TW202220954A - Modified maleimide compound and preparation method and application thereof capable of being used as a curing agent to react with epoxy resin to obtain a cured product - Google Patents

Abstract

The present invention provides a modified maleimide compound and a preparation method and application thereof. The preparation raw materials of the modified maleimide compound include: a maleimide group-containing compound and an active ester group-containing aromatic monoamine compound with a structure shown in a formula I. The modified maleimide compound is prepared from specific raw materials. The molecular structure of the modified maleimide compound contains maleimide groups and active ester groups, and the two active groups are synergistic with each other, so that the modified maleimide compound has higher reaction crosslinking sites, low water absorption, low dielectric constant and dielectric loss. The modified maleimide compound is used as a curing agent to react with epoxy resin, and the obtained cured product has low water absorption, high glass transition temperature, excellent dielectric property, heat resistance, wet heat resistance, low thermal expansion coefficient and strong metal bonding force, and 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 a preparation method and application thereof.

In recent years, with the rapid development of the information industry, electronic products have become increasingly shorter, thinner, higher-performance and more multi-functional. Integrated circuits are advancing in the direction of high density, high precision and high integration, which requires the printed circuit substrate material to have good dielectric properties, and also requires the substrate to have good heat resistance to meet the reliability requirements of the printed circuit board process. For example, in the substrates of smart mobile phones, etc., which are driven by thinning and price reduction, materials with low relative permittivity are required to cope with thinning; in the equipment of communication systems represented by servers, routers, and mobile base stations, etc. , In order to be able to be used in higher frequency bands 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 in 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 bismaleimide-modified epoxy resin and its preparation method and its use. The preparation method includes: firstly reacting a modifier, epoxy resin and bismaleimide to form A resin glue solution is formed, and the resin glue solution continues to react with the curing agent and the curing accelerator to obtain a bismaleimide modified epoxy resin; wherein, the modifier is selected from the group consisting of o-diallyl bisphenol A dicondensation Allyl compounds of glycerol ether, bisphenol A bisallyl 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 substrate 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: firstly reacting bismaleimide resin with an allyl compound to obtain a prepolymer; then combining the prepolymer with phosphorus-containing epoxy resin, composite curing After the glue is coated on the glass fiber cloth and baked to make a B-stage prepreg, it is superposed 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 weak polarity, and cannot directly react with epoxy resins. It is often modified or mixed with amines, diallyl compounds, etc. When epoxy resin is used in combination, the grid structure formed after the reaction contains a large number of secondary alcohol hydroxyl groups with high polarity and easy water absorption, 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 comprises a maleimide compound, an epoxy resin, a structural unit derived from an aromatic vinyl compound and a The copolymer resin of the structural unit, the silica treated with the aminosilane-based coupling agent, the organic solvent, etc., the maleimide compound used contains an acidic substituent and a maleimide group, so as to obtain a 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 the resin varnish contains an acidic substituent such as a hydroxyl group, a carboxyl group or a sulfonic acid group. Electrical properties, water absorption, Moisture and heat resistance is adversely affected.

Therefore, the development of 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 is a research focus in this field. .

【Prior technical literature】

【Patent Literature】

[Patent Document 1] CN105385105A

[Patent Document 2] CN101652026A

[Patent Document 3] CN108401433A

In view of the deficiencies of the prior art, the object of the present invention is to provide a modified maleimide compound and its preparation method and application, wherein the modified maleimide compound is prepared from specific raw materials, and its molecular structure is Contains maleimide group and active ester group, and the two active groups cooperate with each other, so that the modified maleimide compound has a higher reaction cross-linking site; The epoxy resin composition using the amine compound as the curing agent has low water absorption after curing, excellent dielectric properties, heat resistance and damp heat resistance, and low thermal expansion coefficient, which can fully meet the application requirements of high-performance circuit substrates.

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

In a first aspect, the present invention provides a modified maleimide compound, and the preparation raw materials of the modified maleimide compound include: a maleimide group-containing compound and a compound having a structure as shown in formula I. Active ester aromatic monoamine compound;

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 group.

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, X ₁ - Y ₁ -X ₂ -substituted or unsubstituted C ₁ -C ₂₀ (eg 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 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 (for example, C ₆ , C ₉ , C ₁₀ or C ₁₂ , etc.) aryl.

Y ₁ is selected from C ₁ -C ₅ (eg C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) straight-chain or branched alkylene, -O-, -S-, sulfanyl or ssene.

The substituted substituents in Ar and X are each independently selected from F, C ₁ -C ₅ (eg C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) linear or branched alkyl.

In the present invention, the "divalent aromatic group" means a group containing an aryl group with two bonding sites, including arylene groups (such as phenylene, naphthylene, biphenylene, Anthracenylene or phenanthrene, etc.), and at least two aryl groups are connected by connecting groups (such as -O-, -S-, carbonyl, sulfanyl, sulfylene, alkylene or cycloalkylene, etc. ) are connected to form a substituent. When referring to the same description hereinafter, all have the same meaning.

