TW202126726A - Modified maleimide compound, preparation method therefor and use thereof - Google Patents

Abstract

The present invention relates to a modified maleimide compound, a preparation method therefor and the use thereof. 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 present invention comprises prepolymerizing compound (B) containing at least two maleimido groups with an amino-containing silane compound (A) or an organometallic salt of an amino-containing silane to obtain a modified maleimide compound containing a silane. When used in a resin composition of a composite material, the modified maleimide compound has a better compatibility with a low-polarity resin, avoids the volatilization of a silane coupling agent during drying of a prepreg, and can reduce the reactivity between bismaleimide and other resins, reduce the curing stress of the resin composition, increase the adhesive force between the resin composition and a reinforcing material or a conductive layer, and maintain a low dielectric loss and a high heat resistance.

Description

Modified maleimide compound and preparation method and application thereof

The invention relates to the technical field of printed circuits, in particular to a modified maleimide compound and a preparation method and application thereof.

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 ester resins with better adhesion. When bismaleimide is combined with a lower polar resin, its adhesion performance is still very poor.

CN106700549A discloses a modified bismaleimide resin, a reinforced laminate and a preparation method thereof. The bismaleimide resin is modified by cyanate ester resin, rubber, dicyandiamide, and silicon dioxide to obtain a modified double The maleimide resin, the modified bismaleimide resin as the adhesive, the glass fiber as the base material, and the reinforced laminate is prepared by dipping and coating, drying the adhesive tape, and laminating. The advantage of this invention is that it provides a modified double horse which can meet the requirements of industrial production. Reinforced laminates prepared by using this modified bismaleimide resin and glass fiber not only have good heat resistance, but also their mechanical properties have also been significantly improved. The comprehensive performance is excellent, and it can be applied to Electrical insulation, aerospace and other fields. However, in this invention, the obtained laminate still has the problem of high dielectric constant and dielectric loss.

CN105295048A discloses a high heat resistance liquid modified bismaleimide resin and a preparation method thereof. 3-aminobenzocyclobutene and bismaleimide monomer are melted and copolymerized by Michael addition to form a prepolymer After cooling, add an active diluent to keep warm, add a solution with a catalyst after cooling, mix uniformly, and vacuum-evaporate the solvent to dissolve the catalyst to obtain a liquid modified bismaleimide resin with high heat resistance. The resin system provided by the invention presents a fluid liquid at room temperature. It is a rare species in the field of double-horse resins. It exhibits good processing technology and is suitable for many current composite material molding processes. It can not only be used as the basic resin for advanced copper clad laminates, but also It can also be used in advanced composite materials or high-temperature adhesives in aerospace, transportation and other fields. However, the composition composed of the bismaleimide resin and the low-polarity resin of the present invention has poor adhesion to materials such as copper foil, glass fiber cloth, and the like, and the prepared laminate has low peel strength.

CN101824148A discloses a bismaleimide-triazine resin containing octavinyl cage silsesquioxane and a preparation method thereof. By weight, 100 parts of bismaleimide are slowly added to O,O'-diallylbisphenol A at 120~140°C to obtain prepolymer I; slowly 1894 parts of octaethylene Base cage silsesquioxane is added to prepolymer I at 120~140℃ to obtain prepolymer II; weigh 215~280 parts of cyanate ester, slowly add it to prepolymer II, and heat up to 140 ~160°C, and then heat and stir for 1~2 hours to obtain a bismaleimide-triazine resin containing octavinyl cage silsesquioxane. The prepared resin can be used as a basic material for preparing high-performance copper clad laminates in the field of electronic information. But the resin has poor adhesion, and the prepared copper clad laminate The peel strength is low.

Therefore, there is an urgent need in the art to develop a new type of maleimide compound to improve the bonding performance of the combination with a low-polar resin, and to obtain a laminate with low dielectric and high heat resistance.

One of the objectives of the present invention is to provide a modified maleimide compound to improve the bonding performance of the combination with a low-polar resin, thereby preparing a laminate with high peel strength, low dielectric and high heat resistance.

