TWI716967B - Resin composition, prepreg, laminate, metal-clad laminate and printed circuit board - Google Patents

Abstract

The present invention provides a resin composition which contains a certain proportion of a specific maleimide compound, a styrene-maleic anhydride copolymer, an epoxy resin and a specific phosphazene flame retardant. The invention also provides prepregs, laminates, metal-clad laminates and printed circuit boards prepared by using them. After curing, the resin composition has excellent dielectric properties, high flame retardancy, good heat resistance, low water absorption, low thermal expansion coefficient and high bonding properties with conductors.

Description

Resin composition, prepreg, laminate, metal-clad laminate, and printed circuit board

The invention relates to a thermosetting resin, in particular to a resin composition and a prepreg, a laminate, a metal-clad laminate and a printed circuit board prepared by using the resin composition

With the development of miniaturization, weight reduction, and multi-function of electronic components, the development of high integration of LSI, chip components, etc., its form is also rapidly changing to diversification and miniaturization. Therefore, in order to increase the mounting density of electronic components, multilayer printed wiring boards are being developed for micro-wiring.

As a manufacturing method of a multilayer printed wiring board that meets these requirements, a buildup method is proposed, and it is gradually becoming the mainstream as a method to adapt to weight reduction, miniaturization, and miniaturization. In addition, in order to increase environmental awareness, the management of restrictions on materials that may generate hazardous substances contained in electronic components during combustion is becoming stricter. In the conventional multilayer printed wiring boards, although bromine compounds for flame retardancy are being used, since harmful substances may be generated during combustion, it is predicted that the bromine compounds cannot be used in the near future.

Among commonly used solders for connecting electronic components in multilayer printed wiring boards, lead-free solders that do not contain lead are also gradually being put into practical use. Compared with the conventional eutectic solder, the use temperature of this lead-free solder is about 20 to 30°C higher. Therefore, higher heat resistance is required for the material than in the past.

At the same time, with the high-speed and multi-functionalization of information processing in electronic products, the application frequency continues to increase, requiring lower and lower dielectric constant (Dk) and dielectric loss (Df), so reducing Dk/Df has become a substrate industry The focus of chasing.

Furthermore, due to the thinning of the multilayer printed wiring board, the insulating resin layer containing no glass fiber tends to show a high thermal expansion coefficient. Therefore, the difference in thermal expansion coefficient from the copper filled and stacked through holes is essential for reliable connection. The performance is greatly affected, so a material with a low thermal expansion rate is required for the insulating resin layer.

When reducing the thermal expansion coefficient in the insulating resin layer, a method of filling a large amount of inorganic fillers with a generally low thermal expansion coefficient to lower the thermal expansion coefficient of the entire insulating layer is used. However, such a method tends to cause many problems such as deterioration of fluidity and deterioration of insulation reliability.

In addition, through selection or improvement of resins, attempts are made to achieve low thermal expansion. For example, as an example of modified bismaleimide resin (see CN106103534_A), although maleimide resin with iminium skeleton or benzene skeleton is used to increase the crosslinking density and increase the glass transition temperature (Tg ), thereby reducing the thermal expansion rate. However, the modified bismaleimide is difficult to control in the process, and the resin varnish is also difficult to store for a long time. The introduction of highly polar amine groups in the modification has an impact on the dielectric properties of the resin composition (Dk/ Df) has a great negative impact.

On the other hand, for reducing Dk/Df, there are measures by introducing various low-polarity curing agents such as acid anhydrides. However, commonly seen acid anhydrides such as methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, alicyclic anhydride and other small molecular anhydrides, due to the reaction rate is too fast, too strong volatility, high moisture absorption rate, poor solubility, low heat resistance Not adopted.

On the other hand, in order to achieve halogen-free flame retardancy, phosphorus-containing compounds are usually introduced to improve the flame retardancy of the resin composition. Phosphorus-containing compounds can be classified into reactive and additive types from the perspective of reactivity. In order to achieve more excellent Dk/Df, an additive phosphorus-containing flame retardant is usually used. However, most of the commercially available added phosphorus-containing flame retardants have a risk of melting and precipitation during PCB processing because their softening point is too low (<260°C), which affects the reliability of PCBs.

For the printed circuit board industry, there is still a need to find resin compositions with high comprehensive performance.

