TWI804796B - A kind of modified maleimide compound and its preparation method and application - Google Patents

Abstract

The invention provides a modified maleimide compound and its preparation method and application. The raw materials for the preparation of the modified maleimide compound include: a maleimide-containing compound and a compound having a structure as shown in formula I Aromatic monoamine compounds containing active ester groups. The modified maleimide compound is prepared from specific raw materials, and its molecular structure contains a maleimide group and an active ester group. The two active groups cooperate with each other to make the modified maleimide The imine compound has higher reactive cross-linking sites, low water absorption, low dielectric constant and dielectric loss; the modified maleimide compound reacts with the epoxy resin as a curing agent, and the obtained cured The product has low water absorption, high glass transition temperature, excellent dielectric properties, heat resistance, heat and humidity resistance, low thermal expansion coefficient and strong metal bonding force, which can fully meet the application requirements of high-performance circuit substrates.

Description

A kind of modified maleimide compound and its preparation method and application

The invention belongs to the technical field of copper clad laminates, and in particular relates to a modified maleimide compound and its preparation method and application.

In recent years, with the rapid development of the information industry, electronic products have become increasingly short, thin, high-performance and multi-functional. In order to meet the development needs of various electronic equipment, information communication equipment tends to increase the speed and frequency of signal transmission. Integrated circuits are advancing towards high density, high precision and high integration, which requires printed circuit substrate materials to have good dielectric properties, and also requires substrates to have good heat resistance to meet the reliability requirements of printed circuit board processes. For example, in the substrates of smart mobile phones, etc., which are being thinned and lowered in price, materials with a low relative dielectric constant are required to cope with thinning; in communication system equipment represented by servers, routers, and mobile base stations, etc. , in order to be able to use in a higher frequency band and to use high melting point lead-free solder in the soldering of electronic components, it is also required to have low dielectric properties (low dielectric constant and low dielectric loss), high glass transition temperature (high T _g ) and excellent reflow heat resistance.

Maleimide resin is a kind of high-performance matrix resin, and its cured product has the advantages of high glass transition temperature, high heat resistance, good mechanical properties and dielectric properties. For example CN105385105A discloses a kind of bismaleimide modified epoxy resin and its preparation method and its purposes, and its preparation method comprises: at first modifying agent, epoxy resin and bismaleimide reaction form Form resin glue solution, described resin glue solution and curing agent, curing accelerator continue to react, obtain bismaleimide modified epoxy resin; Wherein, modifier is selected from ortho-diallyl bisphenol A two shrinkage Allyl compound of glyceryl ether, bisphenol A diallyl ether, 2-allylphenol bisphenol S or diallyl ether. The modified epoxy resin obtained by the above method can be used to prepare a copper clad laminate base material with high temperature resistance, low loss, good heat and humidity resistance, and better mechanical properties. CN101652026A discloses a method for preparing a copper clad laminate, which specifically includes: first reacting a bismaleimide resin and an allyl compound to obtain a prepolymer; then compounding and curing the prepolymer with a phosphorus-containing epoxy resin The glue solution is obtained by mixing with other agents, etc.; the glue solution is coated on glass fiber cloth and baked to form a B-stage prepreg, which is stacked with copper foil and hot-pressed to obtain a copper-clad laminate; the obtained copper-clad laminate can meet the requirements of halogen-free flame retardant Requirements, excellent heat resistance, heat and humidity resistance, low dielectric loss, good processing toughness.

However, maleimide resin is brittle, has poor solubility in organic solvents with low polarity, and cannot directly react with epoxy resins. It is often modified or mixed with amines, diallyl compounds, etc. When the epoxy resin is used together, the grid structure formed after the reaction contains a large number of highly polar and water-absorbing secondary alcohol hydroxyl groups, which greatly reduces the performance of the cured product in terms of dielectric properties and heat and humidity resistance.

CN108401433A discloses a resin varnish, a prepreg, a laminate, and a printed circuit board. The resin varnish contains a maleimide compound, an epoxy resin, has a structural unit from an aromatic vinyl compound and a The copolymer resin of the structural unit, the silicon dioxide and the organic solvent after treatment with the aminosilane coupling agent, etc., the maleimide compound used in it contains acidic substituents and maleimide groups, so as to obtain Good heat resistance and adhesion, high glass transition temperature, relatively low dielectric constant and low thermal expansion, excellent formability and plating coverage of thermosetting resin composition material. However, the maleimide compound used in this resin varnish contains acidic substituents such as hydroxyl, carboxyl or sulfonic acid groups, and reacts with epoxy resins to generate secondary alcoholic hydroxyl groups that are highly polar and easy to absorb water, thereby affecting the mediation of cured products. electrical properties, water absorption, Resistance to heat and humidity will be adversely affected.

Therefore, it is a research focus in this field to develop a curing agent suitable for epoxy resin systems with excellent dielectric properties, low water absorption and more cross-linking reaction sites to meet the performance and application requirements of high-performance circuit substrates. .

[Prior technical literature] 【Patent Literature】

[Patent Document 1] CN105385105A

[Patent Document 2] CN101652026A

[Patent Document 3] CN108401433A

For the deficiencies in the prior art, the object of the present invention is to provide a kind of modified maleimide compound and its preparation method and application, described modified maleimide compound is prepared by specific raw material, in its molecular structure Containing maleimide groups and active ester groups, the two active groups cooperate with each other, so that the modified maleimide compound has a higher reactive crosslinking site; The epoxy resin composition with an amine compound as a curing agent has low water absorption after curing, excellent dielectric properties, heat resistance, and heat and humidity resistance, and a low thermal expansion coefficient, which can fully meet the application requirements of high-performance circuit substrates.

For reaching this purpose, the present invention adopts following technical means:

In the first aspect, the present invention provides a modified maleimide compound. The raw materials for the preparation of the modified maleimide compound include: a maleimide-containing compound and a compound containing Active ester-based aromatic monoamine compounds;

In formula I, Ar is selected from substituted or unsubstituted C ₆ ~C ₃₀ (such as C ₆ , C ₉ , C ₁₀ , C ₁₂ , C ₁₄ , C 16 , C ₁₈ , C ₂₀ , C ₂₂ , _{C 24 ,} C ₂₆ or C ₂₈ etc.) divalent aromatic groups.

In formula I, X is selected from substituted or unsubstituted C ₆ ~C ₂₀ (such as C ₆ , C ₉ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , C ₁₈ or C ₂₀ etc.) aryl groups, X ₁ - Y ₁ -X ₂ -, substituted or unsubstituted C ₁ ~C ₂₀ (such as C ₂ , C ₃ , C ₄ , C ₅ , C ₇ , C ₉ , C ₁₀ , C 12 , C ₁₄ , _{C 16 ,} C ₁₈ or C ₂₀ etc.) straight chain or branched chain alkyl, substituted or unsubstituted C ₃ ~ C ₂₀ (such as C ₃ , C ₄ , C ₅ , C 7 , C ₉ , C ₁₀ , C ₁₂ , C _{14 ,} C ₁₆ , C ₁₈ or C ₂₀ etc.) cycloalkyl.

X ₁ and X ₂ are each independently selected from substituted or unsubstituted C ₆ -C ₁₂ (eg C ₆ , C ₉ , C ₁₀ or C ₁₂ etc.) aryl groups.

Y ₁ is selected from C ₁ to C ₅ (such as C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) straight or branched chain alkylene, -O-, -S-, pyrenyl or pyrenylene.

The substituted substituents in Ar and X are each independently selected from F, C ₁ -C ₅ (such as C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) straight or branched chain alkyl groups.