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

The present invention provides a modified maleimine compound which is composed of compound (A) or an organometallic salt containing aminosilane, and containing at least two maleimine groups The compound (B) is prepared, and the molecular structure of the compound (A) is as follows:

The 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 Y is -Y ₁ -Y ₂ -or

；

、

、

、

或

中的任意一種； The 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 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 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 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), which can exemplarily form a modified maleimide compound with the following structure:

The above structure only expresses the connection mode of compound (A) or organometallic salt of aminosilane and compound (B) after the 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 compound (A) has any one of the following structures shown in formula I to formula III:

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

Ideally, the 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.

Ideally, the Y ₁ and Y ₂ are each independently selected from

、

、

或

中的任意一種。

,

,

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 after curing on the silicone, and can further improve the bonding performance of the resin. The main chain has higher rigidity, which is conducive to high heat resistance.

Ideally, the compound (B) has a structure shown in the following formula IV or formula V:

、

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

,

Any of

、

或

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

、

或

中的任意一種； The 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 the ideal -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 n is an integer of 1-10, such as 2, 3, 4, 5, 6, 7, 8, 9, etc.

The second object of the present invention is to provide a method for preparing the modified maleimide compound described in the first object. The preparation method comprises: compound (A) or an organometallic salt containing aminosilane and containing at least two The compound (B) with one maleimine group undergoes a heating reaction to obtain the modified maleimine compound.

Ideally, the temperature of the 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 1-30 hours, ideally 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 10 hours, 12 hours, 16 hours, 21 hours, 28 hours. Hour.

Ideally, the heating reaction is carried out under the condition of condensation and reflux.

Ideally, the heating reaction is carried out under stirring.

Ideally, the molar ratio of the compound (A) or the organometallic salt containing aminosilane to the 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) to react with the compound (B) 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 heating reaction.

Ideally, the amount of the 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 accelerator includes dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxide isopropyl carbonate, 2,5-dimethyl-2,5 -Di-tert-butylcumylperoxyhexyne-3, 2,5-dimethyl 2,5-di-tert-butylperoxyhexane, p-menthane peroxide, 1,1-bis(tert-pentyl Peroxy) cyclohexane, diisopropylbenzene hydrogen peroxide, benzyl peroxide, benzyl peroxide derivatives, metal salts of acetone, metal salts of naphthenic acid, vanadium pentoxide, amines Any one or a combination of at least two of the compound, quaternary ammonium salt, imidazole, triphenylphosphine, or triphenylphosphine derivative.

Ideally, a solvent is added during the heating reaction.

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

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

The third object of the present invention is to provide a resin composition containing the modified maleimide compound described in one of the objects.

The fourth object of the present invention is to provide a prepreg sheet comprising a reinforcing material and the resin composition of the third object attached to it after being impregnated and dried.

Ideally, the reinforcing material includes glass fiber cloth.

The fifth object of the present invention is to provide an insulating board comprising at least one prepreg sheet according to the fourth object.

The sixth object of the present invention is to provide a metal-clad laminate, the metal-clad laminate comprising at least one prepreg sheet according to the fourth object and on one or both sides of the laminated prepreg Metal foil.

The seventh object of the present invention is to provide a printed circuit board comprising at least one prepreg according to object four, or at least one insulating board according to object five, or at least one object The sixth metal-clad laminate.

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

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, and avoids silane coupling during the drying process of the prepreg The volatilization of the agent can reduce the reactivity between the bismaleimide and other resins, reduce the curing stress of the resin composition, increase the adhesion of the resin composition to the reinforcing material or the conductive layer, and maintain a low dielectric Electrical loss and high heat resistance.

The technical means of the present invention will be further explained below through specific implementations. Those with ordinary knowledge in the technical field should understand that the 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 the reaction vessel with reflux, stirring and heating, heating and stirring to reflux, the solvent in the reactant is distilled off and 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.

