WO2020173216A1

WO2020173216A1 - Thermosetting resin composition

Info

Publication number: WO2020173216A1
Application number: PCT/CN2019/129925
Authority: WO
Inventors: 李兵兵; 席奎东; 粟俊华
Original assignee: 南亚新材料科技股份有限公司
Priority date: 2019-02-26
Filing date: 2019-12-30
Publication date: 2020-09-03
Also published as: CN109943072A; JP7170137B2; KR102523920B1; KR20210087072A; JP2022508174A

Abstract

The present invention relates to a thermosetting resin composition, the raw material components of which comprise a biphenyl-type maleimide resin, a carbodiimide, a rubber toughening agent with a core-shell structure, and a thermosetting resin, wherein the carbodiimide has a cyclic structure, and a number-average molecular weight of 200-5000 g/mol, and the thermosetting resin comprises a cyanate ester resin or a benzoxazine resin. Compared with the prior art, the invention has excellent heat resistance, stability, wet-heat reliability, and dielectric properties, and can be used for making prepregs and laminates.

Description

Thermosetting resin composition

Technical field

The invention relates to the technical field of thermosetting materials, in particular to a thermosetting resin composition.

Background technique

The invention relates to a resin composition and prepregs, laminates and copper clad laminates made of the resin composition. With the rapid development of electronic technology, the high performance and miniaturization of electronic and electrical equipment are rapidly developing, and the installation With the increase of power of electronic components, the heat generation thereof is also greatly increased. In this context, the densification and miniaturization of electronic components have put forward higher requirements for the heat resistance, humidity and heat insulation and environmental reliability of metal-based circuit substrates.

The insulating resin layer used in the metal-based circuit board is usually a thermosetting resin material obtained by curing a resin composition. Although maleimide is a well-known high-performance resin with excellent heat resistance in the industry, since ordinary maleimide cannot be fully cured with other resins, secondary curing will occur under high temperature conditions, resulting in material size The stability is poor, and the high water absorption rate of the maleimide material leads to poor damp and heat reliability of the material, resulting in performance failures, bursts, etc. in applications such as high multilayer circuit boards or high density interconnect circuit boards problem.

In order to improve the moist heat reliability of the maleimide resin system, patents JPH02218751A and CN104910621B respectively disclose a resin composition, which is composed of a cyanate ester resin and a carbodiimide compound. Since the dielectric properties and thermal stability of the material after curing of the cyanate ester resin are not as good as those of the maleimide resin, there are restrictions on the application products that require higher electrical performance and reliability, so the composition of the resin system needs to be adjusted in order to obtain Better performance.

Summary of the invention

The purpose of the present invention is to provide a thermosetting resin composition in order to overcome the above-mentioned defects in the prior art.

The purpose of the present invention can be achieved through the following technical solutions:

A thermosetting resin composition, the raw material composition of which includes the following parts by weight:

The basic formula of the present invention is biphenyl maleimide resin, carbodiimide, thermosetting resin and core-shell structure rubber toughening agent; the resin composition further contains flame retardant, filler and curing accelerator. Compared with traditional epoxy resins, high-performance resin materials, such as maleimide resin, cyanate ester resin, and benzoxazine resin, exhibit better mechanical properties, thermal properties, and dielectric properties.

In the thermosetting resin composition, carbodiimide is combined with high-performance resin materials, such as maleimide resin, cyanate ester resin, and benzoxazine resin. The introduction of carbodiimide promotes the curing of the thermosetting resin. Low water absorption, high heat resistance materials can be obtained, reducing the risk of laminate explosion. At the same time, the core-shell rubber with a specific structure is used as a toughening agent in the resin composition. When introduced into the resin system as micro-nano particles, it will not only have no effect on the performance of the material itself, but also reduce the dielectric properties, increase the peel strength, and resist stress damage .

