阅读说明：本技术 一种电子产品组件用热固性树脂组合物及其应用 (Thermosetting resin composition for electronic product component and application thereof ) 是由 林立成 孙启辉 粟俊华 席奎东 蒋剑 王洁洁 于 2020-11-30 设计创作，主要内容包括：本发明涉及一种电子产品组件用热固性树脂组合物及其应用,该组合物包括以下质量份组分：乙烯基热固性树脂50-90份；硅烷封端乙烯基热固性树脂5-40份；固化剂1-5份；阻燃剂10-40份；中空玻璃微球5-40份；所述的热固性树脂组合物用于制备电子产品组件,包括半固化片、覆铜层压板或印刷电路板。与现有技术相比,本发明能赋予覆铜基板低的吸水率、低介电常数、低介电损耗以及优良的耐湿热特性。(The invention relates to a thermosetting resin composition for electronic product components and application thereof, wherein the composition comprises the following components in parts by mass: 50-90 parts of vinyl thermosetting resin; 5-40 parts of silane-terminated vinyl thermosetting resin; 1-5 parts of a curing agent; 10-40 parts of a flame retardant; 5-40 parts of hollow glass microspheres; the thermosetting resin composition is used for preparing electronic product components, including prepregs, copper-clad laminates or printed circuit boards. Compared with the prior art, the invention can endow the copper-clad substrate with low water absorption, low dielectric constant, low dielectric loss and excellent damp-heat resistance.)

1. The thermosetting resin composition for the electronic product component is characterized by comprising the following components in parts by mass:

2. the thermosetting resin composition for electronic product components as claimed in claim 1, wherein the vinyl thermosetting resin comprises one or more of polybutadiene, polybutadiene copolymer, styrene-divinylbenzene oligomer, polyphenylene oxide, vinyl crosslinking agent.

3. The thermosetting resin composition for electronic product components of claim 2, wherein the polybutadiene comprises one or more of non-functionalized polybutadiene, maleic anhydride grafted polybutadiene, epoxy modified polybutadiene, hydroxyl terminated polybutadiene, methacrylate terminated polybutadiene, or isocyanate terminated polybutadiene;

the polybutadiene copolymer comprises one or more of butadiene-styrene copolymer, butadiene-styrene-butadiene copolymer, styrene-butadiene-styrene copolymer or butadiene-isoprene copolymer;

the polyphenyl ether comprises polyphenyl ether resin with 1-3 unsaturated functional groups; specifically, the modified polyphenylene ether comprises one or more of styrene modified polyphenylene ether or acryl modified polyphenylene ether;

the vinyl crosslinking agent is selected from compounds which have C ═ C unsaturated double bonds on molecular chains and can generate free radical polymerization reaction to form crosslinking products, and specifically comprises one or more of triallyl isocyanurate, triallyl cyanurate, styrene, divinyl benzene and bismaleimide.

4. The thermosetting resin composition for electronic product components of claim 1, wherein said silane-terminated vinyl thermosetting resin comprises silane-terminated liquid polybutadiene;

the molecular weight of the silane terminated liquid polybutadiene is 3000-5000, and the vinyl content is 20-90%.

5. The thermosetting resin composition for electronic product components of claim 1, wherein the curing agent comprises one or more of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 3-dimethyl-2, 3-diphenylbutane, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t-butylperoxy dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, or dicyclohexyl peroxycarbonate.

6. The thermosetting resin composition for electronic product assemblies as claimed in claim 1, wherein the flame retardant is one or more of brominated styrene, decabromodiphenyl ether, decabromodiphenylethane, ethylenebistetrabromophthalimide, tris (2, 6-dimethoxybenzene) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide.

7. The thermosetting resin composition for electronic product components as claimed in claim 1, wherein the hollow glass microspheres have a particle size of less than 70 μm.

8. The thermosetting resin composition for electronic component parts according to claim 1, further comprising one or more of a filler, a silane coupling agent, a toughening agent or a solvent.

9. The thermosetting resin composition for electronic component assemblies as claimed in claim 8, wherein the filler comprises one or more of crystalline silica, fused silica, spherical silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, aluminum nitride, boron nitride, silicon nitride, aluminum silicon carbide, sodium carbonate, magnesium carbonate, titanium dioxide, zinc oxide, zirconium oxide, potassium titanate, strontium titanate, barium titanate, ceramic fiber, zinc molybdate, ammonium molybdate, calcium phosphate, boehmite, or polytetrafluoroethylene powder.

