned resin composition has high bonding performance, can be prepared to obtain high peel strength, low dielectric, high heat resistance and high flame retardant laminate.

To achieve this goal, the present invention adopts the following technical means:

The present invention provides a resin composition, the aforementioned resin composition comprising a combination of a modified maleimide compound and a polymer containing an olefin group;

The aforementioned modified maleimine compound is prepared from compound (A) or an organometallic salt containing aminosilane and a compound (B) containing at least two maleimine groups. The molecule of the aforementioned compound (A) The structure is as follows:

The aforementioned R ₁ , R ₂ and R ₃ are each independently selected from C1 to C6 (e.g. C1, C2, C3, C4, C5 or C6) alkyl groups;

； The structure of the aforementioned Y is -Y ₁ -Y _{2 -or}

；

、

、

、

或

中的任意一種； The aforementioned Y ₁ and Y ₂ are each independently selected from -CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C ₅ H ₁₀ -, -C ₃ H _6- N-, -C ₂ H ₄ -N-,

,

,

,

or

Any of

，

或

中的任意一種； The aforementioned Y _{3 is} selected from -H, -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , -C ₅ H ₁₁ , -C ₈ H ₁₇ , -C ₁₅ H ₃₁ ,

,

or

Any of

The aforementioned m is 0 or 1.

In the present invention, a compound (B) containing at least two maleimine groups is heated to react with an amino-containing silane compound (A) or an organometallic salt of amino-containing silane to obtain a modified horse containing silane Leimine compounds. When it is used in the resin composition of composite materials, it has better compatibility with low-polarity resins, avoids the volatilization of the silane coupling agent during the drying process of the prepreg, and can reduce the bismaleimide Reactivity with other resins reduces the curing stress of the resin composition, increases the adhesion of the resin composition to the reinforcing material or the conductive layer, and maintains low dielectric loss and high heat resistance. In addition, the modified maleimide compound has good compatibility with the resin and is not easy to crystallize during processing.

In the present invention, the N atom of the compound (A) or the organometallic salt of aminosilane is connected to the ortho position of the carbonyl group in the compound (B), exemplarily forming a modified maleimide compound with the following structure:

The above structure only expresses the connection method of compound (A) or organometallic salt of aminosilane and compound (B) after reaction, and is not limited to the above structure. Depending on the structure of the raw material, the obtained modified maleimide compound The structure will also be different.

Ideally, the aforementioned compound (A) has any one of the following structures shown in formula I to formula III:

The aforementioned R ₁ , R ₂ , R ₃ , Y ₁ , Y ₂ and Y ₃ all have the same selection range as the foregoing.

Ideally, the aforementioned R ₁ , R ₂ and R ₃ are each independently selected from any one of _{CH 3} , C ₂ H ₅ or C ₃ H _7.

、

或

中的任意一種。 Ideally, the aforementioned Y ₁ and Y ₂ are each independently selected from

,

or

Any of them.

The ideal compound (A) of the present invention contains the above-mentioned linking groups. These linking groups can extend the chain length, avoid the influence of the cross-linked structure of the resin on the silicone after curing, and can further improve the bonding performance of the resin. The main chain of the structure has higher rigidity, which is conducive to high heat resistance.

Ideally, the aforementioned compound (B) has a structure represented by the following formula IV or formula V:

、

或

中的任意一種； The aforementioned X is selected from -CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C ₅ H ₁₀ -,

,

or

Any of

、

或

中的任意一種，理想為-H、-CH₃、-C₂H₅、-C₃H₇、-C₄H₉、-C₅H₁₁、-C₈H₁₇、-C₁₅H₃₁、

、

或

中的任意一種； The aforementioned R, R ₄ to R ₁₁ are each independently selected from -H, C1 to C15 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, etc.) alkyl,

,

or

Any one of them, ideally -H, -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , -C ₅ H ₁₁ , -C ₈ H ₁₇ , -C ₁₅ H ₃₁ ,

,

or

Any of

The aforementioned n is an integer of 1-10, such as 2, 3, 4, 5, 6, 7, 8, 9 and the like.