Moreover, compared to the composition of the polycarbodiimide compound and cyanate ester resin composition disclosed in CN104910621, the present invention uses cyclic carbodiimide, biphenyl maleimide resin, and cyanate ester resin Or benzoxazine resin, two thermosetting resins as a composition. Since the dielectric properties and thermal stability of the material after curing of the cyanate ester resin are inferior to that of the maleimide resin and benzoxazine resin, there are restrictions on the application products that require higher electrical performance and reliability. In order to cope with higher demands, the invention adopts a system composed of maleimide and cyanate ester resin or benzoxazine resin in order to obtain better performance.

The carbodiimide is a cyclic structure, and its number average molecular weight is 200-5000 g/mol; the structure is as shown in formula I:

In formula I, X is selected from one or a chemical structure formed by any combination of one or more of aromatic groups, aliphatic groups, and alicyclic groups.

The present invention selects the cyclic structure of carbodiimide, the selected cyclic carbodiimide structure is a cyclic molecular formula structure, and the molecular formula contains one or more carbodiimide groups (-C=N=C-), And any combination with one or more of arylene, alkylene, and cycloalkylene forms a closed ring structure.

X is selected from one or more combinations of aromatic groups, aliphatic groups, and alicyclic groups. Among them, the aromatic groups include, for example, phenylene, biphenylene, naphthylene, and anthracene Group; aliphatic groups include, for example, methylene, ethylene, propylene, isopropylene, and butylene; alicyclic groups include, for example, cyclopropylene, cyclobutylene, and cyclopentylene Group, cyclohexylene.

The aromatic group, aliphatic group, and alicyclic group selected from X may have a substituent group. Examples of the substituent group include a halogen group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cycloalkyl group, Acyl.

For electronic and electrical materials, the durability of resin materials will change with various conditions such as temperature, ultraviolet rays, and oxygen. Among them, humidity, rain, and condensation have a great influence on the reliability of electronic materials. , The use of carbodiimide as an anti-hydrolysis agent can effectively inhibit the deterioration of the material's performance caused by structural damage in a hot and humid environment.

However, it is known that carbodiimide monomers or linear carbodiimide compounds may generate toxic isocyanate gas when reacting with resins. Isocyanate gas has different chemical structures, and exposure to very low concentrations can also cause irritation to the skin, eyes, and respiratory tract. It is a gas that has specified the allowable value of the working environment at the production site. Therefore, the carbodiimide compound having a cyclic structure is used in the thermosetting resin composition, which does not generate toxic isocyanate gas when reacting with the resin, and is not restricted by the working environment at the production site, and can be used safely. The manufacture and use of. In addition, the cyclic carbodiimide compound itself has more advantages in terms of production, storage and transportation than the usual carbodiimide compound. At the same time, the cyclic carbodiimide, like the previous carbodiimide compounds, can be applied to a wide range of fields such as plastics, electronics, and rubber without reducing the performance of each resin.

Cyclic carbodiimide can achieve higher hydrolysis resistance and high temperature resistance than traditional carbodiimide monomers or carbodiimide linear structure compounds with a smaller amount of addition. The cyclic carbodiimide generally has a heat resistance of 300°C or higher, and therefore, the formed resin material can have a higher heat-resistant decomposition temperature. In addition, it can also be used as a crosslinking agent for adjusting the viscosity of the resin composition or hardening it.

Although cyclic carbodiimide has a higher boiling point than ordinary carbodiimide monomers, in order to avoid gas volatilization that may occur during high-temperature thermal curing, the number average molecular weight of cyclic carbodiimide is preferably 200g /mol or more, more preferably 500 g/mol or more. Considering the solubility of the cyclic carbodiimide in solvents and compatibility with other resin components in the resin composition, the upper limit of the number average molecular weight of the cyclic carbodiimide is preferably 5000 g/mol or less, and more preferably Below 3500g/mol.

The thermosetting resin is a cyanate ester resin.

The cyanate resin is selected from bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylene Bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4 -Cyanate) phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylphenyl)methane, 1,3 -Bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatophenyl)sulfide, bis(4-cyanatophenyl)ether One or a mixture of polyfunctional cyanate resins derived from phenol phenolic resins or polyfunctional cyanate resins derived from cresol phenolic resins.