10. An electronic component made of the thermosetting resin composition for electronic component parts according to any one of claims 1 to 9, wherein the electronic component part comprises a prepreg, a copper clad laminate or a printed circuit board.

Technical Field

The invention relates to the field of thermosetting resin, in particular to a thermosetting resin composition for electronic product components and application thereof.

Background

The mobile internet and the internet of things are developing towards the direction of network diversification, broadband, integration and intellectualization. With the popularization of various mobile internet and intelligent terminals, the mobile data traffic will show explosive growth towards the future. 5G is used as a new generation mobile communication network system, the data transmission rate of a mobile user is improved by 10 times to 100 times compared with that of 4G, the peak transmission rate can reach 10Gbit/s, and the end-to-end time delay reaches the millisecond level, so that the requirements on electronic circuit materials for high-frequency plates are more rigorous.

In the environment of 5G communication, reducing the dielectric constant of electronic circuit materials becomes an important means for reducing the signal delay time. The hollow glass microsphere is a hollow closed sphere, has low dielectric constant (DK is between 1.2 and 2.0), can reduce the dielectric constant and dielectric loss of an electronic circuit substrate after being mixed with low-polarity vinyl thermosetting resin for use, and is an important technical route for developing high-frequency plates at present.

For high-frequency plates, the high-frequency plates are required to still keep normal operation under wide frequency, temperature, humidity and other environmental condition changes. However, the hollow glass microsphere material has a large water absorption rate and poor interface bonding with low-polarity thermosetting vinyl resin, so that the water absorption rate of the substrate material is too large due to the comprehensive influence, the critical index characteristics such as dielectric constant and dielectric loss of the material are easy to change under severe environments such as humidity, and the stability of the material in long-term use is poor.

Chinese patent CN109233244A discloses a thermosetting resin composition, which utilizes inorganic oxide to coat hollow glass microspheres, can improve the binding force between the hollow glass microspheres and matrix resin, and reduce the water absorption of substrate material, wherein the inorganic coating layer accounts for 0.1-20% of the total weight of the inorganic coated hollow glass microspheres. Chinese patent CN109836631A discloses a vinyl thermosetting resin composition. The vinyl thermosetting resin composition comprises: vinyl thermosetting resin, curing agent and surface vinyl polyphenyl ether resin chemically modified hollow glass microspheres. The hollow glass microspheres chemically modified by the surface vinyl polyphenyl ether resin are added into the vinyl thermosetting resin composition, so that the interaction between the hollow glass microspheres and the molecular chain segments of the vinyl thermosetting resin can be increased, the upward floating tendency of the hollow glass microspheres in glue solution is reduced, and the uniformity of the glue solution is improved. And the vinyl polyphenyl ether resin chemically modifies the hollow glass microspheres, so that the water absorption of the prepared laminated board can be reduced.

The above special materialsThe bonding force between the hollow glass microspheres and the thermosetting resin can be improved, the water absorption of the substrate material is reduced, and the long-term use stability of the substrate material is improved, but the hollow glass microspheres need to be chemically pretreated at first, and a series of subsequent impurity removal and drying processes are involved. The density of the hollow glass microspheres is 0.08-0.25g/cm³The light weight of the material determines that the wet chemical modification process is complex and troublesome, and a large amount of organic solvent is consumed.

Disclosure of Invention

The present invention has been made to overcome the above-mentioned drawbacks of the prior art, and an object of the present invention is to provide a thermosetting resin composition for electronic component, which can provide a copper-clad substrate with low water absorption, low dielectric constant, low dielectric loss, and excellent moisture and heat resistance, and use thereof.

The purpose of the invention can be realized by the following technical scheme:

designers find that the hollow glass microspheres have high water absorption rate and poor interface bonding with low-polarity thermosetting vinyl resin, so that the substrate material has high water absorption rate, the critical index characteristics of the material, such as dielectric constant, dielectric loss and the like, are easy to change under severe environments, such as humidity and the like, and the material has poor long-term use stability. In the prior art, the interaction between the hollow glass microspheres and the vinyl thermosetting resin is enhanced by chemically modifying the hollow glass microspheres, so that the binding force of an inorganic-organic interface is improved, the water absorption of the material is reduced, and the long-term use stability of the substrate material is improved. However, the chemical modification process of the hollow glass microspheres is complex, and a large amount of organic solvent is used, so that the production efficiency is low, and the energy consumption is high.