（I） 其中，R₁ 為亞苯基、亞聯苯基、亞萘基或二環戊二烯基，R₂ 、R₃ 各自獨立地為氫原子、烷基、芳基或芳烷基，n為1至20的整數；

（II） 其中，Rp為氫原子、碳原子數為1至5的烷基、羥基或烯丙基中的一種； 其中以式（I）所示的馬來醯亞胺化合物、苯乙烯-馬來酸酐共聚物、環氧樹脂的總重量為100重量份計， 所述馬來醯亞胺化合物為10重量份至80重量份； 所述苯乙烯-馬來酸酐共聚物為5重量份至50重量份，其中，苯乙烯單元與馬來酸酐單元的莫耳比為0.5至10，所述苯乙烯-馬來酸酐共聚物的酸值為80～800 mgKOH/g； 所述環氧樹脂為10重量份至60重量份； 所述磷腈阻燃劑中的磷相對於所述馬來醯亞胺化合物、所述苯乙烯-馬來酸酐共聚物、所述環氧樹脂和所述磷腈阻燃劑的總重量為0.1重量%至5重量%。The invention provides a resin composition comprising a maleimide compound represented by formula (I), a styrene-maleic anhydride copolymer, an epoxy resin, and a phosphazene flame retardant represented by formula (II);

(I) Wherein, R ₁ is a phenylene group, a biphenylene group, a naphthylene group or a dicyclopentadienyl group, R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, n is an integer from 1 to 20;

(II) where Rp is one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, or an allyl group; wherein the maleimide compound represented by formula (I), styrene-male The total weight of the acetic anhydride copolymer and the epoxy resin is 100 parts by weight, the maleimide compound is 10 to 80 parts by weight; the styrene-maleic anhydride copolymer is 5 to 50 parts by weight Parts by weight, wherein the molar ratio of the styrene unit to the maleic anhydride unit is 0.5-10, the acid value of the styrene-maleic anhydride copolymer is 80-800 mgKOH/g; the epoxy resin is 10 Parts by weight to 60 parts by weight; the phosphorus in the phosphazene flame retardant is relative to the maleimide compound, the styrene-maleic anhydride copolymer, the epoxy resin and the phosphazene inhibitor The total weight of the fuel is 0.1% to 5% by weight.

Total weight Preferably, the equivalent ratio of the maleic anhydride group in the styrene-maleic anhydride copolymer to the epoxy group in the epoxy resin is 0.5 to 1.5.

Preferably, based on 100 parts by weight of the total weight of the maleimide compound, styrene-maleic anhydride copolymer, and epoxy resin represented by formula (I), the styrene-maleic anhydride copolymer is 10 parts by weight to 40 parts by weight.

Preferably, the epoxy resin is phosphorus-containing epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, naphthol novolac epoxy resin , Biphenyl epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene novolac epoxy resin, aralkyl epoxy resin, aralkyl phenol novolac epoxy resin, arylene ether structure containing The epoxy resin, or their mixture.

Preferably, based on the total weight of the maleimide compound, styrene-maleic anhydride copolymer, and epoxy resin represented by formula (I) being 100 parts by weight, the epoxy resin is between 20 parts by weight and 50 parts by weight. Parts by weight.

Preferably, the phosphorus in the phosphazene flame retardant is relative to the total of the maleimide compound, the styrene-maleic anhydride copolymer, the epoxy resin and the phosphazene flame retardant. The weight is 0.5% to 4% by weight.

Preferably, the resin composition further includes one or more of a co-curing agent, a filler, a curing accelerator, a silane coupling agent, a release agent, a pigment, and an emulsifier.

The present invention also provides a prepreg, which is obtained by impregnating or coating a substrate with the resin composition according to the above and curing it.

The present invention also provides a laminated board comprising at least one prepreg according to the above.

The present invention also provides a metal-clad laminate. The metal-clad laminate includes at least one prepreg according to the above and metal foils covering one or both sides of the prepreg.

The present invention also provides a printed circuit board including at least one prepreg according to the above.

The thermosetting resin composition of the present invention has good compatibility, and has excellent dielectric properties, high flame retardancy, good heat resistance, low water absorption, low thermal expansion coefficient and high bonding properties with conductors.

The present invention will be described in further detail below in conjunction with specific embodiments. It will be understood that other embodiments are considered and can be implemented without departing from the scope or spirit of the invention. Therefore, the following detailed description is non-limiting.

The present invention provides a resin composition comprising a maleimide compound represented by formula (I), a styrene-maleic anhydride copolymer, an epoxy resin; and a phosphazene flame retardant represented by formula (II) The total weight of the maleimide compound, styrene-maleic anhydride copolymer, and epoxy resin represented by formula (I) is 100 parts by weight, and the maleimide compound is 10 parts by weight. Parts by weight to 80 parts by weight, the styrene-maleic anhydride copolymer is from 5 parts by weight to 50 parts by weight, the epoxy resin is from 10 parts by weight to 60 parts by weight, and the phosphorus in the phosphazene flame retardant is relative to The total weight of the maleimide compound, the styrene-maleic anhydride copolymer, the epoxy resin and the phosphazene flame retardant is 0.1% to 5% by weight. The inventor unexpectedly discovered that a resin combination containing a maleimide compound with a specific molecular structure, a styrene-maleic anhydride copolymer with a specific molecular structure, an epoxy resin, and a phosphazene flame retardant with a specific molecular structure was used. The prepregs and laminates of the material exhibit excellent dielectric properties, high flame retardancy, good heat resistance, low water absorption, low thermal expansion coefficient, and high bonding properties with conductors.