In the present invention, the "divalent aromatic group" means a group containing aryl groups with two bonding sites, including arylene groups (such as phenylene, naphthylene, biphenylene, anthracenyl or phenanthrenyl, etc.), and at least two aryl groups are connected through a linking group (such as -O-, -S-, carbonyl, arganyl, arkenyl, alkylene or cycloalkylene, etc. ) are connected to form a substituent. When referring to the same description below, all have the same meaning.

In the present invention, the short straight lines on one or both sides of the group structure (such as the short straight line on the right side in X ₁ -Y ₁ -X ₂ -) represent the access bond of the group, and do not represent the methyl group.

The raw materials for the preparation of modified maleimide compounds provided by the present invention include two types: compounds containing maleimide groups and aromatic monoamine compounds containing active ester groups; The amine compound contains two functional groups, a maleimide group and an active ester group, and the two cooperate with each other, so that the modified maleimide compound has a high reactive crosslinking site and a low dielectric constant. , low dielectric loss, high heat resistance and low coefficient of thermal expansion; compared to maleimide compounds containing acidic substituents such as hydroxyl, carboxyl or sulfonic acid groups in the prior art, the modified maleimide of the present invention The compound can further reduce the dielectric constant, dielectric loss, and water absorption, and is excellent in heat resistance and heat and humidity resistance. The modified maleimide compound is used as a curing agent to undergo a curing reaction with an epoxy resin, and the obtained cured product has a low water absorption rate and a high glass transition temperature, and has excellent dielectric properties, heat resistance, heat and humidity resistance, low Coefficient of thermal expansion and strong metal bonding.

進行反應，得到含活性酯基芳香單硝基化合物

；所述含活性酯基芳香單硝基化合物經過還原反應，得到所述含活性酯基芳香單胺化合物；其中，Ar、X具有與式I中相同的限定範圍，Z₁選自羥基或鹵素(例如F、Cl、Br或I)。 In the present invention, the active ester group-containing aromatic monoamine compound having the structure shown in formula I can be prepared by the following method: monofunctional nitrophenol compound HO-Ar-NO ₂ and compound

Carry out a reaction to obtain an aromatic mononitro compound containing an active ester group

; The aromatic mononitro compound containing active ester group undergoes a reduction reaction to obtain the aromatic monoamine compound containing active ester group; wherein, Ar and X have the same limited range as in formula I, and _Z is selected from hydroxyl or halogen (eg F, Cl, Br or I).

Ideally, the Ar is selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene; the substituted substituent is selected from F, C ₁ ~ C ₅ (eg C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) straight or branched chain alkyl.

Ideally, the X is selected from C ₁ ~C ₁₀ (such as C ₁ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C ₉ or C ₁₀ ) straight or branched chains Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted biphenyl ether group; the substituted substituent is selected from F, C ₁ ~C ₅ (eg C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) straight or branched chain alkyl.

In the present invention, the maleimide-containing compound includes a maleimide-containing monomer and/or a maleimide-containing polymer.

Ideally, the maleimide-containing monomers include 4,4'-diphenylmethane bismaleimide, N,N'-m-phenylene bismaleimide, bisphenol A diphenyl Base ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1, 3-m-phenylene bismaleimide, 1,6-bismaleimide-2,2,4-trimethyl-hexane, 2,3-dimethylbenzmaleimide, Any one or a combination of at least two of 2,6-dimethylphenylmaleimide or N-phenylmaleimide.

Ideally, the maleimide-containing polymers include maleimide resins, benzylmaleimide oligomers (or polyphenylmethanemaleimides) or _C5 -C-containing ₅₀ (e.g. C ₆ , C ₈ , C ₁₀ , C ₁₂ , C ₁₅ , C ₁₈ , C 20 , C ₂₂ , C ₂₅ , C ₂₈ , C ₃₀ , C ₃₂ , C ₃₅ , C ₃₈ , _C40 , C ₄₂ , C ₄₅ or C ₄₈ etc.) any one or a combination of at least two of the maleimide compounds of the aliphatic long-chain structure.

Exemplarily, the maleimide-containing compound can be BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI- Any one or a combination of at least two of 4000H, BMI-5000, BMI-5100, BMI-7000, BMI-7000H, BMI-70, BMI-80, MIR-3000-70MT or MIR-5000-60T; the above list The names of all are trade names, among them, BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI -5100, BMI-7000, BMI-7000H were purchased from Japan Daiwakasei Company, BMI-70, BMI-80 were purchased from Japan K.I Chemical Company, MIR-3000-70MT, MIR-5000-60T were purchased from Japan NIPPON KAYAKU Company.

Exemplarily, the maleimide compound containing C ₅ ~C ₅₀ aliphatic long chain structure can be BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI -Any one or a combination of at least two of 5000 or BMI-6000; the names listed above are trade names, purchased from Designer Molecules Inc.

Ideally, based on 1 mol of the maleimide group in the maleimide group-containing compound, the amount of the active ester group-containing aromatic monoamine compound is 0.05-1 mol, such as 0.08 mol, 0.1 mol, 0.15mol, 0.2mol, 0.25mol, 0.3mol, 0.35mol, 0.4mol, 0.45mol, 0.5mol, 0.55mol, 0.6mol, 0.65mol, 0.7mol, 0.75mol, 0.8mol, 0.85mol, 0.9mol or 0.95mol , and the specific point values between the above-mentioned point values, limited to the space and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range, ideally 0.1~0.75mol, and further ideally 0.15~0.5mol .

As an ideal technical means of the present invention, based on 1 mol of the maleimide group in the maleimide group-containing compound, the amount of the active ester group-containing aromatic monoamine compound is 0.05-1 mol. The less the amount of the aromatic monoamine compound containing the active ester group, the lower the degree of modification of the maleimide-containing compound (matrix), the modified maleimide compound of the reaction gained, on the one hand in The solubility improvement effect in organic solvents is not obvious. On the other hand, the proportion of functional groups that can react with epoxy groups in its structure is low, and the effect of improving the brittleness of its cured product is not good; on the contrary, the active ester-containing The more the amount of aromatic monoamine compound is used, the higher the degree of modification is, the more beneficial it is to the solubility and toughness of the modified maleimide compound, but it also greatly sacrifices the maleimide-containing compound. (Matrix) advantages in terms of high glass transition temperature and low expansion coefficient.

In the present invention, the preparation raw materials also include an aromatic diamine compound having the structure shown in formula II; H ₂ N-Ar ₁ -Y-Ar ₂ -NH ₂ formula II.

In formula II, Ar ₁ and Ar ₂ are each independently selected from substituted or unsubstituted C ₆ ~C ₃₀ (such as C ₆ , C ₉ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , C ₁₈ , C ₂₀ , C ₂₂ , C ₂₄ , C ₂₆ or C ₂₈ etc.) arylene group; the substituents described in Ar ₁ and Ar ₂ are each independently selected from F, C ₁ ~ C ₅ (such as C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) straight or branched chain alkyl.

、

或

In formula II, Y is selected from C ₁ ~C ₅ (such as C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) straight or branched chain alkylene, -O-,

,

or

Ar ₃ and Ar ₄ are each independently selected from substituted or unsubstituted C ₆ ~C ₃₀ ( _such as C ₆ , C ₉ , C ₁₀ , C 12 , C ₁₄ , C ₁₆ , C ₁₈ , C ₂₀ , C ₂₂ , C ₂₄ , C ₂₆ or C ₂₈ , etc.) divalent aromatic groups; the substituents described in Ar ₃ and Ar ₄ are each independently selected from halogen (such as F, Cl, Br or I), unsubstituted or halogenated C ₁ ~ C ₅ (such as C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) straight chain or branched chain alkyl group, group containing aryl phosphorus oxygen structure.