Through intensive research, designers find that the bonding force between the hollow glass microspheres and the thermosetting vinyl resin can be effectively improved by directly adding the silane-terminated liquid polybutadiene into the composition. The molecular chain of the silane-terminated liquid polybutadiene contains siloxy groups and C ═ C unsaturated double bonds at the same time, the siloxy groups have reactivity on inorganic substances such as hollow glass microspheres, and the C ═ C unsaturated double bonds have reactivity on vinyl thermosetting resin. Therefore, the silane-terminated liquid polybutadiene can be used as a bonding layer of the hollow glass microsphere and the vinyl resin to form an organic matrix- (organic matrix-silane coupling agent) -inorganic matrix structure, so that the compatibility of the hollow glass microsphere and the vinyl resin is improved, and the water absorption is reduced, and the specific scheme is as follows:

a thermosetting resin composition for electronic product components comprises the following components in parts by mass:

further, the vinyl thermosetting resin comprises one or more of polybutadiene, polybutadiene copolymer, styrene-divinylbenzene oligomer, polyphenylene oxide and vinyl crosslinking agent. One of the above-listed compounds may be used alone, and two or more of the above-listed compounds may be used in combination.

Further, the polybutadiene comprises one or more of non-functionalized polybutadiene, maleic anhydride grafted polybutadiene, epoxy modified polybutadiene, hydroxyl terminated polybutadiene, methacrylate terminated polybutadiene or isocyanate terminated polybutadiene; the polybutadiene preferably has a molecular weight of 1000-; the polybutadiene preferably has a high vinyl content, preferably a 1, 2-double bond content of greater than 50%, and more preferably a 1, 2-double bond molar content of greater than 85%.

The polybutadiene copolymer comprises one or more of butadiene-styrene copolymer, butadiene-styrene-butadiene copolymer, styrene-butadiene-styrene copolymer or butadiene-isoprene copolymer;

the polyphenyl ether comprises polyphenyl ether resin with 1-3 unsaturated functional groups; specifically, the modified polyphenylene ether comprises one or more of styrene modified polyphenylene ether or acryl modified polyphenylene ether; the molecular weight of polyphenylene ether is not specifically limited. Specifically, the molecular weight is preferably 1000-4000.

The polyphenylene ether used in the present invention has an average number of functional groups per molecular chain of 1 to 3. If the number of reactive functional groups is small, the cured product has a low crosslinking density, a low glass transition temperature, a large expansion coefficient, and good heat resistance is difficult to obtain; if the number of reactive functional groups is too large, the reaction rate is high, the fluidity of the resin is poor, the impregnation property into the glass fiber cloth is poor, and defects are likely to occur in the formed substrate material. In addition, too much number of functional groups deteriorates the symmetry of polyphenylene ether, and the dielectric properties of the cured product deteriorate.

The vinyl crosslinking agent comprises one or more of triallyl isocyanurate, triallyl cyanurate, styrene, divinyl benzene and bismaleimide.

The vinyl crosslinking agent is a compound which has carbon-carbon unsaturated double bonds on the molecular chain and can generate free radical polymerization reaction to form a crosslinking product.

Further, the silane-terminated vinyl thermosetting resin comprises silane-terminated liquid polybutadiene; the molecular weight of the silane terminated liquid polybutadiene is 3000-5000, and the vinyl content is 20-90%.

The silane-terminated vinyl thermosetting resin is a resin having both a siloxy group and a C ═ C unsaturated double bond in the molecular chain. The siloxy group is reactive with inorganic materials and the C ═ C unsaturated double bond is reactive or compatible with vinyl thermosetting resins. Thus, the silane-terminated vinyl thermoset intervenes between the inorganic and organic interfaces, and can form a bond of organic matrix- (organic matrix-silane coupling agent) -inorganic matrix. The silane-terminated vinyl thermosetting resin is preferably silane-terminated liquid polybutadiene with the vinyl content of 20-90%, the double bond content of the silane-terminated liquid polybutadiene is high, the silane-terminated liquid polybutadiene has higher reactivity and compatibility with the vinyl thermosetting resin, the crosslinking density is high after the silane-terminated liquid polybutadiene reacts with the vinyl thermosetting resin, the gap of a formed inorganic-organic interface is small, and the water absorption of a cured product is favorably reduced.

The molecular weight of the silane terminated liquid polybutadiene is 3000-5000. If the molecular weight is too large, the steric hindrance of a molecular chain is large, and the reactivity and the reaction curing degree with the hollow glass microsphere are reduced; if the molecular weight is too small, the content of carbon-carbon unsaturated double bonds in the molecular chain is low, and the crosslinking density with the vinyl thermosetting resin is low.