Each component is described in detail below:

Maleimide compounds:

（I）The maleimide compound having an unsaturated maleimide group used in the present invention is represented by the following general formula (I). There is no particular limitation on the synthetic method of the maleimine compound, and those skilled in the art can Choose based on existing technology combined with your own professional knowledge. Specifically, for example, it can be obtained by reacting maleic anhydride with an amine compound having at least two primary amino groups in one molecule. This reaction is preferably carried out in an organic solvent. As an example of a product, there is MIR-3000 manufactured by Nippon Kayaku Co., Ltd. The compound is a multifunctional biphenylmethane maleimide, which has good compatibility in the system of the present invention, high reaction rate, high heat resistance, and good solvent solubility, thereby achieving high dielectric properties , Peel strength, heat resistance and flame retardancy.

(I)

Wherein, R ₁ is phenylene, biphenylene, naphthylene or dicyclopentadienyl, R ₂ and R ₃ are each independently a hydrogen atom, alkyl group, aryl group or aralkyl group, and n is 1. Integer to 20.

Preferably, in the maleimide compound (A) having a structure of formula (I), n is an integer of 1-15, and more preferably n is an integer of 1-10.

For the content of the maleimide compound, from the viewpoint of glass transition temperature and water absorption, the maleimide compound, styrene-maleic anhydride copolymer, and epoxy resin total 100 parts by weight. The imine compound is in the range of 10 to 80 parts by weight. When the content is too high, there will be insufficient curing or severe curing conditions, and when the content is too low, its excellent heat resistance cannot be fully demonstrated; more preferably, it is 20-60 parts by weight.

Styrene-maleic anhydride copolymer:

The styrene-maleic anhydride copolymer used in the present invention has a great influence on the curing of the resin composition. The styrene-maleic anhydride copolymer includes styrene units and maleic anhydride units, and the molar ratio of the styrene units to the maleic anhydride units is between 0.5:1 and 10:1, and the acid value is 80～ 800 mgKOH/g. Such styrene-maleic anhydride copolymer has good compatibility in the system of the present invention, thereby achieving high dielectric properties, peel strength, heat resistance, and humidity and heat resistance. When the molar ratio or acid value of the two units is not within the above range, the obtained styrene-maleic anhydride copolymer has poor compatibility with the system, and it is difficult to obtain excellent dielectric strength, peel strength, heat resistance and Humidity and heat resistance. The content of the styrene-maleic anhydride copolymer is 5 to 50 parts by weight with respect to 100 parts by weight of the maleimide compound, styrene-maleic anhydride copolymer, and epoxy resin in total. When the content is too high, the flame retardancy and heat resistance of the resin composition are not good, and when the content is too low, the dielectric properties of the resin composition cannot be guaranteed. Preferably, the content of the styrene-maleic anhydride copolymer is 10 to 40 parts by weight.

Epoxy:

The epoxy resin of the present invention is not particularly limited. It is selected from epoxy resins containing at least two epoxy groups. For example, it can be selected from bisphenol A epoxy resins, bisphenol E epoxy resins, Bisphenol F epoxy resin, tetramethyl bisphenol F epoxy resin, bisphenol M epoxy resin, bisphenol P epoxy resin, bisphenol S epoxy resin, bisphenol Z epoxy resin , Bisphenol AP epoxy resin, bisphenol TMC epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, trifunctional phenol epoxy resin, four Functional phenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, phenolphthalein type epoxy resin, phenoxy type epoxy resin, norbornol Ethylene type epoxy resin, adamantane type epoxy resin, pen type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene phenolic aldehyde Type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin, epoxy resin containing arylene ether structure in the molecule, alicyclic epoxy resin, polyol type epoxy resin, Silicone epoxy resin, nitrogen-containing epoxy resin, phosphorus-containing epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, etc. From the viewpoints of compatibility with the composition of the present invention, high heat resistance, low relative permittivity, high adhesiveness, low thermal expansion, and high glass transition temperature, phosphorus-containing epoxy resins, linear Phenolic type epoxy resin, cresol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin , Dicyclopentadiene novolac type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin, epoxy resin containing arylene ether structure, or mixtures thereof, more preferably novolac type ring Oxygen resin, o-cresol novolac epoxy resin, naphthol epoxy resin, naphthol novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene novolac epoxy resin Oxygen resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin. From the viewpoint of low dielectric constant and low cost, dicyclopentadiene epoxy resin and dicyclopentadiene novolac epoxy resin are more preferable. The epoxy resin may be used individually by 1 type, and may use 2 or more types together.

