CN113088061A - Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same - Google Patents

Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same Download PDF

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CN113088061A
CN113088061A CN201911342697.XA CN201911342697A CN113088061A CN 113088061 A CN113088061 A CN 113088061A CN 201911342697 A CN201911342697 A CN 201911342697A CN 113088061 A CN113088061 A CN 113088061A
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weight
parts
component
resin composition
flame retardant
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CN113088061B (en
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罗成
孟运东
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention provides a thermosetting resin composition, and a prepreg, a laminated board and a metal foil-clad laminated board using the thermosetting resin composition. The thermosetting resin composition comprises the following components in parts by weight: 1-8 parts by weight of component A aminosilane, 20-70 parts by weight of component B modified or unmodified polyolefin resin, 5-50 parts by weight of component C resin containing at least two maleimide functional groups, and 0-70 parts by weight of component D acrylic acid or methacrylic acid terminated resin; the total amount of the component A, the component B, the component C and the component D is 100 parts by weight. The prepreg comprises a reinforcing material and the thermosetting resin composition attached to the reinforcing material after impregnation and drying. The thermosetting resin composition provided by the invention can provide excellent dielectric properties required by a laminated board, can effectively improve the phase separation phenomenon in the pre-curing process of a resin system with large polarity difference, and can prevent the phenomena of layering and board explosion in the production process of a PCB (printed circuit board).