Z is selected from C ₁ ~ C ₂₀ (such as C ₂ , C ₃ , C ₄ , C ₅ , C ₇ , C ₉ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , C ₁₈ or C ₂₀ , etc.) straight chain or Branched chain alkylene, C ₃ ~ C ₂₀ (such as C ₃ , C ₄ , C ₅ , C ₇ , C ₉ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , C ₁₈ or C ₂₀ etc.) cycloalkane C ₆ ~ C ₂₀ (such as C ₆ , C ₉ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , C ₁₈ or C ₂₀ etc.) arylene or biphenylene ether group.

n represents the average value of repeating units, selected from 0~10, such as 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.3, 3.5, 3.7, 4, 4.2, 4.5 . For the sake of consideration, the present invention does not exhaustively list the specific point values included in the stated range.

Ideally, the Ar ₁ and Ar ₂ are each independently selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene or substituted or unsubstituted biphenylene; each of the substituted substituents independently selected from F, C ₁ -C ₅ (such as C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) straight or branched chain alkyl groups.

、

Ideally, the Ar ₃ and Ar ₄ are each independently selected from

,

、

、

、

Y ₂ is selected from unsubstituted or halogenated C ₁ ~C ₅ (such as C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) linear or branched alkylene, -O-, -S-,

,

,

,

或

。 R ₁ and R ₂ are each independently selected from halogen, unsubstituted or halogenated C ₁ to C ₅ (such as C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) straight chain or branched alkyl,

or

.

n ₁ and n ₃ are each independently selected from an integer of 0-4, such as 0, 1, 2, 3 or 4.

n ₂ is an integer selected from 0 to 6, such as 0, 1, 2, 3, 4, 5 or 6.

、

、

Ideally, the Ar ₃ and Ar ₄ are each independently selected from

,

,

Ideally, the Z is selected from C ₁ ~ C ₅ (such as C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) linear or branched alkylene, C ₃ ~ C ₁₂ (such as C ₃ , C ₄ , C ₅ , C ₇ , C ₉ , C ₁₀ or C ₁₂ etc.) cycloalkylene, phenylene, naphthylene, biphenylene or phenylene ether group.

Ideally, based on 1 mol of the maleimide group in the maleimide group-containing compound, the total amount of amine groups in the aromatic monoamine compound containing active ester groups and the aromatic diamine compound is 0.05~1mol, such as 0.08mol, 0.1mol, 0.15mol, 0.2mol, 0.25mol, 0.3mol, 0.35mol, 0.4mol, 0.45mol, 0.5mol, 0.55mol, 0.6mol, 0.65mol, 0.7mol, 0.75mol, 0.8mol, 0.85mol, 0.9mol or 0.95mol, and the specific point values between the above-mentioned point values are limited by space and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the range.

As an ideal technical means of the present invention, based on 1 mol of the maleimide group in the maleimide group-containing compound, the active ester group-containing aromatic monoamine compound and the aromatic diamine compound The total amount of amine groups is 0.05~1mol. The less the amount of the described active ester-containing aromatic monoamine compound and the aromatic diamine compound, the lower the degree of modification of the maleimide-containing compound (matrix), the modified maleimide obtained from the reaction will Compound, on the one hand, the solubility improvement effect in organic solvents is not obvious, on the other hand, the proportion of functional groups that can react with epoxy groups in its structure is low, and the effect on improving the brittleness of its cured product is not good; on the contrary, The more the amount of the aromatic monoamine compound and the aromatic diamine compound containing the active ester group, although the degree of modification is higher, it is more beneficial to the solubility and toughness of the modified maleimide compound obtained, but it is also greatly The advantages of the maleimide-containing compound (matrix) in terms of high glass transition temperature and low expansion coefficient are sacrificed. because Here, the maleimide group in the maleimide-containing compound is 1 mol, and the total amount of amine groups in the aromatic monoamine compound containing active ester group and the aromatic diamine compound is ideally 0.1 ~0.6mol, ideally 0.15~0.4mol.

Ideally, based on 1 mol of the maleimide group in the maleimide-containing compound, the amount of the aromatic diamine compound used is 0.01-0.25 mol, such as 0.03 mol, 0.05 mol, 0.08 mol, 0.1mol, 0.12mol, 0.15mol, 0.18mol, 0.2mol, 0.21mol, 0.22mol, 0.23mol or 0.24mol, and the specific point values between the above-mentioned point values, limited by space and for the sake of simplicity, the present invention does not An exhaustive enumeration of the specific point values included in the range is then made.

As an ideal technical means of the present invention, the raw materials for the preparation of the modified maleimide compound include a combination of a maleimide-containing compound, an active ester group-containing aromatic monoamine compound and an aromatic diamine compound. The ester-based aromatic monoamine compound and the aromatic diamine compound are prepared by addition reaction of the amine group in the maleimide group-containing compound with the maleimide group. Wherein, the active ester-containing aromatic monoamine compound reacts with the maleimide-containing compound to play a capping effect, which can prevent the molecular chain of the modified maleimide compound from continuing to grow, and is beneficial to control the modified horse The molecular weight of the maleimide compound; and the reaction of the aromatic diamine compound and the maleimide-containing compound plays a chain extension effect, so that the molecular chain of the modified maleimide compound can continue to grow, thereby Reasonably control the molecular weight of the final modified maleimide compound to avoid problems such as poor solubility due to too large a molecular weight. The amount of the aromatic diamine compound should not be too much, that is, based on 1 mol of the maleimide group in the maleimide-containing compound, the amount of the aromatic diamine compound is 0.01-0.25 mol.

，所述芳香二胺化合物的結構為

(記為式II-1)，可通過如下方法製備得 到：二酚化合物HO-Ar₃-OH、化合物

和化合物

進行反應，得到芳香二硝基化合物

；所述芳香二硝基化合物經過還原反應，得到具有式II-1所示結構的芳香二胺化合物；其中，Ar₁、Ar₂、Ar₃具有與式II中相同的限定範圍，Z₂、Z₃各自獨立地選自羥基或鹵素(例如F、Cl、Br或I)。 As an ideal technical means of the present invention, said Y is

, the structure of the aromatic diamine compound is

(Denoted as formula II-1), can be prepared by the following method: diphenolic compound HO-Ar ₃ -OH, compound

and compound

The reaction is carried out to obtain aromatic dinitro compounds

; The aromatic dinitro compound undergoes a reduction reaction to obtain an aromatic diamine compound with a structure shown in formula II-1; wherein, Ar ₁ , Ar ₂ , and Ar ₃ have the same limited range as in formula II, and Z ₂ , _{Each Z3} is independently selected from hydroxyl or halogen (eg, F, Cl, Br or I).

，所述芳香二胺化合物的結構為

(記為式II-2)，可通過如下方法製備得到：二酚化合物HO-Ar₄-OH、雙官能化合物

、單官能硝基酚化合物HO-Ar₂-NO₂和單官能硝基酚化合物HO-Ar₁-NO₂進行反應，得到芳香二硝基化合物

；所述芳香二硝基化合物經過還原反應，得到具有式II-2所示結構的芳香二胺化合物；其中，Ar₁、Ar₂、Ar₄具有與式II中相同的限定範圍，Z₄、Z₅各自獨立地選自羥基或鹵素(例如F、Cl、Br或I)。 As an ideal technical means of the present invention, said Y is

, the structure of the aromatic diamine compound is

(Denoted as formula II-2), can be prepared by the following method: diphenolic compound HO-Ar ₄ -OH, bifunctional compound

, monofunctional nitrophenol compound HO-Ar ₂ -NO ₂ and monofunctional nitrophenol compound HO-Ar ₁ -NO ₂ react to obtain aromatic dinitro compounds

; The aromatic dinitro compound undergoes a reduction reaction to obtain an aromatic diamine compound with a structure shown in formula II-2; wherein, Ar ₁ , Ar ₂ , and Ar ₄ have the same limited range as in formula II, and Z ₄ , _{Each Z5} is independently selected from hydroxyl or halogen (eg, F, Cl, Br or I).