Cyanate resin, as an alternative to the traditional curing material epoxy resin, has good reactivity. After curing, the material has a higher crosslink density, high glass transition temperature, low shrinkage, and excellent heat resistance and Dielectric properties. The cyanate ester resin and the maleimide resin in the resin composition are co-cured to form a BT resin (maleimide-triazine resin) material, which has good dielectric properties, heat resistance, low water absorption, CAF resistance and other properties, especially a good balance between high heat resistance and excellent dielectric properties.

During the curing process of cyanate ester resin and maleimide resin, triazine cyclization reaction of cyanate ester, diene addition reaction of bismaleimide, and cyanate ester (or triazine ring) will occur Copolymerization with bismaleimide. Under non-catalytic conditions, these reactions can only occur at higher temperatures, generally greater than 150°C, which will cause the resin to gel for a longer time and the curing is not complete. When the carbodiimide structure exists in the resin composition, the introduction of the carbodiimide compound promotes the curing of the maleimide and the cyanate ester or benzoxazine resin, which is beneficial to the complete reaction of the thermosetting resin material.

Specific examples of cyanate ester curing agents include PT30 and PT60 (phenol novolac type polyfunctional cyanate resin) manufactured by Lonza Corporation, ULL-950S (polyfunctional cyanate resin), BA230, BA3000S, BA230S75 (part or all of bisphenol A dicyanate is triazineized to form a trimer).

The thermosetting resin may also be a benzoxazine resin.

The benzoxazine resin may be bisphenol A type benzoxazine, bisphenol F type benzoxazine, bisphenol S type benzoxazine, bisphenol diamine type benzoxazine, dicyclopentadiene One or a mixture of phenolic benzoxazines or modified benzoxazines.

Using benzoxazine resin as a part of the resin composition, because benzoxazine resin is a new type of thermosetting resin material, it has good processing technology, wide processing window and no release of small molecules during curing. The dimensional shrinkage during curing is almost zero. In terms of dimensional stability, benzoxazine resin has more advantages than maleimide resin and cyanate ester. In addition, the use of benzoxazine resin in the resin composition can further optimize the moisture and heat resistance and bonding performance of the cyanate ester resin as a thermosetting material. At the same time, it can make the material brittle, improve toughness, and make it have good processing properties. Adding too much will adversely affect the dielectric properties and toughness of the resin system.

The core-shell structure rubber toughening agent is a cross-linked polymer particle with an average particle size of 20nm-5μm; the core-shell structure rubber toughening agent includes a shell part and a core part; the core part of the core-shell rubber is selected From diene polymers and organosiloxane polymers, the shell part of the core-shell rubber toughening agent is selected from styrene polymers and (meth)acrylate polymers, and the shell part is a high glass The chemical structure of the transition temperature.

The core part of the core-shell rubber is selected from diene-based polymers and organosiloxane-based rubbers. Examples of diene-based polymers include polybutadiene, polyhexadiene, polyisoprene, and polycyclopentadiene. Examples of olefin and organosiloxane polymers include polydimethylsiloxane, polymethylethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, and polydiphenylsilicon. Oxyane; The shell part of the core-shell rubber toughening agent is selected from styrenic polymers and (meth)acrylate polymers, the styrenic polymers can be polystyrene, poly-α-methylstyrene , Polydivinylbenzene, (meth)acrylate polymers can exemplify polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polyisooctyl acrylate, polymethyl methacrylate , Polyethyl methacrylate, polybutyl methacrylate.

In the resin composition, core-shell rubber particles are used as a toughening agent, and rubber micro-nano particles are used as an additive auxiliary. The cross-linked structure is insoluble in the resin system and can play a role in adjusting the viscosity of the resin system. Since maleimide resin and cyanate ester resin are the main components of the resin composition, the viscosity of the resin glue and the prepreg will decrease, making it difficult to produce. Therefore, the core-shell rubber particles are introduced into the resin system to adjust the viscosity of the resin system, improve processing technology, and eliminate product appearance defects or thickness unevenness caused by viscosity problems.