In the present invention, the short straight line on one or both sides of the group structure (for example, the short straight line on the right side in X ₁ -Y ₁ -X ₂ -) represents the access bond of the group, not a methyl group.

The preparation raw materials of the modified maleimide compound provided by the present invention include two categories: maleimide group-containing compounds and active ester group-containing aromatic monoamine compounds; the modified maleimide group The amine compound contains two functional groups, maleimide group and active ester group. The two are synergistic with each other, so that the modified maleimide compound has both high reactive crosslinking sites and low dielectric constant. , low dielectric loss, high heat resistance and low thermal expansion coefficient; compared with the 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 damp heat resistance. The modified maleimide compound is used as a curing agent to undergo a curing reaction with epoxy resin, and the obtained cured product has low water absorption, high glass transition temperature, and has excellent dielectric properties, heat resistance, humidity and heat resistance, low temperature. Thermal expansion coefficient and strong metal bonding force.

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 the reaction to obtain an aromatic mononitro compound containing an active ester group

; The active ester group-containing aromatic mononitro compound is subjected to reduction reaction to obtain the active ester group-containing aromatic monoamine compound; wherein, Ar and X have the same limited range as in formula I, and Z ₁ 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 (eg C ₁ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C ₉ or C ₁₀ ) linear or branched chain Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted biphenyl ether; 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 group-containing compound includes a maleimide group-containing monomer and/or a maleimide group-containing polymer.

Ideally, the maleimide group-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-dimethylbenzenemaleimide, Any one or a combination of at least two of 2,6-dimethylbenzenemaleimide or N-phenylmaleimide.

Ideally, the maleimide group-containing polymer comprises maleimide resin, phenylmethane maleimide oligomer (or polyphenylene methane maleimide) or containing C ₅ ~C ₅₀ (e.g. _C6 , C8, _C10 , _C12 , _C15 , _C18 , _C20 , _C22 , _C25 , _C28 , _C30 , _C32 , _C35 , _C38 , _C40 , _C42 , C ₄₅ or C ₄₈ etc.) any one or a combination of at least two of the maleimide compounds of aliphatic long-chain structure.

Exemplarily, the maleimide group-containing compound may 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; enumerated above The names of BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI -5100, BMI-7000, and BMI-7000H were purchased from Daiwakasei Company, Japan, BMI-70 and BMI-80 were purchased from K.I Chemical Company, Japan, and MIR-3000-70MT and MIR-5000-60T were purchased from NIPPON KAYAKU Company, Japan.

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 of -5000 or BMI-6000 or a combination of at least two; the names listed above are all trade names, available from Designer Molecules Inc.

Ideally, based on the maleimide group in the maleimide group-containing compound being 1 mol, 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, due to space limitations and for the sake of simplicity, the present invention will not exhaustively enumerate 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, the amount of the active ester group-containing aromatic monoamine compound is 0.05-1 mol based on the maleimide group in the maleimide group-containing compound being 1 mol. The less the amount of the active ester group-containing aromatic monoamine compound is used, that is, the lower the degree of modification of the maleimide group-containing compound (matrix), the modified maleimide compound obtained by the reaction is, on the one hand, in the The solubility improvement effect in the organic solvent is not obvious. On the other hand, the proportion of functional groups that can react with epoxy groups in its structure is relatively low, and the effect of improving the brittleness of the cured product is also poor; on the contrary, the active ester-containing The more the amount of the base aromatic monoamine compound is used, although the higher the degree of modification is, the more favorable the solubility and toughness of the obtained modified maleimide compound are improved, but it also greatly sacrifices the maleimide group-containing compound. (matrix) advantages in terms of high glass transition temperature and low coefficient of expansion.

In the present invention, the preparation raw materials also include an aromatic diamine compound having a structure as shown in formula II;

H2N-Ar1 _- Y-Ar2 _{- NH2 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; the substituted substituents described in Ar ₁ and Ar ₂ are each independently selected from F, C ₁ -C ₅ (eg C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) linear or branched 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 (eg 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 group; the substituted substituents described in Ar ₃ , 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 or branched chain alkyl, groups containing aryl phosphorus oxygen structure.

Z is selected from C ₁ -C ₂₀ (eg 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.) linear or Branched 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 base, 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 to 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 , 4.7, 5, 5.3, 5.5, 5.8, 6, 6.2, 6.5, 6.8, 7, 7.5, 8, 8.5, 9, 9.5 or 10, and specific point values between the above-mentioned point values, are limited by space and for brevity Considering that the present invention does not exhaustively list the specific point values included in the 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; the substituted substituents are each Independently 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 Ar ₃ and Ar ₄ are independently selected from

,

、

、

、

或

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

,

,

,

or

.

或

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

or

.

n ₁ and n ₃ are each independently selected from an integer of 0 to 4, for example, 0, 1, 2, 3 or 4.