Ideally, the aforementioned preparation method comprises: the compound (A) or the organometallic salt containing aminosilane and the compound (B) containing at least two maleimine groups are subjected to a heating reaction to obtain the aforementioned modified maleimide group. Amine compound.

Ideally, the temperature of the aforementioned heating reaction is 100-200°C, ideally 110°C, 120°C, 130°C, 136°C, 141°C, 145°C, 151°C, 156°C, 160°C, 165°C and 170°C.

Ideally, the heating reaction time is 1-30h, ideally 2h, 3h, 4h, 5h, 6h, 7h, 8h, 10h, 12h, 16h, 21h, 28h.

Ideally, the aforementioned heating reaction is carried out under condensing reflux conditions.

Ideally, the aforementioned heating reaction is carried out under stirring.

Ideally, the molar ratio of the aforementioned compound (A) or the organometallic salt containing aminosilane to compound (B) is 10:90~80:20, such as 10:90, 15:85, 20:80, 24:76 , 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, etc. In order to allow the compound (A) and the compound (B) to react sufficiently, it is further desirable that the molar ratio is 30:70~50:50, such as 30:70, 35:65, 38:62, 40:60, 45:55, 50:50, etc.

Ideally, an accelerator is added to the aforementioned heating reaction.

Ideally, the amount of the aforementioned accelerator is 0.01-10% of the mass of compound (B), such as 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% , 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc.

Ideally, the aforementioned accelerators include dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxide isopropyl carbonate, 2,5-dimethyl-2,5- Di-tert-butylcumyl peroxyhexyne-3, 2,5-dimethyl 2,5-di-tert-butylperoxyhexane, p-menthane peroxide, 1,1-bis(tert-amylperoxide) Oxygen) cyclohexane, diisopropylbenzene hydrogen peroxide, benzyl peroxide, benzyl peroxide derivatives, metal salts of acetone, metal salts of naphthenic acid, vanadium pentoxide, amine compounds , Quaternary ammonium salt, imidazole, triphenylphosphine, or triphenylphosphine derivative, or any one or a combination of at least two of them.

Ideally, a solvent is added in the aforementioned heating reaction.

Ideally, the amount of the aforementioned solvent is 10~500% of the mass of compound (B), such as 50%, 100%, 150%, 200%, 250%, 300%, 350%, 400%, 450%, 480%, etc. , Ideally 50~400%.

Ideally, the aforementioned solvent contains any one or a combination of at least two of toluene, xylene, cyclohexane, tetrahydrofuran, N,N-dimethylformamide (DMF) or methyl ethyl ketone.

Ideally, the aforementioned polymers containing olefin groups include polybutadiene, polydivinylbenzene, copolymers of butadiene and styrene, copolymers of butadiene and divinylbenzene, butadiene and styrene In terpolymers with divinylbenzene, bifunctional or at least three functional bismaleimide compounds or their prepolymers, vinyl-containing polyphenylene ether resins or acrylic-containing polyphenylene ether resins Any one or a combination of at least two of them.

Ideally, the aforementioned resin composition further contains an inorganic filler and/or a flame retardant.

Ideally, the aforementioned inorganic filler contains any one or a combination of at least two of silicon dioxide, boron nitride or aluminum hydroxide.

Ideally, the particle size of the aforementioned inorganic filler is <50μm, such as 5μm, 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm, etc., ideally <20μm.

Ideally, the aforementioned flame retardant comprises decabromodiphenyl ether, decabromodiphenyl ethane, ethylene bis tetrabromophthalimide, melamine phosphate, melamine polyphosphate, dimelamine pyrophosphate, three (Tribromophenyl) cyanurate, tris(2,6-dimethylphenyl)phosphorus, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa -10-Phenanthroline-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphorylbenzene, 10-phenyl-9,10-dihydro-9-oxa-10- Any one or a combination of at least two of phenanthrene-10-oxide or phosphazene compounds, ideally tris(2,6-dimethylphenyl)phosphorus, 10-(2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphorylbenzene, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, hexachlorocyclotriphosphazene, alkoxy cyclotriphosphazene, phenoxycyclotriphosphazene, hexaaminocyclotriphosphazene , Any one or a combination of at least two of polybromoalkoxyphosphazenes or aryloxy substituted polyphosphazenes.