In addition, the use of core-shell rubber particles as a toughening agent can not only improve the brittleness of the material and increase the toughness, but because the core-shell rubber particles are dispersed throughout the resin continuous phase structure, it can not only reduce the dielectric properties, increase the peel strength, and improve the It can also play a buffering role when stress is broken.

The present invention limits the average particle size of the core-shell rubber particles used. When the core-shell rubber particles are too small, it is difficult to uniformly disperse in the resin system and agglomeration occurs. When the core-shell rubber particles are too large, the appearance of the material will deteriorate and the performance of the material will also deteriorate. Therefore, the average particle diameter of the core-shell rubber particles is 20 nm to 5 μm, more preferably 100 to 500 nm.

The biphenyl maleimide resin is a biphenyl maleimide resin with a structure of formula II, and its number average molecular weight is 500-5000 g/mol;

In formula II, n is any integer in 1-10.

Using biphenyl type maleimide resin (biphenyl type BMI), compared to the maleimide resin used in the prior art, usually phenyl type bismaleimide or phenyl type multifunctional horse To imide, for example, from unsubstituted maleimide, N-phenyl maleimide, N-(o-methylphenyl)-maleimide, N-(m-methyl (Phenyl)-maleimide, N-(p-methylphenyl)-maleimide, N-cyclohexylmaleimide, maleimidophenol, maleimide Aminobenzocyclobutene, phosphorus-containing maleimide, phosphate maleimide, oxysilyl maleimide, N-(tetrahydropyranyl-oxyphenyl)maleimide A group consisting of imines and 2,6-xylylmaleimides, the resin substrate composed of biphenyl-type BMI in the present invention exhibits metal peel strength, heat resistance, flame resistance and reliability For better performance. Although conventional BMI has good heat resistance and thermomechanical properties, its peel strength from metal is not high, the dielectric properties are poor, and the water absorption rate is large, which has an adverse effect on the final material. The use of biphenyl-type BMI and the peeling strength of metals have been greatly improved, and the water absorption rate of the material is low, thereby improving the heat and humidity resistance of the product, and the biphenyl-type structure has better heat resistance than phenyl-type BMI And dielectric properties, suitable for high-end copper clad laminate materials.

The components of the present invention also include flame retardants and inorganic fillers.

The inorganic filler is selected from aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, cubic boron nitride, crystalline silica, synthetic silica, hollow silica, spherical silica, fused silica, talc One or a mixture of powder, alumina, barium sulfate, barium titanate, strontium titanate, calcium carbonate, titanium dioxide, etc.

The flame retardant is selected from one or a mixture of bromine-containing flame retardants and phosphorus-containing flame retardants;

The bromine-containing flame retardant is selected from one or a mixture of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or decabromodiphenyl ether;

The phosphorus-containing flame retardant is selected from tris(2,6-dimethylphenyl)phosphorus, 10(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphorus Phenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphorylbenzene or 10-phenyl-9,10-dihydro-9-oxa-10-phosphorphenanthrene-10 -One or a mixture of several oxides.

detailed description

The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be pointed out that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

A thermosetting resin composition whose basic raw material composition includes (A) biphenyl maleimide resin (biphenyl BMI), (B) carbodiimide, and (C) core-shell structure rubber toughening agent And (D) thermosetting resin. The content of each component in the raw material is: 10-70 parts of biphenyl maleimide resin, 5-20 parts of carbodiimide; 1-10 parts of core-shell structure rubber toughening agent; 20 parts of thermosetting resin -80 servings.

The following is the specific selection of each component:

Biphenyl type maleimide resin (biphenyl type BMI):

In formula II, n is any integer in 1-10.