The content of the epoxy resin is 10 to 60 parts by weight with respect to 100 parts by weight of the maleimide compound, the styrene-maleic anhydride copolymer, and the epoxy resin in total. When the content is too high, the dielectric properties of the resin composition are insufficient, and when the content is too low, the bonding strength of the resin composition will decrease. Preferably, the content of the epoxy resin is 20 to 50 parts by weight.

In the composition of the present invention, when the styrene-maleic anhydride copolymer and the epoxy resin meet a certain ratio relationship, the resin composition can achieve a balance of heat and humidity resistance, dielectric properties and bonding strength. Preferably, the equivalent ratio of the maleic anhydride group in the styrene-maleic anhydride copolymer to the epoxy group in the epoxy resin is 0.5 to 1.5, more preferably 0.80 to 1.20.

Phosphazene flame retardant:

（II）The phosphazene flame retardant represented by formula (II) has a high melting point, and has good compatibility with the system of the composition of the present invention, so that the composition of the present invention has flame retardant properties while still having high peeling properties. Strength, heat resistance, humidity and heat resistance and heat migration resistance. The present invention has been researched and found that the maleimide compound of specific formula (I), styrene-maleic anhydride copolymer, and epoxy composition provide excellent dielectric properties, good heat resistance, low water absorption, and low The coefficient of thermal expansion and high adhesion to the conductor, but the flame retardancy is still insufficient. In order to improve the flame retardancy of the composition, flame retardants, especially halogen-free phosphorus-containing flame retardants can be added. However, the low melting point halogen-free phosphorus-containing flame retardant is not compatible with the resin system after being added, which reduces the heat resistance of the resin system, and the problem of melting and precipitation under the high temperature process of PCB affects the heat resistance, dielectric performance and reliability of the laminate Sex. The inventor unexpectedly discovered that the phosphazene flame retardant represented by formula (II) has good system compatibility with the resin composition of the present invention, so that the resin composition has high-efficiency flame-retardant properties while still having high peeling properties. Strength, heat resistance, damp and heat resistance and good dielectric properties, and there will be no migration problems of phosphorus-containing flame retardants.

(II)

Among them, Rp is one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, or an allyl group.

From the viewpoint of phosphorus content, the phosphorus in the phosphazene flame retardant is relative to the maleimide compound, the styrene-maleic anhydride copolymer, the epoxy resin and the phosphazene The total weight of the flame retardant is 0.1 wt% to 5 wt%, preferably the weight of phosphorus contained in the phosphazene flame retardant accounts for 0.5 wt% to 4 wt% of the composition, and more preferably 1 wt% to 3 wt% .

The present invention may also include optional one or more of co-curing agent, filler, curing accelerator, silane coupling agent, release agent, pigment, and emulsifier.

Co-curing agent:

The composition of the present invention may also contain a co-curing agent. As a co-curing agent, it includes one or more of amine curing agent, thiol curing agent, cyanate curing agent, isocyanate curing agent, active ester curing agent, phenol curing agent and benzoxazine . Among them, from the viewpoint of high adhesiveness and low thermal expansion, amine curing agents, cyanate ester curing agents, active ester curing agents, and phenol curing agents are preferred, and amine curing agents and phenol curing agents are more preferred. Agent. The amount of co-curing agent added can be adjusted as required.

Examples of the amine-based curing agent may include: dicyandiamide; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropyl Amine, tetramethylguanidine, triethanolamine and other chain aliphatic amines other than dicyandiamide; isophorone diamine, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, bis(4- Amino-3-methyldicyclohexyl)methane, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro [5.5] eleven Cyclic aliphatic amines such as alkanes; aromatic amines such as xylylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenyl alkane, and diaminodiphenyl ether (ODA). Among them, from the viewpoints of low relative permittivity and low water absorption, diaminodiphenyl ether and dicyandiamide are preferred.