Ideally, the aforementioned resin composition contains the following components in parts by weight:

The content of the modified maleimide compound is 5-40 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 38 parts by weight, etc.;

The content of the olefin group-containing polymer is 30 to 70 parts by weight, such as 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 68 parts by weight, etc.;

The content of inorganic filler is 10-60 parts by weight, such as 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight , 45 parts by weight, 50 parts by weight, 55 parts by weight, etc.;

The flame retardant content is 10 to 35 parts by weight, such as 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight Parts, 32 parts by weight, 34 parts by weight, etc.

Ideally, the aforementioned resin composition further contains an initiator.

Ideally, the aforementioned initiator includes a peroxide initiator, ideally α,α'-bis(tert-butylperoxy m-isopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butyl Peroxide)-3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-diphenoxyquinone, chloranil, 2,4,6-tris(tert Butylphenoxy) or tert-butylperoxyisopropyl monocarbonate or a combination of at least two.

The second object of the present invention is to provide a resin glue solution, which contains the resin composition and solvent described in one of the objects.

Ideally, the aforementioned solvent contains any one or a combination of at least two of toluene, xylene, cyclohexane, methyl ethyl ketone, or dimethylformamide.

The third objective of the present invention is to provide a prepreg, the aforementioned prepreg comprising Reinforcement material and the resin composition described in the first purpose or the resin glue solution described in the second purpose attached to it after being impregnated and dried.

Ideally, the aforementioned reinforcing material includes glass fiber cloth.

The fourth object of the present invention is to provide an insulating board, which includes at least one prepreg sheet described in the third object.

The fifth object of the present invention is to provide a metal-clad laminate. The aforementioned metal-clad laminate includes at least one of the prepregs described in the third object and a laminate on one or both sides of the laminated prepreg. Metal foil.

The sixth object of the present invention is to provide a printed circuit board comprising at least one prepreg as described in object three, or at least one insulating board as described in object four, or at least one insulating board as described in object four Five metal-clad laminates.

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

A modified maleimide compound is added to the resin composition provided by the present invention, and the compound (B) containing at least two maleimine groups is combined with the amine-containing silane compound (A) or the amine-containing silane The organometallic salt is prepolymerized to obtain a modified maleimide compound containing silane. When it is used in the resin composition of composite materials, it has better compatibility with low-polarity resins, and reduces the volatilization of the silane coupling agent during the drying process of the prepreg, and can reduce the bismaleimide Reactivity with other resins reduces the curing stress of the resin composition, increases the adhesion of the resin composition to the reinforcing material or the conductive layer, and maintains low dielectric loss and high heat resistance. The obtained laminate has high peel strength, and at the same time has low dielectric loss, high heat resistance and high flame resistance. and The modified maleimide compound has good compatibility with the resin and is not easy to crystallize during processing.

The technical means of the present invention will be further explained by specific embodiments below. Those with ordinary knowledge in the technical field should understand that the foregoing embodiments are only to help understand the present invention and should not be regarded as specific limitations to the present invention.

The detailed information of the compounds involved in the following is as follows:

KBM-602: N-2-(β-aminoethyl)-3-γ-aminopropylmethyldimethoxysilane, Shin-Etsu;

KBM-603: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, Shin-Etsu Japan;

KBM-903: 3-Aminopropyltrimethoxysilane, Shin-Etsu Japan;

KBE-903: 3-Aminopropyltriethoxysilane, Shin-Etsu Japan;

1,2-Ethylenediamine, N,N'-bisbenzyl-N-[3-(trimethoxysilyl)propyl]-hydrochloride, CAS: 145151-33-3, reagent, commercially available;