Using biphenyl type maleimide resin (biphenyl BMI), the maleimide resin used in the prior art is usually phenyl type bismaleimide or phenyl type multifunctional maleimide The present invention uses biphenyl maleimide resin. Compared with the traditional BMI composed of phenyl, for example, it is composed of unsubstituted maleimide and N-phenylmaleimide resin. Imine, N-(o-methylphenyl)-maleimide, N-(m-methylphenyl)-maleimide, N-(p-methylphenyl)-maleimide , N-cyclohexane maleimide, maleimide phenol, maleimide benzocyclobutene, phosphorus-containing maleimide, phosphate maleimide, oxygen The group consisting of silyl maleimide, N-(tetrahydropyranyl-oxyphenyl) maleimide, and 2,6-xylyl maleimide, in the present invention The resin substrate composed of biphenyl-type BMI shows better performance in metal peel strength, heat resistance, flame resistance and reliability. Although conventional BMI has good heat resistance and thermomechanical properties, its peel strength from metal is not high, the dielectric properties are poor, and the water absorption rate is large, which has an adverse effect on the final material. The use of biphenyl-type BMI and the peeling strength of metals have been greatly improved, and the water absorption rate of the material is low, thereby improving the heat and humidity resistance of the product, and the biphenyl-type structure has better heat resistance than phenyl-type BMI And dielectric properties, suitable for high-end copper clad laminate materials.

Carbodiimide:

The carbodiimide is a cyclic structure with a number average molecular weight of 200-5000g/mol; the structure is shown in formula I:

The selected cyclic carbodiimide structure is a cyclic molecular formula structure, and the molecular formula contains 1 or more carbodiimide groups (-C=N=C-), and is combined with arylene, alkylene, and sub-ring One or more of the alkyl groups arbitrarily combine to form a closed ring structure.

Core-shell structure rubber toughening agent:

Thermosetting resin:

The thermosetting resin includes cyanate ester resin or benzoxazine resin.

The cyanate ester resin is selected from bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylene Bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4 -Cyanate) phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylphenyl)methane, 1,3 -Bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatophenyl)sulfide, bis(4-cyanatophenyl)ether One or a mixture of polyfunctional cyanate resins derived from phenol phenolic resins or polyfunctional cyanate resins derived from cresol phenolic resins.

Using cyanate ester resin or benzoxazine resin instead of epoxy resin as the curing agent, cyanate ester resin as an alternative to the traditional curing material epoxy resin, has good reactivity, and the cured material has higher interaction Link density, high glass transition temperature, low shrinkage and excellent heat resistance and dielectric properties. The cyanate ester resin and the maleimide resin in the resin composition are co-cured to form a BT resin (maleimide-triazine resin) material, which has good dielectric properties, heat resistance, low water absorption, CAF resistance and other properties, especially a good balance between high heat resistance and excellent dielectric properties.

During the curing process of cyanate ester resin and maleimide resin, triazine cyclization reaction of cyanate ester, diene addition reaction of bismaleimide, and cyanate ester (or triazine ring) will occur Copolymerization with bismaleimide. Under non-catalytic conditions, these reactions can only occur at higher temperatures, generally greater than 150°C, which will cause the resin to gel for a longer time and the curing is not complete. When the carbodiimide structure is present in the resin composition, the introduction of the carbodiimide compound promotes the curing of the maleimide and the cyanate ester or benzoxazine resin, which is beneficial to the complete reaction of the thermosetting resin material.

If necessary, cyanate ester resin or benzoxazine resin can be used instead of part of the epoxy resin as the curing agent, that is, the thermosetting resin is a cyanate ester resin or a mixture of benzoxazine resin and epoxy resin.

Inorganic filler:

Flame retardant:

If necessary, the thermosetting resin composition of the present invention can also be added with other additives, such as imidazole accelerators, specifically 2-methylimidazole, 2-ethyl-4methylimidazole, 1,2-dimethylimidazole, 2 -Phenylimidazole, 2-phenyl-4methylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl One or more of -2-phenylimidazole, etc.; such as cobalt acetylacetonate (Ⅱ), cobalt acetylacetonate (Ⅲ) and other organic cobalt complexes, copper acetylacetonate (Ⅱ) and other organic copper complexes, acetylacetone One or more of organic zinc complexes such as zinc (II), and organic iron complexes such as iron (III) acetylacetonate; for example, organic metal salts, specifically zinc octoate, tin octoate, zinc stearate, etc. One or more of.