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

、

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

,

,

Ideally, the Z is selected from C ₁ -C ₅ (eg C ₁ , C ₂ , C ₃ , C ₄ or C ₅ ) straight or branched chain alkylene, C ₃ -C ₁₂ (eg C ₃ , C ₄ , C ₅ , C ₇ , C ₉ , C ₁₀ or C ₁₂ , etc.) cycloalkylene, phenylene, naphthylene, biphenylene or phenylene ether.

Ideally, based on the maleimide group in the maleimide group-containing compound being 1 mol, the total amount of amine groups in the active ester group-containing aromatic monoamine compound 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, as well as specific point values between the above-mentioned point values, due to space limitations 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 the maleimide group in the maleimide group-containing compound being 1 mol, the amount of the active ester group-containing aromatic monoamine compound and the aromatic diamine compound in the The total amount of amine groups is 0.05~1mol. The less the amount of the active ester group-containing aromatic monoamine compound and the aromatic diamine compound is used, that is, the lower the degree of modification of the maleimide group-containing compound (matrix), the modified maleimide obtained by the reaction. On the one hand, the solubility improvement effect of the compound in organic solvents is not obvious; The more the amount of the active ester group-containing aromatic monoamine compound and the aromatic diamine compound is used, although the degree of modification is higher, the solubility and toughness of the obtained modified maleimide compound are improved. The advantages of the maleimide-containing compound (matrix) in terms of high glass transition temperature and low expansion coefficient are sacrificed. because Therefore, the maleimide group in the maleimide group-containing compound is 1 mol, and the total amount of amine groups in the active ester group-containing aromatic monoamine compound and the aromatic diamine compound is ideally 0.1 ~0.6mol, more ideally 0.15~0.4mol.

Ideally, based on the maleimide group in the maleimide group-containing compound being 1 mol, the amount of the aromatic diamine compound 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, as well as specific point values between the above-mentioned point values, limited by space and for the sake of simplicity, the present invention does not The specific point values included in the range are then exhaustively enumerated.

As an ideal technical means of the present invention, the preparation raw materials of the modified maleimide compound include a combination of a maleimide group-containing compound, an active ester group-containing aromatic monoamine compound and an aromatic diamine compound. The amine group in the ester-based aromatic monoamine compound and the aromatic diamine compound undergoes an addition reaction with the maleimide group in the maleimide group-containing compound and is prepared. Wherein, the reaction between the active ester group-containing aromatic monoamine compound and the maleimide group-containing compound plays an end-capping role, which can prevent the molecular chain of the modified maleimide compound from continuing to grow, and is beneficial to control the modified maleimide group. The molecular weight of the lyimide compound; and the reaction between the aromatic diamine compound and the maleimide group-containing compound acts as a chain extension, 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 molecular weight. The amount of the aromatic diamine compound should not be too much, that is, based on the maleimide group in the maleimide group-containing compound being 1 mol, 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, the Y is

, the structure of the aromatic diamine compound is

(referred to as formula II-1), it can be prepared by the following method: diphenol compound HO-Ar ₃ -OH, compound

and compounds

Carry out the reaction to obtain aromatic dinitro compounds

; The aromatic dinitro compound undergoes a reduction reaction to obtain an aromatic diamine compound having a structure shown in formula II-1; wherein, Ar ₁ , Ar ₂ , Ar ₃ have the same limited range as in formula II, Z ₂ , Each Z ₃ is independently selected from hydroxy 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, the Y is

, the structure of the aromatic diamine compound is

(referred to as formula II-2), which can be prepared by the following methods: diphenol compound HO-Ar ₄ -OH, bifunctional compound

, the monofunctional nitrophenol compound HO-Ar ₂ -NO ₂ reacts with the monofunctional nitrophenol compound HO-Ar ₁ -NO ₂ to obtain an aromatic dinitro compound

; The aromatic dinitro compound undergoes a reduction reaction to obtain an aromatic diamine compound having the structure shown in formula II-2; wherein, Ar ₁ , Ar ₂ , Ar ₄ have the same limited range as in formula II, Z ₄ , Each Z ₅ is independently selected from hydroxy or halogen (eg, F, Cl, Br or I).

On the other hand, the present invention provides a preparation method of the above-mentioned modified maleimide compound, the preparation method comprising: a maleimide group-containing compound, an active ester-containing compound having 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 temperature of the reaction 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, as well as specific point values between the above-mentioned point values. The specific point value included in the range is not exhaustively listed, and it is more preferably 80 to 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 will not exhaustively list the specific point values included in the range.