KBM-403: 3-Glycidyloxypropylmethyltrimethoxysilane, Shin-Etsu;

DDM: Diaminodiphenylmethane, Attu, India;

DDS: Diaminodiphenyl sulfide, Atu, India;

CAS: 92-87-5, 4,4'-diaminobiphenyl, reagent, commercially available;

BMI-50P: Multifunctional maleimide resin, Japan KI;

BMI-70: Bis (3-ethyl-5-methyl-4-maleiminobenzene) methane, Japan KI;

BMI-80: 2,2-bis(4-(4-maleiminophenoxy)phenyl)propane, Japan KI.

Synthesis example 1~6

Synthesis examples 1 to 6 provide a modified maleimide compound, and the preparation steps are as follows:

Amino-containing silane compounds (KBM-602, KBM-603, KBM-903, KBE-903), compounds containing at least two maleimine groups (BMI-70, BMI-80, BMI-50P) ), the accelerator and the solvent are added to a reaction vessel with reflux, stirring and heating, heating and stirring to reflux, the solvent in the reactant is evaporated, and the mixture is cooled to normal temperature to obtain modified maleimide compounds P1 to P6.

The raw material composition, reaction time and reaction temperature of Synthesis Examples 1 to 6 are shown in Table 1.

In Table 1, - means that no corresponding substances are added.

Synthesis example 7~10

This synthesis example provides a modified maleimide compound P7~P10, and the preparation method is as follows:

Add KBM-403, diamine compound (DDM, DDS or 4,4'-diaminobiphenyl) and DMF into a reaction vessel with reflux, stirring and heating, heating to 160℃, stirring and refluxing for 2h, Then add the compound (BMI-70 or BMI-50P) containing more than two maleimine groups, heat and stir to reflux, distill the solvent of the reactant, and cool to room temperature to obtain the modified maleimide Compound P7~10.

The raw material composition, reaction time and reaction temperature of Synthesis Examples 7-10 are shown in Table 2.

In Table 2, - means that no corresponding substances are added.

Comparative Synthesis Example 1

The modified bismaleimide resin (D1) prepared according to Example 1 of patent application CN101775139A, the specific steps are as follows:

Mix 100 parts of bismaleimide, 50 parts of diallyl phenyl compound, 12 parts of γ-aminopropyl triethoxysilane and 0.50~1.50 parts of water at room temperature under the condition of 40°C Reacting for 60 minutes; then the temperature is raised to 150°C, after 120 minutes of pre-polymerization reaction, a modified bismaleimide resin D1 is obtained.

Examples 1~10, Comparative Examples 1~2

Examples 1 to 10 and Comparative Examples 1 to 2 respectively provide a resin glue and laminate, which are specifically prepared The process is as follows:

(1) Preparation of resin glue:

First dissolve the modified maleimide compound (one of P1~P10, D1) or unmodified maleimide compound in DMF, and then mix it with the other components in the formula to obtain the resin Glue; see Table 3 for the specific formula;

(2) Preparation of laminate:

Take a glass fiber cloth of model 2116 and evenly impregnate the above resin glue solution, and bake in a blast oven at 155°C for 5 minutes to prepare a prepreg sheet. Overlap 6 of the above prepreg sheets, and cover the top and bottom with 35μm inverted copper foil. In a vacuum hot press, press for 90 min at a pressure of 3 MPa and a temperature of 220° C. to obtain a laminate.

Performance Testing:

(1) Glass transition temperature Tg: use dynamic thermomechanical analysis (DMA) test, refer to the DMA test method specified in IPC-TM-6502.4.24.

(2) Thermal decomposition temperature (Td): Use thermal weight loss analysis (TGA) test, refer to standard IPC-TM-650 2.4.24.6.

(3) Peel strength (PS): refers to the tensile force required to peel off the copper clad laminate per millimeter of copper foil at room temperature.

(4) Dielectric constant (Dk) and dielectric loss factor (Df): measured using the plate capacitance method, refer to the standard IPC-TM-650 2.4.24.