Examples of the phenolic curing agent may include: a biphenyl type phenolic curing agent, a naphthalene type phenolic curing agent, a novolak resin type curing agent, a naphthylene ether type phenolic curing agent, and a phenolic curing agent containing a triazine skeleton.

filler:

The resin composition of the present invention may further contain an inorganic filler. The inorganic filler of the present invention is not particularly limited. The inorganic filler may be an inorganic filler known in the field of prepregs and laminates, as long as it does not significantly degrade the performance of the resin composition of the present invention. Inorganic fillers are added to the resin composition to obtain a resin composition with better mechanical properties, heat resistance, flame retardancy, dielectric properties, and coefficient of thermal expansion. The inorganic filler can be selected from silicon dioxide, metal hydrate, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, aluminum nitride, silicon carbide, aluminum oxide , Zinc borate, zinc stannate, clay, kaolin, talc, mica, composite silica powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, Q glass Any one or a mixture of at least two of powder, quartz glass powder, short glass fiber or hollow glass, preferably crystalline silica, fused silica, amorphous silica, spherical silica, and hollow silica , Aluminum hydroxide, boehmite, magnesium hydroxide, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, aluminum nitride, silicon carbide, aluminum oxide , Zinc borate, zinc stannate, clay, kaolin, talc, mica, composite silica powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, Q glass Any one or a mixture of at least two of powder, quartz glass powder, short glass fiber or hollow glass, such as a mixture of crystalline silica and fused silica, amorphous silica and spherical silica The mixture of hollow silicon dioxide and aluminum hydroxide, the mixture of boehmite and magnesium hydroxide, the mixture of molybdenum oxide and zinc molybdate, the mixture of titanium oxide, zinc oxide, strontium titanate and barium titanate, barium sulfate , A mixture of boron nitride and aluminum nitride, a mixture of silicon carbide, aluminum oxide, zinc borate and zinc stannate, a mixture of composite silica powder, E glass powder, D glass powder, L glass powder and M glass powder, S glass A mixture of powder, T glass powder, NE glass powder and quartz glass powder, a mixture of clay, kaolin, talc and mica, a mixture of short glass fibers and hollow glass. In terms of being able to mix more inorganic fillers, the aforementioned fused silica is preferred. The aforementioned fused silica can be pulverized or spherical fused silica in any shape. In order to increase the amount of fused silica blended and suppress the increase in the melt viscosity of the curable composition, it is preferable to mainly use spherical fused silica. Silicon dioxide.

The average particle size (d50) of the inorganic filler is not particularly limited, but from the viewpoint of dispersibility, the average particle size (d50) is preferably 0.1-10 microns, such as 0.2 microns, 0.8 microns, 1.5 microns, 2.1 microns, 2.6 microns , 3.5 microns, 4.5 microns, 5.2 microns, 5.5 microns, 6 microns, 6.5 microns, 7 microns, 7.5 microns, 8 microns, 8.5 microns, 9 microns, 9.5 microns, and more preferably 0.2 to 5 microns. Inorganic fillers of different types, different particle size distributions or different average particle diameters can be used alone or in combination as required.

The present invention does not specifically limit the amount of inorganic filler. Based on 100 parts by weight of the maleimide compound, styrene-maleic anhydride copolymer and epoxy resin in total, the amount of the inorganic filler may be 10 to 200 parts by weight, for example 20 parts by weight, 40 parts by weight , 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 140 parts by weight, 160 parts by weight, 180 parts by weight, preferably 20 to 150 parts by weight, more preferably 30 to 100 parts by weight.

The inorganic filler of the present invention can be used in combination with a surface treatment agent, a wetting agent, or a dispersing agent. The surface treatment agent is not particularly limited, and it can be selected from commonly used surface treatment agents for inorganic surface treatment. It is specifically ethyl orthosilicate compounds, organic acid compounds, aluminate compounds, titanate compounds, organosilicon oligomers, macromolecular treatment agents, silane coupling agents, and the like. There is no particular limitation on the silane coupling agent, which is selected from silane coupling agents commonly used in the surface treatment of inorganic substances, which are specifically amino silane coupling agents, epoxy silane coupling agents, vinyl silane coupling agents, and phenyl silane coupling agents. Coupling agents, cationic silane coupling agents, mercaptosilane coupling agents, etc. are preferably aminosilane coupling agents, epoxy silane coupling agents, phenylsilane coupling agents, and more preferably aminosilane coupling agents. There are no special restrictions on the wetting agent and dispersing agent, which are selected from the wetting agents and dispersing agents commonly used in coatings. In the present invention, different types of surface treatment agents, wetting agents, and dispersing agents can be used alone or in appropriate combination as required.

The resin composition of the present invention may also include organic fillers. The organic filler is not particularly limited, and can be selected from any one or a mixture of at least two of silicone, liquid crystal polymer, thermosetting resin, thermoplastic resin, rubber or core-shell rubber. The organic filler may be powder or granules. The amount of organic filler added can be adjusted as required.

Curing accelerator:

The resin composition of the present invention may further include a curing accelerator, which reduces the curing temperature of the resin and accelerates the curing speed of the resin. Examples of curing accelerators may include phosphorus-based accelerators, tertiary amines, imidazoles, metal salts of organic acids, Lewis acid, amine salts, and the like.