Ideally, the reaction is carried out in 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 hinder the reaction, and exemplarily includes but is not limited to: alcohol-based solvents, ether-based solvents, ketone-based solvents, aromatic hydrocarbon-based solvents, ester-based solvents, nitrogen-containing solvents, or sulfur-containing solvents Any one or a combination of at least two of the solvent-like substances. 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 any one or a combination of at least two; the ketone solvent includes any one or at least two in acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone 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 ethoxyethyl acetate; The sulfur-containing solvent includes dimethylsulfite. From the viewpoint of solubility, any one or a combination of at least two of alcohol-based solvents, ketone-based solvents, ester-based solvents, and nitrogen-containing solvents is desirable; from the viewpoint of low toxicity, cyclohexanone, Any one of propylene glycol monomethyl ether, methyl cellosolve, or γ-butyrolactone, or a combination of at least two of them; if high volatility is also considered, and it does not remain in the form of residual solvent during later production, it is further ideal 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 can be appropriately adjusted according to the different solubility of the raw materials and products, so that the raw materials and products can be dissolved in the solvent. In terms 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, and 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. 0.4~5 times.

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

The thermosetting resin composition provided by the present invention includes epoxy resin and the above-mentioned modified maleimide compound, and the molecular structure of the modified maleimide compound contains both active ester group and maleimide group The amine group has more reactive sites. When it reacts with the epoxy resin as a curing agent, on the one hand, when the active ester group reacts with the epoxy resin, it will not generate a strong secondary hydroxyl group, so that the cured product It has low dielectric loss, low water absorption and low dielectric constant; on the other hand, the maleimide group can be cured and self-polymerized to form a structure with high rigidity and high heat resistance, so it has excellent heat resistance, 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, bifunctional 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, isophthalic Phenol-type epoxy resin, naphthalene-type epoxy resin, phosphorus-containing epoxy resin, silicon-containing epoxy resin, glycidylamine-type epoxy resin, alicyclic epoxy resin, polyethylene glycol-type epoxy resin, four Phenolethane tetraglycidyl ether, trisphenol methane type epoxy resin, condensate of bifunctional cyanate ester and epoxy resin, or condensate of bifunctional isocyanate and epoxy resin, or a combination of at least two of them ; Exemplary combinations include: a combination of a bifunctional bisphenol A-type epoxy resin and a bifunctional bisphenol F-type epoxy resin, a combination of a bifunctional bisphenol S-type epoxy resin and a phenol formaldehyde-type epoxy resin, m-phenylene A combination of a diphenol type epoxy resin and a naphthalene type epoxy resin, and 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 agent is selected from amine curing agent, phenol curing agent, benzoxazine curing agent, cyanate ester curing agent, common active ester curing agent (with the modified horse according to the present invention). any one or a combination of at least two of them, an acid anhydride curing agent or an amine-modified maleimide curing agent.

Ideally, the flame retardant is selected from any one or a combination of at least two of halogen-based 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; further ideally, molten Silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, titanium Any one or a 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 sintered powder.

Ideally, the curing accelerator includes any one or a combination of at least two of imidazoles, derivatives of imidazoles, piperidines, pyridines, organic metal salt Lewis acids or triphenylphosphine.

In the present invention, "comprising" means that in addition to the above-mentioned components, other components may be included, and these other components impart different properties to the thermosetting resin composition. In addition, "comprising" in the present invention can also be replaced by closed "is" or "consisting of".

The preparation method of the thermosetting resin composition of the present invention can be as follows: firstly put the solid matter, then add the solvent, stir until the solid matter is completely dissolved, then add the liquid resin and the 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-based solvents, ether-based solvents, aromatic hydrocarbon-based solvents, ester-based solvents, ketone-based solvents or nitrogen-containing solvents, ideally ketone-based 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 , any one or a combination of at least two of butyl acetate or ethoxyethyl acetate; the ketone solvent includes any one of acetone, butanone, methyl ethyl ketone or cyclohexanone or A combination of at least two; 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 prepared by curing the aforementioned thermosetting resin composition.

In another aspect, the present invention provides a semiconductor sealing material, the raw material of which includes the thermosetting resin composition as described above.

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

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

The non-woven fabric is ideally an aramid non-woven fabric.

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

The thickness of the substrate is not particularly limited; for the consideration of good dimensional stability, the thickness of the substrate is ideally 0.01-0.2 mm, such as 0.02 mm, 0.05 mm, 0.08 mm, 0.1 mm, 0.12 mm, 0.15 mm 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 an epoxy silane coupling agent, an amino silane coupling agent or a vinyl silane coupling agent.

Exemplarily, the preparation method of the prepreg is as follows: the base material is immersed in the resin glue solution of the thermosetting resin composition, taken out and then dried 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 comprising at least one prepreg as described above, and metal foils disposed on one 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 preparation method of the circuit substrate is as follows: pressing a metal foil on one side or both sides of a prepreg, and curing it to obtain the circuit substrate; or, adhering at least two prepregs to make a laminate, and then press metal foil on one side or both sides of the laminate, and cure it to obtain the circuit substrate.