In another aspect, the present invention provides a method for preparing the modified maleimide compound as described above, the preparation method comprising: a maleimide-containing compound, an active ester containing a structure as shown in formula I A base aromatic monoamine compound and an optional aromatic diamine compound having the structure shown in formula II are reacted to obtain the modified maleimide compound.

Ideally, the reaction temperature is 70-200°C, such as 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C , 135°C, 140°C, 145°C, 150°C, 160°C, 170°C, 180°C, 190°C or 195°C, and the specific point values between the above point values, limited by space and for the sake of simplicity, the present invention It is not exhaustive to enumerate the specific point values included in the range, and it is further ideal to be 80~170°C.

Ideally, the reaction time is 0.5 to 8 hours, such as 0.6 hours, 0.8 hours, 1 hour, 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours, 2.8 hours, 3 hours, 3.2 hours , 3.5 hours, 3.8 hours, 4 hours, 4.2 hours, 4.5 hours, 4.8 hours, 5.0 hours, 5.5 hours, 6.0 hours, 6.5 hours, 7.0 hours, 7.5 hours, or 7.8 hours, and specific point values between the above point values , due to space limitations and for the sake of brevity, the present invention does not exhaustively enumerate the specific point values included in the range.

Ideally, the reaction is performed under a protective atmosphere, ideally nitrogen.

Ideally, the reaction is carried out in the presence of a solvent.

The solvent is not particularly limited, as long as it does not interfere with the reaction, exemplarily including but not limited to: alcohol solvents, ether solvents, ketone solvents, aromatic hydrocarbon solvents, ester solvents, nitrogen-containing solvents or sulfur-containing solvents Any one or a combination of at least two of the solvent-like solvents. Wherein, the alcohol solvent includes any one or a combination of at least two of methanol, ethanol, propanol or butanol; the ether solvent includes tetrahydrofuran, 1,4-dioxane, methyl cellosolve , butyl cellosolve or propylene glycol monomethyl ether or a combination of at least two; the ketone solvents include any one or at least two of acetone, butanone, methyl isobutyl ketone or cyclohexanone combination; the aromatic hydrocarbon solvent includes any one or a combination of at least two of toluene, xylene or benzene; the nitrogen-containing solvent includes N,N-dimethylformamide and/or N,N -Dimethylacetamide; the ester solvent includes any one or a combination of at least two of ethyl acetate, butyl acetate, γ-butyrolactone or ethoxy ethyl acetate; The sulfur-containing solvent includes dimethylsulfoxide. From the viewpoint of solubility, it is ideal to be any one or a combination of at least two of alcohol solvents, ketone solvents, ester solvents or nitrogen-containing solvents; from the viewpoint of low toxicity, it is more desirable to be cyclohexanone, Any one or a combination of at least two of propylene glycol monomethyl ether, methyl cellosolve, or γ-butyrolactone; it is further ideal if high volatility is also considered and it does not remain in the form of residual solvents during post-manufacturing It is any one or a combination of at least two of cyclohexanone, propylene glycol monomethyl ether, N,N-dimethylformamide or N,N-dimethylacetamide.

The amount of the solvent used can be properly adjusted according to the different solubilities of the raw materials and products, so that each raw material and product can be dissolved in the solvent. From the comprehensive consideration of solubility and reaction efficiency, the ideal solvent quality is 0.2 to 10 times the sum of the raw materials, such as 0.25 times, 0.3 times, 0.5 times, 0.7 times, 0.9 times, 1 times, 1.5 times, 2 times , 2.5 times, 3 times, 3.5 times, 4 times, 4.5 times, 5 times, 5.5 times, 6 times, 6.5 times, 7 times, 7.5 times, 8 times, 8.5 times, 9 times or 9.5 times, etc., more ideally 0.4~5 times.

In another aspect, the present invention provides a thermosetting resin composition comprising an epoxy resin and the above-mentioned modified maleimide compound.

The thermosetting resin composition provided by the present invention comprises epoxy resin and the above-mentioned modified maleimide compound, and the molecular structure of described modified maleimide compound contains active ester group and maleimide simultaneously. Amino group has more reactive active sites. When it is used as a curing agent to react with epoxy resin, on the one hand, when the active ester group reacts with epoxy resin, it will not produce strong polar secondary hydroxyl groups, so that the cured product It has low dielectric loss, low water absorption and low dielectric constant; on the other hand, maleimide group can be cured and self-polymerized to form a high rigidity and high heat resistance structure, so it has excellent heat resistance and high T _g and mechanical properties, as well as a low coefficient of thermal expansion.

Ideally, the epoxy resin refers to an epoxy resin having at least two epoxy groups in one molecule, exemplarily including but not limited to: bifunctional bisphenol A epoxy resin, bifunctional bisphenol F type epoxy resin, difunctional bisphenol S type epoxy resin, phenol formaldehyde type epoxy resin, methyl Phenol novolac epoxy resin, bisphenol A novolac epoxy resin, dicyclopentadiene (DCPD) epoxy resin, biphenyl epoxy resin, DCPD novolac epoxy resin, biphenyl novolac epoxy resin, resorcinol Phenol-type epoxy resin, naphthalene-based epoxy resin, phosphorus-containing epoxy resin, silicon-containing epoxy resin, glycidylamine-type epoxy resin, alicyclic epoxy resin, polyethylene glycol-type epoxy resin, four Any one or combination of at least two of phenol ethane tetraglycidyl ether, trisphenol methane type epoxy resin, condensate of difunctional cyanate and epoxy resin or condensate of difunctional isocyanate and epoxy resin ; Exemplary combinations include: a combination of a difunctional bisphenol A epoxy resin and a bifunctional bisphenol F epoxy resin, a combination of a bifunctional bisphenol S epoxy resin and a phenol formaldehyde epoxy resin, m-benzene A combination of a diphenol-type epoxy resin and a naphthalene-based epoxy resin, a combination of an alicyclic-type epoxy resin and a polyethylene glycol-type epoxy resin.

Ideally, the thermosetting resin composition further includes any one or a combination of at least two of other curing agents, flame retardants, inorganic fillers, organic fillers or curing accelerators.

Ideally, the other curing agents are selected from the group consisting of amine curing agents, phenolic curing agents, benzoxazine curing agents, cyanate ester curing agents, common active ester curing agents (with the modified horses described in the present invention) Any one or a combination of at least two of maleimide curing agents), acid anhydride curing agents or amine-modified maleimide curing agents.

Ideally, the flame retardant is selected from any one or a combination of at least two of halogenated organic flame retardants, phosphorus-based organic flame retardants, nitrogen-based organic flame retardants or silicon-containing organic flame retardants.

Ideally, the inorganic filler includes any one or a combination of at least two of non-metal oxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus; Silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, titanium Any one or a combination of at least two of strontium acid, calcium carbonate, calcium silicate or mica.

Ideally, the organic filler includes any one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfide powder.