Preferably, the curing accelerator is an imidazole-based curing accelerator or a pyridine-based curing accelerator, wherein the imidazole-based curing accelerator may include, for example: 2-methylimidazole, 2-undecylimidazole, 2 -Heptadecyl imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-benzene 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl 2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2 ,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methyl Imidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl 3-benzyl imidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins. The pyridine curing accelerator is selected from triethylamine, benzyldimethylamine and dimethylaminopyridine. When a curing accelerator (except the metal-based curing accelerator) is blended in the resin composition of the present invention, the total weight of the maleimine compound, styrene-maleic anhydride copolymer, and epoxy resin is 100%. In parts, the curing accelerator is preferably in the range of 0.005 to 5 parts by mass, more preferably in the range of 0.01 to 3 parts by mass. If it is within this range, thermal curing can be more efficiently performed, and the storage stability of the resin varnish can also be improved.

In addition, various compounding agents such as silane coupling agents, mold release agents, pigments, and emulsifiers can be added to the resin composition of the present invention as necessary.

The resin composition of the present invention exhibits excellent solvent solubility. Therefore, the resin composition may be compounded with an organic solvent in addition to the aforementioned components. For example, aromatic hydrocarbons, aprotic polar solvents, alcohols, ketones, glycol ethers, etc. can be cited. Preferred are aprotic polar solvents, alcohols, ketones, and amide solvents. Examples of aromatic hydrocarbons include benzene, toluene, and xylene. Examples of alcohols include methanol, ethanol, propanol, and butanol. Ketones can include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisopropyl ketone, di-tert-butyl ketone, 2-heptanone, 4-heptanone, 2-octanone, ring Pentanone, cyclohexanone, cyclohexyl methyl ketone, acetophenone, acetone, dioxane, etc. Specific examples of aprotic polar solvents include dimethyl sulfide (DMSO), formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methyl Acetamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, etc. Specific examples of glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl Ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether Acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, etc.

The resin composition of the present invention can also be used in combination with maleimide resins other than the specific maleimide resin, as long as it does not impair the inherent properties of the resin composition. The maleimide resin that can be selected can be bis(4-maleimidphenyl) methane, bis(4-maleimidphenyl) ether, bis(4-maleimid) Phenyl) sulfide, bis(4-maleimidinyl phenyl) sulfide, bis(4-maleimidinyl phenyl) ketone, 4-methyl-1,3-phenylene bis Maleimide, m-phenylene bismaleimide, 1,3-bis(3-maleiminophenoxy)benzene, 1,3-bis(4-maleimide) Phenyloxy)benzene, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(4-(4-maleimidophenoxy) )-Phenyl) ash, bis(3,5-dimethyl-4-maleimidphenyl) methane, bis(3-ethyl-5-methyl-4-maleimid Any one or at least two of phenyl)methane, bis(3,5-diethyl-4-maleiminophenyl)methane, polyphenylmethane maleimide (Polyphenylmethane maleimide) mixture. These maleimide resins can be used alone or in combination of multiple types as required, or these maleimide resins can be modified with an allyl compound or an amine compound.

The resin composition of the present invention can also be used in combination with various polymers, rubbers, and elastomers, as long as it does not impair the inherent properties of the resin composition. Specifically, for example, liquid crystal polymers, thermosetting resins, thermoplastic resins, different flame retardant compounds or additives can be used. The thermosetting resin may be selected from phenolic resins, cyanate ester resins, benzoxazine resins, polyphenylene ether resins, silicone resins, allyl resins, amine compounds and dicyclopentadiene resins. They can be used alone or in combination as required.

The "comprising" in the present invention means that in addition to the aforementioned components, it can also include other components, which impart different characteristics to the resin composition. In addition, the "including" mentioned in the present invention can also be replaced with a closed "being" or "consisting of".

The resin composition of the present invention can be used for various electronic material applications, and can be prepared, for example, by using an extruder, a kneader, a roller, etc., to thoroughly mix various single components until uniform.

When manufacturing a printed circuit board using the thermosetting resin composition of the present invention, the following method may be mentioned: impregnating a reinforced base material with a varnish-like thermosetting resin composition containing the resin of the present invention, a curing agent, an organic solvent, other additives, etc. , Overlap copper foil and heat and crimp. The reinforcing base material that can be used here includes paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, and the like. If the above method is described in further detail, first, the varnish-like thermosetting resin composition is heated at a heating temperature suitable for the type of solvent used, preferably 50 to 170°C for 3 to 15 minutes, to obtain a cured product Prepreg. The mass ratio of the thermosetting resin composition and the reinforcing substrate used at this time is not particularly limited, but usually, it is preferably prepared so that the resin component in the prepreg reaches 30 to 90% by mass. Next, the prepreg obtained as described above is laminated by a conventional method, and the copper foil is appropriately overlapped, and heated and pressed at 170 to 250°C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours to obtain the target printed circuit Substrate.