Compared with the prior art, the thermosetting resin composition obtained in the present invention is used as a binder to prepare copper clad laminates, with Tg>270°C (DMA); Z axis CTE<1.5%; heat resistance: Td>380°C , T288＞60min; electrical properties: dielectric constant Dk＜3.9(10GHz); dielectric loss Df＜0.0057(10GHz); copper foil peeling strength＞1.0N/mm; in addition, it has very low water absorption and good mechanical properties Processing performance, and flame retardant reaches UL94V-0 level. It has excellent heat resistance, stability, humidity and heat reliability, and dielectric properties; it can be used to make prepregs and laminates.

The test method of the thermosetting composition in this embodiment is:

Glass transition temperature (Tg): Use a DMA instrument to test and measure it in accordance with the DMA test method specified in IPC-TM-650 2.4.24.4.

Coefficient of Thermal Expansion (CTE) of Z-axis: Use TMA instrument to test and measure according to the TMA test method specified in IPC-TM-650 2.4.24.

288°C layered lysis time (T288): Use TMA instrument to test and measure according to the test method specified in IPC-TM-650 2.4.24.1.

Copper foil peel strength (PS): Use Shimadzu tensile machine to test and measure according to the test method specified in IPC-TM-650 2.4.8.

Dielectric constant (Dk) and dielectric loss factor (Df): The dielectric constant and dielectric loss factor test methods are determined in accordance with the test methods specified in IPC-TM-650 2.5.5.9.

Pressure cooker cooking experiment (PCT): The laminate is subjected to a high-temperature cooking experiment at 120°C, and measured according to the test method specified in IPC-TM-650 2.6.16.

Flame retardancy: According to the material flammability method specified by UL-94, it is tested and classified.

Water absorption: Measured in accordance with the test method for water absorption of laminates specified in IPC-TM-650 2.6.2.1. Resin fluidity: The resin fluidity was measured by Shimadzu capillary rheometer. 2g resin powder pressed ingot extruded the resin from the small hole at a certain pressure, and evaluated based on the resin flow out of the rheometer. The longer the outflow stroke, the better the resin fluidity.

Dimensional stability: superimpose 10 layers of 500mm*500mm prepregs and quickly press them in a press. After 180°C for 2 hours, take out the thickness of each position of the test plate. When the difference between the maximum thickness and the minimum thickness is less than 5%, the size of the material is stable Sex is considered good.

The following embodiments specifically illustrate the application of the present invention:

Examples 1-11

A thermosetting resin composition whose basic raw material composition includes (A) biphenyl maleimide resin (biphenyl BMI), (B) carbodiimide, and (C) core-shell structure rubber toughening agent , And (D) Thermosetting resin. The trade names and specific compositions of the components used in this example are shown in Table 1. In order to better illustrate the present invention, the thermosetting resin composition was prepared using the components and proportions in Table 2 below.

Table 1 Commodity model and composition parameters of each component in this embodiment

Table 2 Raw material composition of Examples 1-11 and Comparative Examples 1-5

Table 2 Raw material composition of Examples 1 to 11 and Comparative Examples 1 to 5 (continued)

Examples 12-13

A thermosetting resin composition whose basic raw material composition includes (A) biphenyl maleimide resin (biphenyl BMI), (B) carbodiimide, and (C) core-shell structure rubber toughening agent , And (D) Thermosetting resin. In order to better illustrate the present invention, the thermosetting resin composition was prepared by using the components and proportions in Table 3 below. In this embodiment, (A) the number average molecular weight of the biphenyl maleimide resin is 500 g/mol; (B) the number average molecular weight of the carbodiimide is 200 g/mol; (C) the core-shell structure rubber increases The toughening agent is a cross-linked polymer particle with an average particle size of 20nm; the core-shell structure rubber toughening agent includes a shell part and a core part; the core part is selected from diene polymers, and the shell part is selected from styrene polymers; (D) The thermosetting resin is a commercially available cyanate ester resin; the flame retardant is a mixture of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene and decabromodiphenyl ether; inorganic filler is silica ; The accelerator is an imidazole accelerator.