Ideally, the curing is carried out in a hot 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 simultaneously contains a maleimide group and an active ester group, has more reaction cross-linking sites, does not contain an acidic substituent, and can It can effectively reduce dielectric loss, dielectric constant and water absorption rate. It acts as a curing agent and undergoes curing reaction with epoxy resin, and the obtained cured product has excellent dielectric properties, heat resistance, damp heat resistance, low thermal expansion coefficient and processing performance.

(2) The thermosetting resin composition provided by the present invention comprises a modified maleimide compound and an epoxy resin with a high cross-linking site. On the one hand, the active ester group in the modified maleimide compound and the The epoxy resin does not produce strong polar secondary hydroxyl groups during the reaction, so that the obtained cured product has low dielectric loss, low dielectric constant and low water absorption; on the other hand, the modified maleimide compound in the The maleimide group self-polymerizes to form a high-rigidity structure, which has excellent heat resistance, so that the cured product has high T _g , excellent heat resistance, heat and humidity resistance, mechanical properties and bonding properties, and good dielectric properties. and processing properties.

(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, heat resistance , heat and humidity resistance and bonding strength with metal, 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 understood by those with ordinary knowledge in the technical field that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.

Preparation Example 1

A kind of aromatic monoamine compound L-1 containing active ester group, the structural formula is as follows:

The preparation method includes the following steps:

。 (1) In the 3L flask equipped with thermometer, dropping funnel and stirring device, add 139.1g (1mol) p-nitrophenol, 140.6g (1mol) benzyl chloride and 1500g methylene chloride, stir and dissolve; Place in the low temperature tank of -5 ℃, slowly drip 106.2g (1.05mol) triethylamine in 2 hours, control the temperature of the system in the range of -5～10 ℃, after the triethylamine is dripped, continue to react 1 Hour. After the reaction, deionized water was added and stirred for 10 minutes, the water layer was removed by standing for liquid separation, and the obtained methylene chloride layer was repeatedly washed with water until the pH of the water layer was 7; finally, concentrated and dried by heating under reduced pressure to obtain Aromatic mononitro compounds containing active ester groups

.

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

Calculated and determined according to the feeding ratio, the primary amino group (-NH ₂ ) equivalent of the active ester group-containing aromatic monoamine compound L-1 is 213.2 g/eq., and the active ester group equivalent is 213.2 g/eq.

Preparation Example 2

A kind of containing active ester group aromatic monoamine compound L-2, the structural formula is as follows:

The preparation method includes the following steps:

。 (1) In a 3L flask equipped with a thermometer, dropping funnel and stirring device, add 139.1g (1mol) p-nitrophenol, 78.5g (1mol) acetyl chloride and 1000g methylene chloride, stir and dissolve; the flask is placed In a low temperature tank at -5°C, 106.2g (1.05mol) of triethylamine was slowly added dropwise over 2 hours, and the temperature of the system was controlled within the range of -5 to 5°C. After the addition of triethylamine, the reaction was continued for 1 hour. . After the reaction, deionized water was added and stirred for 10 minutes, the water layer was removed by standing for liquid separation, and the obtained methylene chloride layer was repeatedly washed with water until the pH of the water layer was 7; finally, concentrated and dried by heating under reduced pressure to obtain Aromatic mononitro compounds containing active ester groups

.

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

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

Preparation Example 3

A kind of aromatic diamine compound L-3, structural formula is as follows:

The preparation method includes the following steps:

(1) In a 3L flask equipped with a thermometer, a dropping funnel and a stirring device, add 55.1g (0.5mol) of hydroquinone, 203g (1mol) of terephthalic chloride and 2000g of dichloromethane, stir and dissolve ; The flask is placed in the low temperature tank of -10 ℃, slowly drip 106.2g (1.05mol) triethylamine, the system temperature is controlled in the scope of -10 ~ 0 ℃, after the triethylamine is dripped, continue to react 1 After 1 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 dropwise addition of triethylamine, the reaction was continued for 2 hours. After the reaction is completed, it is left to stand for 2 hours, and the precipitated triethylamine salt is removed by filtration at room temperature. The filtrate is distilled under reduced pressure and dried to obtain the primary product powder. The primary product is washed successively with ionized water and ethanol for many times, and then filtered and the filter residue is dried. from And obtain aromatic dinitro compounds, the structure is as follows:

(2) in the 3L flask that is equipped with thermometer, dropping funnel, stirring device, reflux condenser, nitrogen tube, add the aromatic dinitro compound that 259.3g step (1) obtains, 6g 5% wet palladium carbon (Pd content be 5%, the water content is 55%), 1000g N,N-dimethylformamide, and stir with nitrogen. The temperature was raised to 50°C, 80 g of hydrazine hydrate was slowly added dropwise for about 2 hours, the reaction temperature was controlled at about 60°C, and the stirring reaction was continued for 6 hours after the dropwise addition. After the reaction is completed, filter, concentrate the filtrate by vacuum distillation, then add it to deionized water-methanol for recrystallization, and wash the precipitated precipitate several times with deionized water and methanol in turn, then filter, and vacuum dry the filter residue, thereby The active ester group-containing aromatic diamine compound L-3 was obtained.