Example

Next, the following examples are used to explain the present invention in more detail, but these examples are not used to limit the present invention in any situation. In each example, a resin varnish, a prepreg, and a copper-clad laminate were produced, and the produced copper-clad laminate was evaluated. The evaluation method is as follows.

Evaluation method

(A) Glass transition temperature (Tg) Using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Rheometric Co., Ltd., rectangular tensile method; frequency 1 Hz, heating rate 5°C/min), the elastic modulus change of the aforementioned evaluation sample was measured The temperature that reaches the maximum (the maximum rate of change of tanδ) is evaluated as the glass transition temperature.

(B) Coefficient of Thermal Expansion (CTE) According to IPC-TM-650 2.4.24 method for determination.

(C) Dielectric constant (Dk) and dielectric loss factor (Df) Test the dielectric constant and dielectric loss factor at 1 GHz according to the plate capacitor method.

(D) Peel strength Measure according to IPC-TM-650 2.4.8 method.

(E) Evaluation of heat and humidity resistance After etching the copper foil on the surface of the copper clad laminate, evaluate the substrate; place the substrate in a pressure cooker, treat it at 120°C and 105 KPa for 3 hours, then immerse it in a tin furnace at 288°C, and record the corresponding Time: The evaluation can be ended when the substrate has been in the tin furnace for more than 5 minutes without blistering or delamination. No blistering and no delamination was recorded as Ο, and blistering or delamination was recorded as ×.

(F) Flame retardancy Measured according to UL 94 vertical combustion method.

(G) Heat migration resistance After 5 times of lead-free reflow soldering process (material temperature>260℃), the copper clad laminate was made into slice samples, and the resin morphology was observed under an electron microscope. No migration or delamination in the resin layer was recorded as Ο, and migration or delamination in the resin layer was recorded as ×.

The raw materials used in the examples include:

Maleimide compounds: (A1) Biphenyl aralkyl maleimide resin "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), having a structure represented by formula (I) (A2) Bis (3-ethyl-5-methyl-4-maleiminophenyl) methane "KI-70" (Japan KI Co., Ltd.) does not have the structure represented by formula (I)

Styrene-Maleic Anhydride Copolymer (B): (B1) "SMA EF30" (styrene/maleic anhydride=3, manufactured by Sartomer), acid value 280 mgKOH/g (B2) "SMA EF40" (styrene/maleic anhydride = 4, manufactured by Sartomer), acid value 215 mgKOH/g

Epoxy resin (C): (C1) Dicyclopentadiene epoxy resin "HP-7200H" (manufactured by DIC Corporation) (C2) Biphenyl aralkyl type epoxy resin "NC-3000-H" (manufactured by Nippon Kayaku Co., Ltd.)

(D2) 磷腈化合物“SPB-100”（大塚化學株式會社） (D3) 磷酸酯化合物“PX-200”（大八化學株式會社）Flame retardant (D): (D1) High melting point phosphazene compound (Otsuka Chemical Co., Ltd.), the chemical formula is as follows

(D2) Phosphononitrile compound "SPB-100" (Otsuka Chemical Co., Ltd.) (D3) Phosphate ester compound "PX-200" (Ohachi Chemical Co., Ltd.)

Co-curing agent (E): (E1) 4,4-Diaminodiphenyl ether "DDE" (manufactured by Shandong Wanda Chemical) (E2) Dicyandiamide "Dicy" (made by Ningxia Daiei) (E3) Biphenyl aralkyl phenolic resin "MEH-7851" (manufactured by Meiwa Chemical Co., Ltd.)

Inorganic filler (F): spherical silica "DQ1028L" (manufactured by Jiangsu Lianrui Company)

Curing accelerator (G): 2-phenylimidazole "2PZ" (manufactured by Shikoku Kasei)

Compare curing agent: (B3) Methylhexahydrophthalic anhydride "MHHPA" (made by Guangdong Shengshida) (B4) Methyl Nadic anhydride "MNA" (made in Changchun, Taiwan)

The resin varnishes of the respective Examples and Comparative Examples were prepared with the compositions listed in the following Tables 1 to 5 and the various necessary components mentioned above.

Each obtained resin varnish was impregnated with a glass cloth (0.1 mm) of 2116, and dried at 155°C for 5 minutes to obtain a prepreg. 8 pieces of this prepreg were stacked and 18 μm inverted copper foil (manufactured by Mitsui Metals Co., Ltd.) was laminated on both sides and heated and pressurized for 90 minutes at a temperature of 200°C and a pressure of 25 kgf/cm ² (2.45 MPa) , The thickness of 1.0 mm copper clad laminate was produced, and the relative dielectric constant, metal foil adhesion, glass transition temperature, thermal expansion, flame retardancy and processability were measured and evaluated according to the above methods.