Examples 14-15

A thermosetting resin composition whose basic raw material composition includes (A) biphenyl maleimide resin (biphenyl BMI), (B) carbodiimide, and (C) core-shell structure rubber toughening agent , And (D) Thermosetting resin. In order to better illustrate the present invention, the thermosetting resin composition was prepared by using the components and proportions in Table 3 below. In this embodiment, (A) the number average molecular weight of the biphenyl maleimide resin is 5000 g/mol; (B) the number average molecular weight of the carbodiimide is 5000 g/mol; (C) the core-shell structure rubber increases The toughening agent is cross-linked polymer particles with an average particle size of 5 μm; the core-shell structure rubber toughening agent includes a shell part and a core part; the core part is selected from styrene polymers, and the shell part is selected from (meth)acrylate Series polymer; (D) thermosetting resin is a commercially available cyanate ester resin; flame retardant is a mixture of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene and decabromodiphenyl ether; inorganic filler It is silicon dioxide; the accelerator is an imidazole accelerator.

Table 3 Raw material composition of Examples 12-14

Comparative example 1

A thermosetting resin composition, its basic raw material composition includes (A2) bis(3-ethyl-5-methyl-4-maleimidobenzene) methane (ie phenyl BMI), (A3) benzene Methane maleimide; (B) carbodiimide, (C) core-shell structure rubber toughening agent and (D) thermosetting resin. The specific raw material composition is shown in Table 2.

Comparative example 2

A thermosetting resin composition, its basic raw material composition includes (A) biphenyl maleimide resin (biphenyl type BMI), (C) core-shell structure rubber toughening agent and (D) thermosetting resin, and The difference in the examples is that it does not contain (B) carbodiimide; see Table 2 for the specific raw material composition.

Comparative example 3

A thermosetting resin composition, the basic raw material composition of which includes (A) biphenyl maleimide resin (biphenyl BMI), (B) carbodiimide and (D) thermosetting resin, which are the same as those in the examples The difference is that it does not contain (C) core-shell structure rubber toughening agent; the specific raw material composition is shown in Table 2.

Comparative example 4

A thermosetting resin composition, its basic raw material composition includes (A) biphenyl maleimide resin (biphenyl type BMI), (B) carbodiimide and (D) thermosetting resin, which are the same as those in the examples The difference is that it does not contain (C) core-shell structure rubber toughening agent; the specific raw material composition is shown in Table 2.

Comparative example 5

A thermosetting resin composition, the basic raw material composition of which includes (A2) bis(3-ethyl-5-methyl-4-maleimidobenzene) methane (ie phenyl BMI) and (D) thermosetting The difference between the resin and the examples is that it does not contain (B) carbodiimide and (C) core-shell structure rubber toughening agent; see Table 2 for specific raw material composition. The properties of the thermosetting resin compositions in the Examples and Comparative Examples were tested. Comparative Examples and Comparative Examples 1. In Comparative Example 1, all phenyl BMI was used, and the Z-axis CTE was measured to be 1.75%, which is greater than any of the Examples. The Z-axis CTE value of the thermosetting resin composition in, and the lower PS value, indicating that the biphenyl-type BMI has better dimensional stability, lower thermal expansion coefficient, and peeling from the copper foil than the conventional phenyl BMI The strength has been significantly improved, and the dielectric properties are more advantageous than conventional BMI.

Comparing Example and Comparative Example 2, since Comparative Example 2 does not contain carbodiimide, the thermosetting resin composition in Comparative Example 2 has a larger Z-axis CTE of 1.72%, and the water absorption rate of the material is higher. The T288 test is within 60 minutes The occurrence of plate bursting indicates that the presence of carbodiimide promotes the curing of the resin composition and significantly reduces the water absorption of the material, thereby reducing the possibility of the material bursting in a high temperature environment and improving the thermal stability of the material. In addition, carbodiimide can also significantly improve the fluidity of materials.