(5) Flame retardant: According to UL94 "50W (20mm) vertical burning test: V-0, V-1 and V-2" test method, V-0 is recognized as flame retardant.

(6) Coefficient of thermal expansion and ratio of thermal expansion at 50~260℃: the test adopts a static thermal analyzer (TMA) test, test reference standard IPC-TM-650 2.4.24.

(7) Thermal stress: Float the laminate with copper on the surface of molten tin at a temperature of 288°C, and use the time of delamination or bubbles as the test result.

The above test results are shown in Table 3.

The detailed information of each component in Table 3 is as follows:

OPE-2St: Mitsubishi Gas, double-end olefin functionalized polyphenylene ether;

B-1000: Japan Soda, polybutadiene resin;

Ricon257: American Kreweller, butadiene-styrene-divinylbenzene branched terpolymer;

A1536: American Kraton, SEBS resin;

NQ1025J: Inorganic filler NQ1025J spherical fused silica, D50=3.0μm, Jiangsu Lianrui New Materials Co., Ltd.;

Bt-93W: American Albemarle, decabromodiphenyl ethylene, flame retardant;

OP935: American Klein, phosphorus-containing flame retardant;

DCP: Dicumyl peroxide, initiator.

In Table 3, - means that no corresponding substances are added.

It can be seen from Table 3 that after the modified maleimide compound provided by the present invention is combined with a low-polarity resin, it has strong bonding performance, and the prepared laminate has high peel strength and good dielectric properties. And heat resistance, where the peel strength is greater than 0.8N/mm, the dielectric constant of 1GHz is less than 3.8, the dielectric loss factor of 1GHz is less than 0.002, the glass transition temperature is greater than 190℃, the thermal decomposition temperature is greater than 400℃, and the thermal expansion is 50~260℃. The ratio is less than 2%, and the thermal stress is greater than 60min.

Comparative Example 1 did not prepolymerize the silane compound containing amine groups and maleimide, but added them to the resin glue solution separately. The final laminate has higher peel strength, lower Tg and Td, and Dk and The Df is higher, the thermal expansion coefficient and expansion ratio are larger, and the heat resistance performance is obviously reduced. This is because, during the curing process of the glue, the silane compound containing amine groups evaporates quickly, and In addition, the curing reaction between bismaleimide and the olefin resin is faster, which in turn reduces the above-mentioned properties.

The preparation raw material of the modified maleimide compound used in Comparative Example 2 further contains a diallyl phenyl compound. Compared with the examples, the dielectric properties are significantly reduced, and the dielectric constant and dielectric loss are obvious. High, this is because the reaction of diallyl phenyl compound and bismaleimide is more complicated, which will adversely affect the dielectric properties.

The present invention uses the above-mentioned embodiments to illustrate the detailed methods of the present invention, but the present invention is not limited to the above-mentioned detailed methods, which does not mean that the present invention must rely on the above-mentioned detailed methods to be implemented. Those with ordinary knowledge in the technical field should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention. Inside.

Claims (18)

A resin composition characterized in that the aforementioned resin composition comprises a combination of a modified maleimide compound and a polymer containing an olefin group; The aforementioned modified maleimine compound is prepared from compound (A) or an organometallic salt containing aminosilane and a compound (B) containing at least two maleimine groups. The molecule of the aforementioned compound (A) The structure is as follows:

The aforementioned R ₁ , R ₂ and R ₃ are each independently selected from C1~C6 alkyl groups; The structure of the aforementioned Y is -Y ₁ -Y _{2 -or}

； The aforementioned Y ₁ and Y ₂ are each independently selected from -CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C ₅ H ₁₀ -, -C ₃ H _6- N-, -C ₂ H ₄ -N-,

,

,

,

or

Any of The aforementioned Y _{3 is} selected from -H, -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₄ H ₉ , -C ₅ H ₁₁ , -C ₈ H ₁₇ , -C ₁₅ H ₃₁ ,