Ideally, the curing accelerator includes any one or a combination of at least two of imidazole compounds, derivatives of imidazole compounds, piperidine compounds, pyridine compounds, organometallic Lewis acids or triphenylphosphine.

The "comprising" in the present invention means that in addition to the above-mentioned components, it may also include other components, and these other components endow the thermosetting resin composition with different characteristics. In addition, the "comprising" in the present invention can also be replaced with the closed "for" or "consisting of".

The preparation method of the thermosetting resin composition of the present invention can be as follows: first put the solid matter in, then add the solvent, stir until the solid matter is completely dissolved, then add the liquid resin and curing accelerator, and continue to stir evenly.

The solvent is not particularly limited, and includes any one or a combination of at least two of alcohol solvents, ether solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents or nitrogen-containing solvents, preferably ketone solvents. Wherein, the alcohol solvent includes any one or a combination of at least two of methanol, ethanol or butanol; the ether solvent includes ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol Or any one or a combination of at least two in butyl carbitol; the aromatic hydrocarbon solvent includes any one or a combination of at least two in benzene, toluene or xylene; the ester solvent includes ethyl acetate , butyl acetate or ethoxy ethyl acetate or a combination of at least two; the ketone solvents include any one of acetone, butanone, methyl ethyl ketone or cyclohexanone or A combination of at least two kinds; the nitrogen-containing solvent includes N,N-dimethylformamide and/or N,N-dimethylacetamide.

The amount of the solvent can be adjusted according to actual processing and application requirements.

The present invention also relates to a cured product, which is prepared by curing the aforementioned thermosetting resin composition.

In another aspect, the present invention provides a semiconductor sealing material, wherein a raw material of the semiconductor sealing material includes the above-mentioned thermosetting resin composition.

In another aspect, the present invention provides a prepreg comprising a substrate, and the above-mentioned thermosetting resin composition attached to the substrate by impregnation and drying.

Ideally, the substrate includes any one or a combination of at least two of glass fiber cloth, non-woven cloth or quartz cloth.

The nonwoven fabric is ideally an aramid nonwoven fabric.

The glass fiber cloth can be E-glass fiber cloth, D-glass fiber cloth, S-glass fiber cloth, T glass fiber cloth or NE-glass fiber cloth, etc.

The thickness of the substrate is not particularly limited; for good dimensional stability, the thickness of the substrate is ideally 0.01-0.2mm, such as 0.02mm, 0.05mm, 0.08mm, 0.1mm, 0.12mm, 0.15 mm, 0.17mm or 0.19mm, etc.

Ideally, the substrate is a substrate that has undergone fiber opening treatment and/or surface treatment with a silane coupling agent. In order to provide good water resistance and heat resistance, the silane coupling agent is ideally any one or a combination of at least two of epoxy silane coupling agents, amino silane coupling agents or vinyl silane coupling agents.

Exemplarily, the preparation method of the prepreg is: immersing the base material in the resin glue of the thermosetting resin composition, taking it out and drying it to obtain the prepreg.

Ideally, the drying temperature is 100-250°C, such as 105°C, 110°C, 115°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C , 210°C, 220°C, 230°C, 240°C or 245°C, etc.

Ideally, the drying time is 1 to 15 minutes, such as 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes or 14 minutes etc.

In another aspect, the present invention provides a circuit substrate, which includes at least one prepreg as described above, and metal foil disposed on one side or both sides of the prepreg.

The material of the metal foil is not particularly limited; ideally, the metal foil includes copper foil, nickel foil, aluminum foil or SUS foil.

Exemplarily, the method for preparing the circuit substrate is: laminating metal foil on one or both sides of a prepreg and curing to obtain the circuit substrate; or, bonding at least two prepregs to form laminated board, and then press metal foil on one or both sides of the laminated board, and solidify to obtain the circuit substrate.

Ideally, the curing is performed in a heated press.

Ideally, the curing temperature is 150-250°C, such as 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C , 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C or 245°C, etc.

Ideally, the curing pressure is 10~60kg/cm ² , such as 15kg/cm ² , 20kg/cm 2 , 25kg/cm ² , 30kg/cm ² , 35kg/cm ^{2 ,} 40kg/cm ² , 45kg/cm 2 ^2. 50kg/cm ² or 55kg/cm ² etc.

In another aspect, the present invention provides a laminated film comprising a base film or metal foil, and the above-mentioned thermosetting resin composition coated on at least one surface of the base film or metal foil.

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

(1) The molecular structure of the modified maleimide compound provided by the present invention contains maleimide group and active ester group simultaneously, has more reactive crosslinking sites, does not contain acidic substituent simultaneously, can Effectively reduce dielectric loss, dielectric constant and water absorption, it acts as a curing agent to react with epoxy resin, and the cured product obtained has excellent dielectric properties, heat resistance, heat and humidity resistance, low thermal expansion coefficient and processing performance.

(2) The thermosetting resin composition provided by the present invention comprises the modified maleimide compound and the epoxy resin of high crosslinking site, on the one hand, the active ester group in the described modified maleimide compound and When the epoxy resin reacts, no strong polar secondary hydroxyl groups are produced, so that the resulting cured product has low dielectric loss, low dielectric constant and low water absorption; on the other hand, the modified maleimide compound The maleimide group self-polymerizes to form a high rigid structure with excellent heat resistance, so that the obtained cured product has high _Tg , excellent heat resistance, heat and humidity resistance, mechanical properties and bonding properties, and good dielectric properties and processing performance.

(3) The thermosetting resin composition comprising the modified maleimide compound and its circuit substrate have low thermal expansion coefficient, low dielectric constant and dielectric loss, and exhibit excellent dielectric properties and heat resistance , resistance to heat and humidity and bonding strength with metals, which can meet the high performance requirements of circuit substrates.

The technical means of the present invention will be further described below through specific embodiments. It should be clear to those skilled in the art that the examples are only to help the understanding of the present invention, and should not be regarded as a specific limitation on the present invention.

Preparation Example 1

製備方法包括如下步驟： An aromatic monoamine compound L-1 containing an active ester group, the structural formula is as follows:

The preparation method comprises the following steps:

。 (1) In a 3L flask equipped with a thermometer, dropping funnel, and stirring device, add 139.1g (1mol) p-nitrophenol, 140.6g (1mol) benzoyl chloride and 1500g methylene chloride, stir and dissolve; Place it in a low-temperature tank at -5°C, slowly add 106.2g (1.05mol) of triethylamine dropwise in 2 hours, control the temperature of the system within the range of -5~10°C, and continue the reaction for 1 Hour. After the reaction, add deionized water and stir for 10 minutes, remove the water layer by static separation, and repeat the washing operation of the obtained dichloromethane layer until the pH of the water layer is 7; finally, concentrate and dry by heating under reduced pressure to obtain Aromatic mononitro compound containing active ester group

.

(2) In a 3L flask equipped with a thermometer, dropping funnel, stirring device, reflux condenser and nitrogen tube, add 243.2g of the aromatic mononitro compound containing active ester groups obtained in step (1), 6g of 5% wet Palladium carbon (Pd content is 5%, water content is 55%) and 1000g of N,N-dimethylformamide, and stirred with nitrogen gas. Raise the temperature to 50°C, slowly add 75g of hydrazine hydrate dropwise for about 2 hours, control the reaction temperature at about 60°C, and continue to stir and react for 6 hours after the dropwise addition is completed. After the reaction was completed, the filtrate was concentrated by distillation under reduced pressure, then added to deionized water-methanol for recrystallization, the precipitate was washed repeatedly with deionized water and methanol, then filtered, and the filter residue was vacuum-dried to obtain Active ester-based aromatic monoamine compound L-1.