Comparative example and comparative example 3 and comparative example 4, since comparative example 3 and comparative example 4 do not contain core-shell structure rubber toughening agent, the lower peel strength value of copper foil in comparative example indicates that core-shell toughening agent acts as a micro-nano Particles added to the material can increase the interface peel strength; and both Comparative Example 3 and Comparative Example 4 failed the 3-hour PCT test, and the dimensional stability was greater than 5%, and the dimensional stability was poor, indicating that this core-shell rubber was used as an enhancement The toughening agent has significantly improved the dimensional stability of the system and the dielectric properties have also been improved.

Comparative example and comparative example 5, because comparative example 5 does not contain biphenyl type BMI, carbodiimide and core-shell rubber toughening agent, only conventional BMI and thermosetting resin combination, the mechanical properties and resistance of the comparative example The thermal and dielectric properties are inferior compared with the examples, and the thermal stability, dimensional reliability, and resin fluidity of the material are poor.

The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various deformations or modifications within the scope of the claims, which does not affect the essence of the present invention.

Claims

A thermosetting resin composition, characterized in that its raw material composition includes the following components by weight:
The thermosetting resin composition according to claim 1, wherein the carbodiimide has a cyclic structure with a number average molecular weight of 200-5000 g/mol; the structure is as shown in formula I:

In formula I, X is selected from one or a chemical structure formed by any combination of one or more of aromatic groups, aliphatic groups, and alicyclic groups.
The thermosetting resin composition according to claim 1, wherein the thermosetting resin is a cyanate ester resin or a benzoxazine resin.
A thermosetting resin composition according to claim 3, wherein the cyanate resin is selected from the group consisting of bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1 ,5-phenylene cyanate), 4,4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate , Hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate Ester-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanate) One of phenyl) sulfide, bis(4-cyanatophenyl) ether, polyfunctional cyanate resin derived from phenol phenolic resin, or polyfunctional cyanate resin derived from cresol phenolic resin, or A mixture of several.
The thermosetting resin composition according to claim 1, wherein the benzoxazine resin is selected from the group consisting of bisphenol A type benzoxazine, bisphenol F type benzoxazine, bisphenol S type benzene One or a mixture of any of oxazine, bisphenol diamine type benzoxazine, dicyclopentadienphenol type benzoxazine or modified benzoxazine.
The thermosetting resin composition according to claim 1, wherein the core-shell structure rubber toughening agent is cross-linked polymer particles with an average particle size of 20nm-5μm; the core-shell structure rubber The toughening agent includes a shell part and a core part; the core part of the core-shell rubber is selected from diene polymers or organosiloxane polymers, and the shell part of the core-shell rubber toughening agent is selected from styrene-based polymers And (meth)acrylate polymers.
A thermosetting resin composition according to claim 1, wherein the biphenyl maleimide resin is a biphenyl maleimide resin having a structure of formula II, and its number average molecular weight 500-5000g/mol;

In formula II, n is any integer in 1-10.
A thermosetting resin composition according to claim 1, characterized in that it further comprises a flame retardant and an inorganic filler.
A thermosetting resin composition according to claim 8, wherein the inorganic filler is selected from aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, cubic boron nitride, crystalline silica, synthetic dioxide One or a mixture of silicon, hollow silica, spherical silica, fused silica, talc, alumina, barium sulfate, barium titanate, strontium titanate, calcium carbonate, and titanium dioxide.
The thermosetting resin composition according to claim 8, wherein the flame retardant is selected from one or a mixture of bromine-containing flame retardants and phosphorus-containing flame retardants;

The bromine-containing flame retardant is selected from one or a mixture of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or decabromodiphenyl ether;

The phosphorus-containing flame retardant is selected from tris(2,6-dimethylphenyl)phosphorus, 10(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphorus Phenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphorylbenzene or 10-phenyl-9,10-dihydro-9-oxa-10-phosphorphenanthrene-10 -One or a mixture of several oxides.