Further, the curing agent comprises one or more of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 2, 3-dimethyl-2, 3-diphenylbutane, 1-bis (tert-hexylperoxy) -3,3, 5-trimethylcyclohexane, benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, di-tert-butylperoxy dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, or dicyclohexyl peroxycarbonate. The above curing agents may be used alone or in combination of two or more in view of control of curing efficiency.

Further, the flame retardant is one or more of brominated styrene, decabromodiphenyl ether, decabromodiphenyl ethane, ethylenebistetrabromophthalimide, tris (2, 6-dimethoxybenzene) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Further, the particle size of the hollow glass microsphere is less than 70 μm. The hollow glass microspheres may be chemically unmodified or chemically modified. The particle size is less than 70 μm, and if the particle size is too large, the roughness of the pore wall in the substrate material in the subsequent processing process is too large, and the consistency of signal transmission is influenced.

Further, the composition also includes one or more of a filler, a silane coupling agent, a toughening agent, or a solvent.

Further, the filler includes one or more of crystalline silica, fused silica, spherical silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, aluminum nitride, boron nitride, silicon nitride, aluminum silicon carbide, sodium carbonate, magnesium carbonate, titanium dioxide, zinc oxide, zirconium oxide, potassium titanate, strontium titanate, barium titanate, ceramic fiber, zinc molybdate, ammonium molybdate, calcium phosphate, boehmite, or polytetrafluoroethylene powder. The main function of the added filler is to adjust the dielectric constant of the resin composition; reducing the coefficient of expansion of the composition; the heat resistance of the composition is improved; the flame retardant effect of the composition is improved; the water absorption of the substrate material is reduced.

An electronic product assembly prepared from the thermosetting resin composition for the electronic product assembly comprises a prepreg, a copper-clad laminate or a printed circuit board.

The thermosetting resin composition can be prepared into a prepreg. The preparation method of the prepreg comprises the following steps: preparing the thermosetting resin composition into glue solution, then soaking the reinforcing material in the glue solution to form a layered object, heating the layered object at high temperature to form a prepreg, and baking the prepreg at the temperature of between 100 ℃ and 175 ℃. Examples of the reinforcing material are not particularly limited, and may be commercially available glass cloth that can be used for various printed circuit boards.

The present invention can also provide a copper-clad laminate. The preparation method can be adopted as follows: and taking at least one prepreg and the metal copper foil coated on one side or two sides of the prepreg, and heating and pressurizing to obtain the composite material. The metallic copper foil may be a standard electrolytic copper foil, a reverse copper foil, a low profile copper foil, or an ultra-low profile copper foil. The heating and pressing conditions may be appropriately adjusted depending on the kind of the composition or the thickness of the copper-clad laminate. For example, the pressing temperature can be set to 170-240 deg.C and the pressure can be set to 1.0-6.0 MPa. The copper clad laminate may be further processed to form a printed circuit board according to various circuit board manufacturing processes known in the art.

Compared with the prior art, the invention has the following advantages:

(1) the hollow glass microspheres do not need to be subjected to chemical modification treatment, so that the production efficiency can be improved, and the energy consumption can be reduced;

(2) the molecular weight of the silane terminated liquid polybutadiene is 3000-5000, and the vinyl content is 20-90%. Compared with the hollow glass microspheres chemically modified by surface vinyl polyphenyl ether resin and the hollow glass spheres chemically modified by vinyl silane coupling agent, the hollow glass microspheres of the technical scheme have more carbon-carbon unsaturated double bonds on the surfaces, can improve the crosslinking density with vinyl thermosetting resin in the curing and crosslinking process, endows the hollow glass microspheres with stronger bonding force with the vinyl thermosetting resin, reduces interface gaps, and can more effectively reduce the water absorption of the substrate material;

(3) compared with the addition of micromolecular vinyl silane coupling agent, the silane-terminated liquid polybutadiene has larger molecular weight, and after being combined with the hollow glass microsphere, the surface of the hollow glass microsphere has a thicker hydrophobic layer, so that water vapor can be effectively prevented from being adsorbed on the rough surface of the hollow glass microsphere;

(4) when the main resin in the resin composition is polybutadiene, the similar compatibility characteristic enables the hollow glass microspheres to have better compatibility with the polybutadiene resin with excellent electrical property, and the prepared substrate material has lower water absorption and more excellent dielectric property.

Detailed Description

The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.