Calculated and measured according to the feed ratio, the active ester group-containing aromatic monoamine compound L-1 has a primary amino group (-NH ₂ ) equivalent of 213.2 g/eq., and an active ester group equivalent of 213.2 g/eq.

Preparation example 2

製備方法包括如下步驟： A kind of aromatic monoamine compound L-2 containing active ester group, structural formula is as follows:

The preparation method comprises the following steps:

。 (1) In a 3L flask equipped with a thermometer, a dropping funnel, and a stirring device, add 139.1g (1mol) of p-nitrophenol, 78.5g (1mol) of acetyl chloride and 1000g of dichloromethane, stir and dissolve; place the flask Slowly add 106.2g (1.05mol) triethylamine dropwise in a low-temperature tank at -5°C for 2 hours, and control the temperature of the system within the range of -5~5°C. After the dropwise addition of triethylamine is completed, continue the reaction for 1 hour . After the reaction, add deionized water and stir for 10 minutes, remove the water layer by standing and separating, and repeat the washing operation of the obtained dichloromethane layer until the pH of the water layer is 7; finally, concentrate and dry by heating under reduced pressure to obtain Aromatic mononitro compound containing active ester group

.

(2) In a 3L flask equipped with a thermometer, dropping funnel, stirring device, reflux condenser and nitrogen tube, add 195.2g of the aromatic mononitro compound containing active ester groups obtained in step (1), 6g of 5% wet Palladium carbon (Pd content is 5%, water content is 55%) and 1000g of N,N-dimethylformamide, and stirred with nitrogen gas. Raise the temperature to 50°C, slowly add 75g of hydrazine hydrate dropwise for about 2 hours, control the reaction temperature at about 60°C, and continue to stir and react for 6 hours after the dropwise addition is completed. After the reaction was completed, the filtrate was concentrated by distillation under reduced pressure, then added to deionized water-methanol for recrystallization, the precipitate was washed repeatedly with deionized water and methanol, then filtered, and the filter residue was vacuum-dried to obtain Active ester-based aromatic monoamine compound L-2.

Calculated and measured according to the feed ratio, the active ester group-containing aromatic monoamine compound L-2 has a primary amino group (-NH ₂ ) equivalent of 165.2 g/eq., and an active ester group equivalent of 165.2 g/eq.

Preparation example 3

製備方法包括如下步驟： A kind of aromatic diamine compound L-3, structural formula is as follows:

The preparation method comprises the following steps:

(1) In a 3L flask equipped with a thermometer, dropping funnel, and stirring device, add 55.1g (0.5mol) of hydroquinone, 203g (1mol) of terephthaloyl chloride and 2000g of dichloromethane, stir to dissolve Place the flask in a low-temperature tank at -10°C, slowly add 106.2g (1.05mol) of triethylamine dropwise, and control the temperature of the system within the range of -10 to 0°C. After the addition of triethylamine is complete, continue the reaction for 1 After one hour, 139.1 g (1 mol) of p-nitrophenol was added, and then 106.2 g (1.05 mol) of triethylamine was slowly added dropwise. After the addition of triethylamine was completed, the reaction was continued for 2 hours. After the reaction was completed, let it stand for 2 hours, filter at room temperature to remove the precipitated triethylamine salt, distill the filtrate under reduced pressure and dry to obtain the primary product powder, wash the primary product with ionized water and ethanol several times in turn, then filter, and dry the filter residue. Thereby obtaining the aromatic dinitro compound, the structure is as follows:

(2) In the 3L flask that thermometer, dropping funnel, stirring device, reflux condenser, nitrogen tube are installed, add the aromatic dinitro compound that 259.3g step (1) obtains, 6g 5% wet palladium carbon (Pd content 5%, the water content is 55%), 1000g N,N-dimethylformamide, and stir with nitrogen gas. Raise the temperature to 50°C, slowly add 80g of hydrazine hydrate dropwise for about 2 hours, control the reaction temperature at about 60°C, and continue to stir and react for 6 hours after the dropwise addition is completed. After the reaction is finished, filter, the filtrate is distilled and concentrated under reduced pressure, and then added to deionized water-methanol for recrystallization, the separated precipitate is repeatedly washed with deionized water and methanol several times, then filtered, and the filter residue is vacuum-dried, thereby The aromatic diamine compound L-3 containing an active ester group was obtained.

Calculated and measured according to the feed ratio, the primary amino group (-NH ₂ ) equivalent of the active ester group-containing aromatic diamine compound L-3 is 147.1 g/eq., and the active ester group equivalent is 147.1 g/eq.

Example 1

A modified maleimide compound M-1, the preparation method is as follows: 4,4'-diphenylmethane bismaleimide 179.2 g (BMI produced by K.I company, the content of maleimide group is 1mol), 36.1g (0.17mol) and 323g of dimethylacetamide containing active ester group aromatic monoamine compound L-1, carry out reduction in the system Nitrogen pressure was used for displacement, stirring and dissolving, and then the temperature was raised to 100° C. for 2 hours to obtain the dimethylacetamide solution of the modified maleimide compound M-1.

Calculated and measured according to the feed ratio, the sum of the equivalents of the active ester group and the secondary amino group in the modified maleimide compound M-1 provided in this example is about 636g/eq.

Example 2

A modified maleimide compound M-2, the preparation method of which is as follows: Put 179.2 g of 4,4'-diphenylmethane bismaleimide into a flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen device (BMI produced by K.I Company, the maleimide group content is 1mol ), 19.8g (0.1mol) of 4,4'-diaminodiphenylmethane, 14.5g (0.068mol) of active ester group-containing aromatic monoamine compound L-1 and 320g of dimethylacetamide. Nitrogen replacement under reduced pressure was carried out, stirring and dissolving was carried out, and then the temperature was raised to 100° C. for 2 hours to react to obtain the dimethylacetamide solution of the modified maleimide compound M-2.

Calculated and measured according to the feed ratio, the sum of the equivalents of the active ester group and the secondary amino group in the modified maleimide compound M-2 provided in this example is about 636 g/eq.

Example 3

A modified maleimide compound M-3, the preparation method is as follows: 4,4'-diphenylmethane bismaleimide 179.2 g (BMI produced by K.I company, maleimide group content is 1mol), aromatic diamine compound L-3 containing active ester group 29.4g (0.1mol), aromatic monoamine compound L-1 containing active ester group 16.4 g (0.076mol) and 338g of dimethylacetamide, the system was replaced with nitrogen under reduced pressure, dissolved while stirring, and then heated to 100°C for 2 hours to obtain the modified maleimide compound M-3 dimethylacetamide solution.

Calculated and measured according to the feed ratio, the sum of the equivalents of the active ester and the secondary amino group in the modified maleimide compound M-3 provided in this example is about 636g/eq.

Example 4

A kind of modified maleimide compound M-4, preparation method is as follows: drop into polyphenylmethane polymaleimide 181g (production of Daiwakasei company) in the flask that thermometer, reflux condenser, stirrer, nitrogen device are installed BMI-2300, maleimide group content is 1mol), active ester group-containing aromatic monoamine compound L-2 82.6g (0.5mol) and dimethylacetamide 395.5g, the system is decompressed nitrogen Replacement, stirring to dissolve, and then heating to 110°C After reacting for 2 hours, a dimethylacetamide solution of the modified maleimide compound M-4 was obtained.

Calculated and determined according to the feed ratio, the sum of the equivalents of the active ester group and the secondary amino group in the modified maleimide compound M-4 provided in this example is about 264 g/eq.