Calculated and determined according to the charging ratio, the active ester group-containing aromatic diamine compound L-3 has a primary amino group (-NH ₂ ) equivalent of 147.1 g/eq., and an active ester group equivalent of 147.1 g/eq.

Example 1

A modified maleimide compound M-1, the preparation method is as follows:

Put 179.2 g of 4,4'-diphenylmethane bismaleimide (BMI produced by K.I company, the content of maleimide group is 1mol) into the flask equipped with thermometer, reflux condenser, stirrer and nitrogen device. ), containing 36.1g (0.17mol) of active ester group aromatic monoamine compound L-1 and 323g of dimethylacetamide, carry out decompression nitrogen replacement in the system, stir and dissolve, then be warming up to 100 DEG C and react for 2 hours, A dimethylacetamide solution of the modified maleimide compound M-1 was obtained.

According to the calculation and determination of the feeding ratio, the sum of the equivalents of the active ester group and the secondary amine group in the modified maleimide compound M-1 provided in this example is about 636 g/eq.

Example 2

A modified maleimide compound M-2, preparation method is as follows:

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

According to the calculation and determination of the feeding ratio, the sum of the equivalents of the active ester group and the secondary amine 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, preparation method is as follows:

Put 179.2 g of 4,4'-diphenylmethane bismaleimide (BMI produced by K.I company, the content of maleimide group is 1mol) into the flask equipped with thermometer, reflux condenser, stirrer and nitrogen device. ), 29.4 g (0.1 mol) of aromatic diamine compound L-3 containing active ester group, 16.4 g (0.076 mol) of aromatic monoamine compound L-1 containing active ester group, and 338 g of dimethylacetamide. Under reduced pressure nitrogen replacement, stirring and dissolving, the temperature was raised to 100° C. and reacted for 2 hours to obtain a dimethylacetamide solution of the modified maleimide compound M-3.

According to the calculation and determination of the feeding ratio, the sum of the equivalents of the active ester and the secondary amine group in the modified maleimide compound M-3 provided in this example is about 636 g/eq.

Example 4

A modified maleimide compound M-4, preparation method is as follows:

181g of polyphenylmethane polymaleimide (BMI-2300 produced by Daiwakasei Company, the content of maleimide group is 1mol), containing 82.6 g (0.5 mol) of active ester-based aromatic monoamine compound L-2 and 395.5 g of dimethylacetamide, the system was replaced with nitrogen under reduced pressure, and dissolved while stirring, and then the temperature was raised to 110°C After 2 hours of reaction, a dimethylacetamide solution of the modified maleimide compound M-4 was obtained.

According to the calculation and determination of the feeding ratio, the sum of the equivalents of the active ester group and the secondary amine group in the modified maleimide compound M-4 provided in this example is about 264 g/eq.

Example 5

A modified maleimide compound M-5, preparation method is as follows:

Put 144.8 g of polyphenylmethane polymaleimide (BMI-2300 produced by Daiwakasei, the content of maleimide group is 0.8mol) into a flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen device. , 68.9g maleimide compound containing aliphatic long chain structure (BMI-689 produced by Designer Molecules Inc., maleimide group content is 0.2mol), aromatic diamine compound L-3 containing active ester group 44.1 g (0.15 mol), 16.5 g (0.1 mol) of active ester group-containing aromatic monoamine compound L-2 and 412 g of dimethylacetamide, replace the system with nitrogen under reduced pressure, stir and dissolve, and then heat up to 150 The reaction was carried out at °C for 2 hours to obtain a dimethylacetamide solution of the modified maleimide compound M-5.

According to the calculation and determination of the feeding ratio, the sum of the equivalents of the active ester and the secondary amine 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:

Put 179.2 g of 4,4'-diphenylmethane bismaleimide (BMI produced by K.I company, the content of maleimide group is 1mol) into the flask equipped with thermometer, reflux condenser, stirrer and nitrogen device. ), p-aminophenol 16.8g (0.15mol) and dimethylacetamide 294g, carry out decompression nitrogen replacement in the system, stir and dissolve, then be warming up to 100 DEG C and react for 2 hours to obtain phenolic hydroxyl and N- A dimethylacetamide solution of the maleimide compound N-1 substituted for the maleimide group.

According to the calculation and determination of the feeding ratio, the sum of the equivalents of the hydroxyl group and the secondary amino group in the maleimide compound N-1 provided by this comparative example is about 636 g/eq.