The results are shown in Tables 1 to 5.

Table 1 Examples 1 to 6

Table 2 Examples 7-12

Table 3 Comparative Examples 1 to 6

Table 4 Comparative Examples 7-12

Table 5 Comparative Examples 13-14

It can be seen from Tables 1 to 2 that in Examples 1 to 12, the performance of the composition is excellent by changing the amount and type of each individual component in the resin composition.

In Comparative Example 1, compared with Example 7, the polyfunctional biphenyl aralkyl maleimide resin represented by formula (I) was replaced with a bifunctional maleimide resin represented by formula (I). For the amine resin, the dielectric properties, peel strength, heat resistance, and flame retardancy of the resin composition are greatly reduced.

In Comparative Examples 2 and 3, compared with Example 7, replacing the styrene-maleic anhydride copolymer with ordinary small molecule anhydride, the dielectric properties, peeling strength, heat resistance, and heat resistance of the resin composition are greatly reduced. .

In Comparative Examples 4, 5, and 6, compared with Example 7, the phosphazene flame retardant was replaced with other phosphorus-containing flame retardants, and the peel strength, heat resistance, heat and humidity resistance, and heat migration resistance of the resin composition were significantly improved. decline.

In Comparative Examples 7-14, after each component exceeds the scope of the claim, the performance of the resin composition has different degrees of deterioration.

The thermosetting resin composition of the present invention has good compatibility, and has excellent dielectric properties, high flame retardancy, good heat resistance, low water absorption, low thermal expansion coefficient and high bonding properties with conductors.

Obviously, those skilled in the art can make various changes and modifications to the embodiments of the present invention without departing from the spirit and scope of the present invention. In this way, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these modifications and variations.

Claims (11)

A resin composition comprising: a maleimide compound represented by formula (I), a styrene-maleic anhydride copolymer, an epoxy resin, and a phosphazene flame retardant represented by formula (II);

(I) Wherein, R ₁ is a phenylene group, a biphenylene group, a naphthylene group or a dicyclopentadienyl group, R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, n is an integer from 1 to 20;

(II) where Rp is one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, or an allyl group; wherein the maleimide compound represented by formula (I), styrene-male The total weight of the acetic anhydride copolymer and the epoxy resin is 100 parts by weight, the maleimide compound is 10 to 80 parts by weight; the styrene-maleic anhydride copolymer is 5 to 50 parts by weight Parts by weight, wherein the molar ratio of the styrene unit to the maleic anhydride unit is 0.5-10, the acid value of the styrene-maleic anhydride copolymer is 80-800 mgKOH/g; the epoxy resin is 10 Parts by weight to 60 parts by weight; the phosphorus in the phosphazene flame retardant is relative to the maleimide compound, the styrene-maleic anhydride copolymer, the epoxy resin and the phosphazene inhibitor The total weight of the fuel is 0.1% to 5% by weight. The resin composition according to claim 1, wherein the equivalent ratio of the maleic anhydride group in the styrene-maleic anhydride copolymer and the epoxy group in the epoxy resin is 0.5 to 1.5. The resin composition according to claim 1 or 2, wherein the total weight of the maleimide compound, styrene-maleic anhydride copolymer, and epoxy resin represented by formula (I) is 100 parts by weight, The styrene-maleic anhydride copolymer is 10 to 40 parts by weight. The resin composition according to claim 1 or 2, wherein the epoxy resin is a phosphorus-containing epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, naphthalene epoxy resin, naphthol epoxy resin Epoxy resin, naphthol novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene novolac epoxy resin, aralkyl epoxy resin, aralkyl phenolic resin Type epoxy resin, epoxy resin containing arylene ether structure, or their mixture. The resin composition according to claim 1 or 2, wherein the total weight of the maleimide compound, styrene-maleic anhydride copolymer, and epoxy resin represented by formula (I) is 100 parts by weight, The epoxy resin is 20 to 50 parts by weight. The resin composition according to claim 1 or 2, wherein the phosphorus in the phosphazene flame retardant is relative to the maleimide compound, the styrene-maleic anhydride copolymer, and the epoxy The total weight of the resin and the phosphazene flame retardant is 0.5% to 4% by weight. The resin composition according to claim 1 or 2, wherein the resin composition further contains one or more of a co-curing agent, a filler, a curing accelerator, a silane coupling agent, a release agent, a pigment, and an emulsifier. A prepreg which is obtained by impregnating or coating a substrate with the resin composition according to any one of claims 1 to 7 and curing it. A laminated board comprising at least one prepreg according to claim 8. A metal-clad laminate comprising at least one prepreg as described in claim 8 and metal foils covering one or both sides of the prepreg. A printed circuit board comprising at least one prepreg as described in claim 8.