,

or

Any of The aforementioned m is 0 or 1. The resin composition described in item 1 of the scope of patent application, wherein the aforementioned compound (A) has any one of the following structures represented by formula I to formula III:

The aforementioned R ₁ , R ₂ , R ₃ , Y ₁ , Y ₂ and Y ₃ all have the same limited scope as the first item of the scope of patent application. The resin composition described in item 1 or 2 of the scope of patent application, wherein the aforementioned R ₁ , R ₂ and R ₃ are each independently selected from any one of _{CH 3} , C ₂ H ₅ or C ₃ H _7; The aforementioned Y ₁ and Y ₂ are each independently selected from

,

,

or

Any of them. The resin composition described in item 1 or 2 of the scope of patent application, wherein the aforementioned compound (B) has a structure represented by the following formula IV or formula V:

The aforementioned X is selected from -CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C ₅ H ₁₀ -,

,

,

or

Any of The foregoing R, R ₄ to R ₁₁ are each independently selected from -H, C1 to C15 alkyl,

,

or

Any of The aforementioned n is an integer of 1-10. The resin composition as described in item 1 or 2 of the scope of patent application, wherein the preparation method of the modified maleimide compound includes: compound (A) or an organometallic salt containing aminosilane and containing at least two The compound (B) of the maleimine group undergoes a heating reaction to obtain the aforementioned modified maleimine compound. The resin composition as described in item 5 of the scope of patent application, wherein the temperature of the aforementioned heating reaction is 100 to 200°C; The heating reaction time is 1~30h; The aforementioned heating reaction is carried out under condensing reflux conditions; The aforementioned heating reaction is carried out under stirring. The resin composition as described in item 5 or 6 of the scope of patent application, wherein an accelerator is added in the heating reaction, and the amount of the accelerator is 0.01-10% of the quality of the compound (B). The resin composition as described in item 5 or 6 of the scope of the patent application, wherein a solvent is added in the heating reaction, and the amount of the solvent is 10 to 500% of the quality of the compound (B). The resin composition as described in item 1 or 2 of the scope of patent application, wherein the molar ratio of the aforementioned compound (A) or the organometallic salt containing aminosilane to the compound (B) is 10:90 to 80:20. The resin composition described in item 1 or 2 of the scope of patent application, wherein the aforementioned polymer containing olefin groups includes polybutadiene, polydivinylbenzene, copolymers of butadiene and styrene, butadiene Copolymer with divinylbenzene, terpolymer of butadiene, styrene and divinylbenzene, difunctional or at least three functional bismaleimide compound or its prepolymer, containing vinyl Any one or a combination of at least two polyphenylene ether resins or polyphenylene ether resins containing acrylic groups. The resin composition as described in item 1 or 2 of the scope of the patent application, wherein the resin composition further contains an inorganic filler and/or a flame retardant. The resin composition described in item 1 or 2 of the scope of the patent application, wherein the aforementioned resin composition contains the following components in parts by weight:

The resin composition described in item 1 or 2 of the scope of patent application, wherein the aforementioned resin composition further contains an initiator. A resin glue liquid, characterized in that the aforementioned resin glue liquid contains the resin composition and solvent described in any one of items 1 to 13 in the scope of the patent application. A prepreg sheet, which is characterized in that the aforementioned prepreg sheet comprises a reinforcing material and a resin composition described in any one of the scope of patent application 1 to 13 attached to it after being impregnated and dried or the scope of patent application 14 The resin glue liquid recorded. An insulating board, characterized in that the aforementioned insulating board includes at least one prepreg described in item 15 of the scope of patent application. A metal-clad laminate, which is characterized in that the aforementioned metal-clad laminate includes at least one prepreg as described in item 15 of the scope of patent application and metal foil covering one or both sides of the laminated prepreg . A printed circuit board, characterized in that the aforementioned printed circuit board contains at least one prepreg described in item 15 of the scope of patent application, or at least one insulating board described in item 16 of the scope of patent application, or at least one application The metal-clad laminate described in item 17 of the scope of the patent.