Comparative Example 2

A maleimide compound N-2, preparation method is as follows:

Put 179.2 g of 4,4'-diphenylmethane bismaleimide (BMI produced by K.I company, the content of maleimide group is 1mol) into the flask equipped with thermometer, reflux condenser, stirrer and nitrogen device. ), 19.8 g (0.1 mol) of 4,4'-diaminodiphenylmethane, 6.8 g (0.06 mol) of p-aminophenol, and 309 g of dimethylacetamide, and the system was replaced with nitrogen under reduced pressure. After stirring and dissolving, the temperature was raised to 100° C. to react for 2 hours to obtain a dimethylacetamide solution of the maleimide compound N-2 having a phenolic hydroxyl substituent and an N-substituted maleimide group.

According to the calculation and determination of the feeding ratio, the sum of the equivalents of the radicals and the secondary amino groups in the maleimide compound N-2 provided by this comparative example is about 635 g/eq.

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

Table 1

Application example 1

A thermosetting resin composition and a prepreg and a circuit substrate comprising the same, the 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 Parts of 2-ethyl-4-methylimidazole (curing accelerator D-2) are mixed evenly in the solvent to obtain a resin glue of thermosetting resin composition, and the solid content of the resin glue is 65%; use 2116 glass fiber cloth Impregnate the above glue solution, control the appropriate thickness, and then bake it in an oven at 160 ° C for 10 minutes to make a prepreg;

(2) Stack 7 sheets of prepreg together, stack 1Oz RTF copper foil on the upper and lower sides, and make a circuit under the conditions of a curing temperature of 200°C, a curing pressure of 45Kg/cm ² and a curing time of 120 minutes. substrate.

Application example 2

A thermosetting resin composition and a prepreg and a circuit substrate comprising the same, the 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 of 4-dimethylaminopyridine (curing accelerator D-1) and 0.06 parts by weight of Parts of 2-ethyl-4-methylimidazole (curing accelerator D-2) are mixed evenly in the solvent to obtain a resin glue of thermosetting resin composition, and the solid content of the resin glue is 65%; use 2116 glass fiber cloth Dip the above glue solution, control the appropriate thickness, and then bake it in an oven at 145 ° C for 15 minutes to make a prepreg;

(2) Stack 7 sheets of prepreg together, stack 1Oz RTF copper foil on the upper and lower sides, and make a circuit under the conditions that the curing temperature is 190°C, the curing pressure is 60Kg/cm ² , and the curing time is 150 minutes substrate.

Application example 3

A thermosetting resin composition and a prepreg and a circuit substrate comprising the same, the 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 of 4-dimethylaminopyridine (curing accelerator D-1) and 0.06 parts by weight of Parts of 2-ethyl-4-methylimidazole (curing accelerator D-2) are mixed evenly in the solvent to obtain a resin glue of thermosetting resin composition, and the solid content of the resin glue is 65%; use 2116 glass fiber cloth Impregnate the above glue, control the appropriate thickness, and then bake it in an oven at 175 ° C for 5 minutes to make a prepreg;

(2) Stack 7 sheets of prepreg together, stack 1Oz RTF copper foil on the upper and lower sides, and make a circuit under the conditions that the curing temperature is 220°C, the curing pressure is 30Kg/cm ² , and the curing time is 90 minutes substrate.

Application examples 4~6, comparative examples 3~5

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

Table 2

Performance Testing:

The thermosetting resin compositions provided in Application Examples 1 to 6 and Comparative Examples 3 to 6 and the circuit substrates containing the thermosetting resin compositions were tested for their performance, and the methods were as follows:

(1) Glass transition temperature (T _g ): use a DMA instrument to test, and measure according to the DMA test method specified in the standard IPC-TM-650 2.4.24;

(2) Coefficient of thermal expansion CTE (Z-axis): use a TMA instrument to measure the thermal expansion coefficient between 50 and 260°C according to the CTE (Z-axis) test method specified in the standard IPC-TM-650 2.4.24;

(3) Dielectric constant D _k and dielectric loss factor D _f : According to the flat plate method specified in the standard IPC-TM-650 2.5.5.9, measure D _k and D _f at 1 GHz;

(4) Thermal delamination time T288 (with copper) or T300 (with copper): use a TMA instrument, according to the T288 (with copper) or T300 (with copper) test method specified in the standard IPC-TM-650 2.4.24.1. determine;

(5) Evaluation of Moisture and Heat Resistance (PCT): After keeping three samples of 100×100 mm in a pressure cooking device at 180°C and 105KPa for 5 hours, immerse them in a solder bath at 288°C for 5 minutes, and observe the samples. Whether stratified bubbling occurred, 3 blocks without stratified bubbling were recorded as 3/3, 2 blocks without stratified bubbling were recorded as 2/3, and 1 block without stratified bubbling was recorded as 1/ 3,0 block without layered bubbling is recorded as 0/3;

(6) PCT water absorption: take the substrate pretreated by the test method (5) PCT test conditions, and measure it according to the water absorption test method specified in the standard IPC-TM-650 2.6.2.1;

(7) Peel strength (PS): Test the peel strength of the metal capping layer in accordance with the "received state" experimental conditions specified in the standard IPC-TM-650 2.4.8;