The parameters of the substances in the following examples are as follows, unless otherwise specified: the polybutadiene preferably has a molecular weight of 1000-10000 and a high vinyl content, the 1, 2-double bond content being greater than 50%; the average number of functional groups of each molecular chain of the polyphenyl ether is 1-3; the silane terminated vinyl thermosetting resin is silane terminated liquid polybutadiene with the vinyl content of 20-90 percent, and the molecular weight of the silane terminated liquid polybutadiene is 3000-5000; the particle size of the hollow glass microspheres is less than 70 micrometers, and the specific mark is shown in table 1:

TABLE 1

Comparative example 1

Dissolving 15G of polyphenyl ether SA-9000, 10G of vinyl crosslinking agent TAIC, 50G of polybutadiene B-2000, 15G of maleic anhydride grafted polybutadiene MA75, 10G of styrene-ethylene-butylene-styrene block copolymer G1648, 15G of bromine-containing flame retardant SAYTEX 3010, 25G of hollow glass microsphere IM16K, 150G of spherical silica FB-3Y and 2G of curing agent DCP in a toluene solvent, and stirring and uniformly dispersing. And (3) soaking 1080 glass fiber cloth in the glue solution, and drying the solvent in an oven at the temperature of 140 ℃ to obtain the prepreg. And (3) overlapping 6 pieces of 1080 prepregs, covering the two sides with ultra-low profile copper foils with the thickness of 1oz, and performing vacuum curing for 2 hours in a press at the curing temperature of 205 ℃ to prepare the copper-clad laminate.

The characteristic test is carried out by referring to the following test methods:

(1) the water absorption test method comprises the following steps: the method described with reference to IPC-TM-6502.6.2.1;

(2) the normal Dk/Df test method comprises the following steps: reference is made to IPC-TM-6502.5.5.5. C, frequency 10 GHz;

(3) the Dk/Df test method after 24h of moisture absorption comprises the following steps: the sample is subjected to moisture absorption treatment for 24 hours according to the method of IPC-TM-6502.6.2.1, and after the surface moisture of the sample is wiped dry, the Dk/Df value (the sample is not subjected to baking treatment) is tested according to the method of IPC-TM-6502.5.5.5. C, and the frequency is 10 GHz;

(4) dk change rate (Dk value-normal Dk value after 24h moisture absorption)/normal Dk value 100%;

df Change rate (Df value-Df Normal State)/Df Normal State 100% after 24h moisture absorption

(5) In the PCT test, referring to IPC-TM-6502.6.16.1, the method absorbs moisture for 5 hours by pressure cooking, and the phenomenon of layering and board explosion is observed after tin immersion in a tin furnace at 288 ℃.

Examples 1-8 are compared to comparative examples 2-3 only in terms of the components, amounts of the composition, as shown in table 2:

TABLE 2

Table 2 (continuation)

As can be seen from the performance tests of the examples and the comparative examples, the copper-clad substrate prepared from the resin composition provided by the invention has low water absorption rate, low dielectric constant, low dielectric loss and excellent damp-heat resistance, and the following concrete argumentations are as follows:

physical property analysis: water molecules are polar substances, and the dielectric properties of the substrate material deteriorate after water absorption, wherein the deterioration of the Df value is the most serious. From example 1 and comparative examples 1-3, it can be seen that the water absorption of the substrate material was reduced from 0.24% to 0.14% and the variability of the Df value was reduced from 194% to 66% after the addition of silane-terminated liquid polybutadiene to the composition. The silane terminated liquid polybutadiene can reduce the water absorption of the substrate material, improve the electrical signal stability of the substrate material in a humid environment, and has unexpected excellent characteristics on the long-term use stability of a substrate circuit. In fact, the silane-terminated vinyl thermosetting resin in the component mainly reduces the water absorption of the substrate material, and does not contribute to the Dk/Df value in a normal state. The contribution of silane terminated vinyl thermoset resins to Dk/Df is only reflected when the substrate material is placed in a humid environment. Since the water absorption of the substrate material is greatly reduced after the silane-terminated vinyl thermosetting resin is added, the rate of change of Dk/Df of the substrate material is small after the water absorption is reduced (water is a polar molecule, which has a negative effect on the Dk/Df value).

From examples 1-3, it is clear that as the fraction of silane-terminated liquid polybutadiene in the composition increases, the substrate material water absorption tends to decrease and the rate of change in Df value decreases accordingly, but the Df value in the normal state increases. The siloxy groups in the structure of the silane-terminated liquid polybutadiene are polar groups, and the Df value of the substrate material in the normal state can be influenced by the excessive addition amount.

From examples 4-8, it can be seen that the amount of hollow glass microspheres, the amount of spherical silica, and the type and amount of thermosetting resin in the composition can be adjusted to meet the requirements of different Dk/Df values.

The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.