Example 5

A kind of modified maleimide compound M-5, preparation method is as follows: drop into polyphenylmethane polymaleimide 144.8g (Daiwakasei company The produced BMI-2300, maleimide group content is 0.8 mol), 68.9 g of maleimide compound containing aliphatic long-chain structure (BMI-689 produced by Designer Molecules Inc., maleimide group content 0.2mol), aromatic diamine compound L-3 containing active ester group 44.1g (0.15mol), aromatic monoamine compound L-2 containing active ester group 16.5g (0.1mol) and dimethylacetamide 412g, The system was replaced with nitrogen under reduced pressure, dissolved while stirring, and then heated to 150° C. for 2 hours to react to obtain the dimethylacetamide solution of the modified maleimide compound M-5.

Calculated and measured according to the feed ratio, the sum of the equivalents of the active ester and the secondary amino group in the modified maleimide compound M-5 provided in this example is about 549 g/eq.

Comparative example 1

A kind of maleimide compound N-1, preparation method is as follows: drop into the flask that thermometer, reflux condenser, stirrer, nitrogen device are installed 179.2g of 4,4'-diphenylmethane bismaleimide ( The BMI that K.I company produces, maleimide group content is 1mol), p-aminophenol 16.8g (0.15mol) and dimethylacetamide 294g, carry out decompression nitrogen replacement in the system, dissolve while stirring, then The temperature was raised to 100° C. for 2 hours to react to obtain a dimethylacetamide solution of maleimide compound N-1 having a phenolic hydroxyl group and an N-substituted maleimide group.

Calculated and measured according to the feed ratio, the sum of the equivalent weights of hydroxyl and secondary amino groups in the maleimide compound N-1 provided in this comparative example is about 636g/eq.

Comparative example 2

A kind of maleimide compound N-2, preparation method is as follows: drop into 4,4'-diphenylmethane bismaleimide 179.2g ( The BMI produced by K.I company, the content of maleimide group is 1mol), 19.8g (0.1mol) of 4,4'-diaminodiphenylmethane, 6.8g (0.06mol) of p-aminophenol and dimethyl Acetamide 309g, carry out decompression nitrogen replacement in the system, stir to dissolve, then raise the temperature to 100 ° C for 2 hours to obtain a maleimide compound with a phenolic hydroxyl substituent and an N-substituted maleimide group N-2 in dimethylacetamide solution.

According to the calculation and determination of the feed ratio, the sum of the equivalent weights of hydroxyl and secondary amino groups in the maleimide compound N-2 provided in this comparative example is about 635g/eq.

The experimental materials used in the following application examples and comparative examples of the present invention are shown in Table 1.

Application example 1

A kind of thermosetting resin composition and its prepreg and circuit substrate, preparation method is as follows: (1) 31.5 parts by weight of epoxy resin A-1, 68.5 parts by weight of modified maleimide compound M-1, 0.04 Parts by weight of 4-dimethylaminopyridine (curing accelerator D-1) and 0.06 parts by weight of 2-ethyl-4-methylimidazole (curing accelerator D-2) are uniformly mixed in a solvent to obtain a thermosetting resin composition The solid content of the resin glue is 65%; impregnate the above glue with 2116 glass fiber cloth to control the appropriate thickness, and then bake it in an oven at 160°C for 10 minutes to make a prepreg; (2) 7 sheets of prepreg were stacked together, and 1Oz RTF copper foil was stacked on the upper and lower sides. The circuit substrate was made under the conditions of curing temperature of 200°C, curing pressure of 45Kg/cm ² and curing time of 120 minutes.

Application example 2

A kind of thermosetting resin composition and its prepreg and circuit substrate, preparation method is as follows: (1) 31.5 parts by weight of epoxy resin A-1, 68.5 parts by weight of modified maleimide compound M-2, 0.04 parts by weight Parts by weight of 4-dimethylaminopyridine (curing accelerator D-1) and 0.06 parts by weight of 2-ethyl-4-methylimidazole (curing accelerator D-2) are uniformly mixed in a solvent to obtain a thermosetting resin composition The solid content of the resin glue is 65%; the above glue is impregnated with 2116 glass fiber cloth to control the appropriate thickness, and then baked in an oven at 145°C for 15 minutes to make a prepreg; (2) 7 sheets of prepreg were stacked together, and 1Oz RTF copper foil was stacked on the upper and lower sides, and the circuit substrate was made under the conditions of curing temperature of 190°C, curing pressure of 60Kg/cm ² and curing time of 150 minutes.

Application example 3

A kind of thermosetting resin composition and its prepreg and circuit substrate, preparation method is as follows: (1) 31.5 parts by weight of epoxy resin A-1, 68.5 parts by weight of modified maleimide compound M-3, 0.04 parts by weight Parts by weight of 4-dimethylaminopyridine (curing accelerator D-1) and 0.06 parts by weight of 2-ethyl-4-methylimidazole (curing accelerator D-2) are uniformly mixed in a solvent to obtain a thermosetting resin composition The solid content of the resin glue is 65%; impregnate the above glue with 2116 glass fiber cloth to control the appropriate thickness, and then bake it in an oven at 175°C for 5 minutes to make a prepreg; (2) 7 prepregs were stacked together, and 1Oz RTF copper foil was stacked on the upper and lower sides. The circuit substrate was made under the conditions of curing temperature of 220°C, curing pressure of 30Kg/cm ² and curing time of 90 minutes.

Application example 4~6, comparative example 3~5

A thermosetting resin composition and a prepreg and circuit substrate comprising it, the components and contents of the thermosetting resin composition are shown in Table 2, the preparation method of the prepreg and circuit substrate is the same as in Application Example 1; Application Example 1 ~6. The parts by weight mentioned in Comparative Examples 3~6 all refer to the parts by weight of solid resin without solvent.

Performance Testing:

Performance tests were performed on the thermosetting resin compositions provided in Application Examples 1-6 and Comparative Examples 3-6 and the circuit substrates containing them. The method is as follows: (1) Glass transition temperature (T _g ): Tested with a DMA instrument, according to the standard Measured according to the DMA test method specified in IPC-TM-650 2.4.24; (2) Coefficient of thermal expansion CTE (Z-axis): using TMA instrument, according to the CTE (Z-axis) specified in standard IPC-TM-650 2.4.24 axis) test method to measure the coefficient of thermal expansion between 50 and 260°C; (3) Dielectric constant D _k and dielectric loss factor D _f : according to the plate method specified in standard IPC-TM-650 2.5.5.9, measured at 1GHz D _k and D _f ; (4) Thermal stratification time T288 (with copper) or T300 (with copper): use TMA instrument, according to T288 (with copper) or T300 specified in standard IPC-TM-650 2.4.24.1 (with copper) test method for measurement; (5) Moisture and heat resistance (PCT) evaluation: After keeping three samples of 100×100mm in a pressure cooking device at 180°C and 105KPa for 5 hours, immerse them in solder at 288°C In the tank for 5 minutes, observe whether the sample has stratified bubbling and other phenomena. If no stratified bubbling occurs in the 3 samples, it will be recorded as 3/3; Layer bubbling is recorded as 1/3, and 0 pieces without delamination bubbling are recorded as 0/3; (6) PCT water absorption: take the substrate pretreated by the test method (5) PCT test conditions, and follow the standard IPC-TM -650 2.6.2.1 specified in the water absorption test method; (7) peel strength (PS): According to the "received state" experimental conditions specified in the standard IPC-TM-650 2.4.8, test the peeling of the metal cover Strength; specific test results are shown in Table 3:

3.90(1GHz)，介電損耗因子低於0.0090(1GHz)，T288(帶銅)>60分鐘，T300(帶銅)熱分層時間

45分鐘，玻璃化轉變溫度達到258~274℃，Z-CTE低至1.4~1.86%，剝離強度達到1.28~1.45N/mm，耐濕熱性可通過PCT(5小時)測試，能夠充分滿足高性能電路基板的應用要求。 According to the performance test data in Table 3, it can be seen that, compared with Comparative Examples 3-6, in the circuit substrates provided by Application Examples 1-6 of the present invention, the thermosetting resin composition used is based on the modified maleimide compound provided by the present invention As a curing component, it has low dielectric constant, low dielectric loss, excellent heat resistance and heat and humidity resistance, as well as high glass transition temperature (T _g ), low coefficient of thermal expansion (Z-CTE) and compatibility with Good bond strength to metals; its dielectric constant

3.90 (1GHz), dielectric loss factor lower than 0.0090 (1GHz), T288 (with copper) > 60 minutes, T300 (with copper) thermal delamination time

In 45 minutes, the glass transition temperature reaches 258~274℃, the Z-CTE is as low as 1.4~1.86%, the peel strength reaches 1.28~1.45N/mm, and the heat and humidity resistance can pass the PCT (5 hours) test, which can fully meet the high performance Application requirements for circuit substrates.

Comparing Application Example 1 and Comparative Example 3, Application Example 2 and Comparative Example 4, Application Example 4 and 5 and Comparative Example 5, Application Example 6 and Comparative Example 6, it can be seen that using the modified maleimide compound of the present invention ( Containing active ester group) cured thermosetting resin composition and circuit substrate, compared with ordinary maleimide compound curing system, in terms of dielectric constant, dielectric loss factor, heat resistance, water absorption and heat and humidity resistance performance more obvious advantages.

The applicant declares that the present invention illustrates a kind of modified maleimide compound of the present invention and its preparation method and application through the above examples, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must rely on The above-mentioned embodiment just can implement. Those with ordinary knowledge in the technical field should understand that any improvement of the present invention, the equal replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention. .

Claims (16)

A modified maleimide compound, characterized in that the raw materials for the preparation of the modified maleimide compound include: a maleimide-containing compound and an active ester-containing aromatic compound having a structure as shown in formula I. Monoamine compounds;

Wherein, Ar is selected from substituted or unsubstituted C ₆ ~C ₃₀ divalent aromatic groups; X is selected from substituted or unsubstituted C ₆ ~C ₂₀ aryl groups, X ₁ -Y ₁ -X ₂ -, substituted or Unsubstituted C ₁ ~C ₂₀ linear or branched alkyl, substituted or unsubstituted C ₃ ~C ₂₀ cycloalkyl; X ₁ , X ₂ are each independently selected from substituted or unsubstituted C ₆ ~C ₁₂ Aryl; Y ₁ is selected from C ₁ ~C ₅ straight chain or branched alkylene, -O-, -S-, arganyl or arylene; the substituted substituents in Ar, X are each independently selected from F, C ₁ ~C ₅ straight chain or branched chain alkyl. The modified maleimide compound as claimed in item 1, wherein, the Ar is selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene; The substituted substituent is selected from F, C ₁ ~C ₅ straight chain or branched chain alkyl; the X is selected from C ₁ ~C ₁₀ straight chain or branched chain alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted Naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted biphenyl ether group; the substituted substituent is selected from F, C ₁ ~ C ₅ straight chain or branched chain alkyl. The modified maleimide compound as described in claim 1, wherein, based on 1 mol of the maleimide group in the maleimide group-containing compound, the active ester group-containing aromatic monoamine compound The dosage is 0.05~1mol. The modified maleimide compound as described in claim 1 or 2, wherein the preparation raw material also includes an aromatic diamine compound having a structure as shown in formula II; H ₂ N-Ar ₁ -Y-Ar ₂ -NH ₂ formula II; wherein, Ar ₁ and Ar ₂ are each independently selected from substituted or unsubstituted C ₆ ~C ₃₀ arylene groups; the substituted substituents in Ar ₁ and Ar ₂ are each independently selected from F, C ₁ ~C ₅ straight chain or branched chain alkyl; Y is selected from C ₁ ~C ₅ straight chain or branched chain alkylene, -O-,

,

or

Ar ₃ and Ar ₄ are each independently selected from substituted or unsubstituted C ₆ ~C ₃₀ divalent aromatic groups; the substituted substituents in Ar ₃ and Ar ₄ are each independently selected from halogen, unsubstituted or halogenated C ₁ ~ C ₅ straight chain or branched chain alkyl, group containing aryl phosphorus oxygen structure; Z is selected from C ₁ ~ C ₂₀ straight chain or branched chain alkylene, C ₃ ~ C ₂₀ cycloalkylene , C ₆ ~C ₂₀ arylene group or biphenylene ether group; n is selected from 0~10. The modified maleimide compound as described in Claim 4, wherein, the Ar ₁ and Ar ₂ are each independently selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene or substituted or unsubstituted Substituted biphenylene; the substituted substituents are each independently selected from F, C ₁ ~ C ₅ straight chain or branched chain alkyl; the Ar ₃ , Ar ₄ are each independently selected from

,

,

_Y2 is selected from unsubstituted or halogenated C1~C5 straight chain or branched chain alkylene, -O-, -S-,

,

R ₁ and R ₂ are each independently selected from halogen, unsubstituted or halogenated C ₁ ~C ₅ straight chain or branched chain alkyl,

n ₁ and n ₃ are each independently selected from an integer of 0-4; n ₂ is selected from an integer of 0-6. The modified maleimide compound as described in claim 4, wherein the Ar ₃ and Ar ₄ are each independently selected from

,

,

,

,

The modified maleimide compound as described in Claim 4, wherein, the Z is selected from C ₁ ~C ₅ linear or branched chain alkylene, C ₃ ~C ₁₂ cycloalkylene, phenylene, Naphthylene, biphenylene or phenylene ether. The modified maleimide compound as described in claim 4, wherein, based on 1 mol of the maleimide group in the maleimide group-containing compound, the active ester group-containing aromatic monoamine compound and The total amount of amine groups in the aromatic diamine compound is 0.05~1mol; Based on 1 mol of maleimide group in the compound, the amount of the aromatic diamine compound is 0.01-0.25 mol. A method for preparing a modified maleimide compound as described in any one of claim items 4 to 8, characterized in that the preparation method comprises: a maleimide-containing compound having a structure as shown in formula I The active ester group-containing aromatic monoamine compound and the optional aromatic diamine compound having the structure shown in formula II are reacted to obtain the modified maleimide compound. The preparation method as described in Claim 9, wherein the reaction temperature is 70-200°C, and the reaction time is 0.5-8 hours. The preparation method as claimed in item 9, wherein the reaction is carried out in a protective atmosphere, and the reaction is carried out in the presence of a solvent. A thermosetting resin composition, characterized in that the thermosetting resin composition includes epoxy resin and the modified maleimide compound as described in any one of claims 1 to 8. A semiconductor sealing material, characterized in that the raw material of the semiconductor sealing material includes the thermosetting resin composition as described in claim 12. A prepreg, characterized in that the prepreg includes a substrate, and the thermosetting resin composition as described in claim 12 adhered to the substrate by impregnation and drying. A circuit substrate, characterized in that the circuit substrate comprises at least one prepreg as described in claim 14, and metal foils disposed on one side or both sides of the prepreg. A laminated film, characterized in that the laminated film comprises a base film or metal foil, and the thermosetting resin composition as described in Claim 12 coated on at least one surface of the base film or metal foil.