The specific test results are shown in Table 3:

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, relative to Comparative Examples 3 to 6, in the circuit substrates provided in Application Examples 1 to 6 of the present invention, the thermosetting resin composition used is 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 moist heat resistance, and simultaneously has high glass transition temperature (T _g ), low coefficient of thermal expansion (Z-CTE) and Good bond strength to metals; its dielectric constant

3.90 (1GHz), dielectric loss factor below 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 humidity and heat 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 known that using the modified maleimide compound of the present invention ( Compared with the common maleimide compound curing system, the thermosetting resin composition and circuit substrate with active ester group) are cured in terms of dielectric constant, dielectric loss factor, heat resistance, water absorption and humidity and heat resistance. more obvious advantages.

The applicant declares that the present invention illustrates a modified maleimide compound of the present invention and its preparation method and application through the above-mentioned examples, but the present invention is not limited to the above-mentioned examples, that is, it does not mean that the present invention must rely on Only the above-mentioned embodiment can be implemented. 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 protection scope and disclosure scope of the present invention. .

Claims (16)

A modified maleimide compound is characterized in that the preparation raw materials of the modified maleimide compound include: a maleimide group-containing compound and an active ester group-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, X ₁ -Y ₁ -X ₂ -substituted or unsubstituted C ₁ -C ₂₀ straight or branched chain alkyl, substituted or unsubstituted C ₃ ~C ₂₀ cycloalkyl; X ₁ and 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-, sulfanyl or sulfylene; The substituted substituents in Ar and X are each independently selected from F, C ₁ -C ₅ straight-chain or branched-chain alkyl groups. The modified maleimide compound according to claim 1, wherein the Ar is selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, and substituted or unsubstituted biphenylene; the The substituted substituent is selected from F, C ₁ ~C ₅ straight or branched chain alkyl; the X is selected from C ₁ ~C ₁₀ straight or branched chain alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted Naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted biphenyl ether; the substituted substituent is selected from F, C ₁ ~C ₅ straight or branched chain alkyl. The modified maleimide compound according to claim 1, wherein, based on the maleimide group in the maleimide group-containing compound being 1 mol, the active ester group-containing aromatic monoamine compound has a The dosage is 0.05~1mol. The modified maleimide compound according to claim 1 or 2, wherein the preparation raw materials also include 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; the substituted substituents in Ar ₁ and Ar ₂ are each independently selected from F, C ₁ -C ₅ chain or branched alkyl; Y is selected from C ₁ ~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 divalent aromatic groups; the substituted substituents in Ar ₃ and Ar ₄ are each independently selected from halogen, unsubstituted or halogenated groups C ₁ ~C ₅ straight-chain or branched-chain alkyl groups, groups containing aryl phosphorus oxygen structure; Z is selected from C ₁ ～C ₂₀ straight-chain or branched alkylene, C ₃ ～C ₂₀ cycloalkylene, C ₆ ～C ₂₀ arylene or biphenylene ether; n is selected from 0~10. The modified maleimide compound according to claim 4, wherein each of Ar ₁ and Ar ₂ is independently selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, or substituted or unsubstituted Substituted biphenylene; the substituted substituents are independently selected from F, C ₁ ~C ₅ straight-chain or branched alkyl; the Ar ₃ and Ar ₄ are each independently selected from

,

,

Y ₂ is selected from unsubstituted or halogenated C1～C5 straight-chain or branched alkylene, -O-, -S-,

,

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

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

,

,

,

,

The modified maleimide compound according to claim 4, wherein Z is selected from C ₁ -C ₅ straight or branched chain alkylene, C ₃ -C ₁₂ cycloalkylene, phenylene, Naphthylene, biphenylene or phenylene ether. The modified maleimide compound according to 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 0.05-1 mol; The maleimide group in the material is 1 mol, and the amount of the aromatic diamine compound is 0.01-0.25 mol. A preparation method of the modified maleimide compound as described in any one of claims 1 to 8, characterized in that the preparation method comprises: a maleimide group-containing compound having a structure as shown in formula I The active ester group-containing aromatic monoamine compound is reacted with an optional aromatic diamine compound having the structure shown in formula II to obtain the modified maleimide compound. The preparation method according to claim 9, wherein the temperature of the reaction is 70-200° C., and the time of the reaction is 0.5-8 hours. The preparation method according to claim 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 comprises an epoxy resin and the modified maleimide compound according to any one of claims 1 to 8. A semiconductor sealing material, characterized in that the raw material of the semiconductor sealing material comprises the thermosetting resin composition according to claim 12. A prepreg, characterized in that the prepreg comprises a base material, and the thermosetting resin composition according to claim 12 adhered to the base material by impregnation and drying. A circuit substrate is characterized in that, the circuit substrate comprises at least one prepreg according to claim 14, and metal foils arranged 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 according to claim 12 coated on at least one surface of the base film or metal foil.