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 2 hours, and then adding Compounds containing two or more maleimine groups (BMI-70 or BMI-50P), after heating, stirring and refluxing, the solvent in the reactant is evaporated, and cooled 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.

Table 2

In Table 2, ── means 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 reaction 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. The specific preparation 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. The laminate was obtained by pressing in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 min.

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): use a flat panel Determination by volumetric method, refer to 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, and the test refers to the 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.

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.

──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. Among them, 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, and the vitrification The transition temperature is greater than 190°C, the thermal decomposition temperature is greater than 400°C, the thermal expansion ratio of 50~260°C 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 finally obtained 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 liquid, the silane compound containing the amine group volatilizes quickly, and the curing reaction between the bismaleimide and the olefin resin is faster, thereby reducing the above-mentioned performance.

The modified maleimide compound used in Comparative Example 2 also includes diallyl phenyl compound as the raw material. Compared with the examples, its 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 has an adverse effect on 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 equal replacement of the raw materials 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. .

Claims (14)

A modified maleimine compound, characterized in that: the aforementioned modified maleimine compound is composed of compound (A) or an organometallic salt containing aminosilane, and containing at least two maleimine groups The compound (B) is prepared, and the molecular structure of the aforementioned compound (A) is as follows:

The aforementioned R ₁ , R ₂ and R ₃ are each independently selected from C1 to 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 groups; 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 groups; The aforementioned m is 0 or 1. The modified maleimide compound described in item 1 of the scope of patent application, wherein the aforementioned compound (A) has any one of the structures shown in the following 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 modified maleimide compound described in item 1 or 2 of the scope of the patent application, wherein the aforementioned R ₁ , R ₂ and R ₃ are each independently selected from CH ₃ , C ₂ H ₅ or C ₃ H ₇ Any of the groups; The aforementioned Y ₁ and Y ₂ are each independently selected from

,

,

or

Any of the groups. The modified maleimide compound described in item 1 or 2 of the scope of patent application, wherein the aforementioned compound (B) has the structure shown in 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 -,

,

Any of the groups; The aforementioned R, R ₄ to R ₁₁ are each independently selected from -H, C1 to C15 alkyl,

,

or

Any of the groups; The aforementioned n is an integer of 1-10. The method for preparing a maleimide compound as described in any one of items 1 to 4 of the scope of the patent application, wherein the foregoing preparation method comprises: compound (A) or an organometallic salt containing aminosilane and containing at least two The compound (B) with one maleimine group undergoes a heating reaction to obtain the aforementioned modified maleimine compound. The preparation method described in item 5 of the scope of patent application, wherein the temperature of the aforementioned heating reaction is 100 to 200°C; The time for the aforementioned heating reaction is 1 to 30 hours; The aforementioned heating reaction is carried out under condensing reflux conditions; The aforementioned heating reaction is carried out under stirring. The preparation method as described in item 5 or 6 of the scope of the 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 preparation method as described in item 5 or 6 of the scope of the patent application, wherein the accelerator is added in the heating reaction, and the amount of the accelerator is 0.01 to 10% of the mass of the compound (B). The preparation method described in item 5 or 6 of the scope of patent application, wherein a solvent is added in the heating reaction, and the amount of the solvent is 10 to 500% of the mass of the compound (B). A resin composition characterized in that the aforementioned resin composition contains the modified maleimide compound described in any one of the first to fourth patent applications. A prepreg sheet, characterized in that: the aforementioned prepreg sheet includes a reinforcing material and the resin composition described in item 10 of the scope of patent application attached to it after being impregnated and dried. An insulating board, characterized in that: the aforementioned insulating board includes at least one prepreg described in item 11 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 sheet described in item 11 of the scope of patent application and metal covering one or both sides of the laminated prepreg sheet Foil. A printed circuit board, characterized in that: the aforementioned printed circuit board contains at least one prepreg described in item 11 of the scope of patent application, or at least one insulating board described in item 12 of the scope of patent application, or at least one The metal-clad laminate described in item 13 of the scope of patent application.