Description

Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same
Technical Field
The invention belongs to the technical field of printed circuit boards, and particularly relates to a thermosetting resin composition, and a prepreg, a laminated board and a metal foil-clad laminated board using the thermosetting resin composition.
Background
With the increase in speed and multifunction of information processing of electronic products, the demand for increased frequency of applications and the size reduction of communication devices have been increasing, and therefore, there is an increasing demand for smaller and lighter electronic devices capable of transmitting information at high speed.
At present, the working frequency of the traditional communication equipment generally exceeds 500MHz, and most of the working frequency is 1-10 GHz; with the demand of transmitting a large amount of information in a short time, the operating frequency of the communication device is also continuously increased, thereby bringing about the problem of signal integrity. As a basic material for signal transmission, the dielectric properties of the copper clad laminate material are one of the main aspects affecting signal integrity. Generally, the smaller the dielectric constant of the substrate material, the faster the transmission rate, and the smaller the dielectric loss tangent, the better the signal integrity. Therefore, how to reduce the dielectric constant and the dielectric loss tangent of the substrate is a hot technical problem in recent years. In addition, in order to meet the requirements of PCB (printed circuit board) processability and performance of terminal electronic products, the copper-clad substrate material must have good dielectric properties, heat resistance and mechanical properties, and also have good process processability.
CN 104725828A discloses a resin composition comprising: (A) the vinyl thermosetting polyphenyl ether and bifunctional maleimide or a prepolymer of the polyfunctional maleimide and (B) polyolefin resin can meet the requirements of high-speed electronic circuit substrates on the comprehensive properties such as dielectric property, heat resistance and the like.
However, the ene addition reaction is easily generated between the maleimide resin with strong polarity and the polyolefin resin with weak polarity, so that the thermosetting resin system containing the maleimide resin and the polyolefin resin is easy to generate phase separation in the pre-curing process due to the excessively high reaction speed, and further the high-speed multilayer PCB substrate is easy to generate delamination and board explosion in the production process. And thus, have to be solved.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide a thermosetting resin composition, and a prepreg, a laminate and a metal-clad laminate using the same. The thermosetting resin composition can provide excellent dielectric properties required by a laminated board, can effectively improve the phase separation phenomenon in the pre-curing process of a resin system with large polarity difference, and can prevent the phenomena of layering and board explosion in the production process of a PCB (printed circuit board).
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a thermosetting resin composition, which comprises the following components in parts by weight:
and (2) component A: 1-8 parts of aminosilane;
and (B) component: 20-70 parts by weight of modified or unmodified polyolefin resin;
and (3) component C: 5-50 parts by weight of a resin containing at least two maleimide functional groups;
and a component D: 0-70 parts by weight of an acrylic or methacrylic end-capped resin;
and the total amount of the component A, the component B, the component C and the component D is 100 parts by weight.
The present invention employs, as the main resin component of the thermosetting resin composition, a vinyl group-containing modified or unmodified polyolefin resin and a resin containing at least two maleimide functional groups, both of which are capable of undergoing an ene addition reaction. However, the inventor finds that the electron-deficient maleimide functional group and the electron-rich vinyl-containing polyolefin have too high reaction speed, so that excessive reaction and premature gelation occur in the subsequent pre-curing process, the phase separation phenomenon is generated, the engineering production control is not facilitated, and the delamination and board explosion phenomena are easy to occur in the production process of the PCB.
According to the invention, the amino silane is introduced into the composition, the amino group of the amino silane is easy to generate Michael addition reaction with electron-deficient C ═ C double bonds in the maleimide, and part of the electron-deficient C ═ C double bonds in the maleimide are consumed, so that the reaction speed of the composition can be reduced, the problem that gel is too early due to excessive reaction of a bonding sheet in the pre-curing process is avoided, the phase separation phenomenon is improved and even eliminated, and the PCB delamination and board explosion are prevented.
In the present invention, aminosilane is one of the components of the matrix resin, and participates in the reaction between the matrix resins, and the necessary amount of addition is large. If the content of aminosilane is insufficient (< 1%), the improvement effect on the phase separation problem is not significant, and the thermosetting resin composition still undergoes phase separation during the pre-curing process; if the content of aminosilane is too large (> 8%), it tends to result in a low glass transition temperature after curing of the resin thermosetting resin composition. Therefore, in the present invention, the aminosilane is contained in an amount of 1 to 8 parts by weight, and may be, for example, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, or the like.
The content of the modified or unmodified polyolefin resin is 20 to 70 parts by weight, and may be, for example, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, or the like.
The content of the resin having at least two maleimide functional groups is 5 to 50 parts by weight, and may be, for example, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 45 parts by weight, 48 parts by weight, 50 parts by weight or the like.
The content of the acrylic or methacrylic end-capped resin is 0 to 70 parts by weight, and may be, for example, 0 part by weight, 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, or the like.
As a preferable technical scheme of the invention, the content of the aminosilane is 2-6 parts by weight based on 100 parts by weight of the total amount of the component A, the component B, the component C and the component D.
Preferably, the preparation method of the thermosetting resin composition is as follows: the aminosilane is pre-reacted with the resin containing at least two maleimide functional groups prior to mixing with the other components. The pre-reaction can pre-react the electron-deficient C ═ C in the maleimide which has a fast reaction speed with the electron-rich C ═ C with the N-H in the aminosilane, so that the reaction speed of the two double bonds can be effectively reduced, the phase separation condition can be improved, and the heat resistance of the plate can be further improved.
Preferably, the temperature of the pre-reaction is 100-; the time is 30-180min, such as 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 180 min.
As a preferred embodiment of the present invention, the modified or unmodified polyolefin resin is one or a combination of at least two selected from the group consisting of polybutadiene, butadiene-styrene copolymer, epoxidized polybutadiene resin, hydroxyl-modified polybutadiene resin, maleic anhydride-modified polybutadiene, maleic anhydride-modified styrene-butadiene copolymer, and olefin-modified polyphenylene ether resin.
As a preferred technical scheme of the invention, the resin containing at least two maleimide functional groups has a structure shown as the following formula I:
Figure BDA0002331864810000041
wherein m is a positive integer greater than 1, and X is selected from
Figure BDA0002331864810000042
Figure BDA0002331864810000043
Figure BDA0002331864810000051
Figure BDA0002331864810000061
Any one of the above;
wherein a is a positive integer of 1-20, R4Is phenyl or alkyl with 1-4 carbon atoms, and represents the access position of the group.
As a preferred embodiment of the present invention, the acrylic or methacrylic terminated resin has a structure represented by the following formula II:
Figure BDA0002331864810000062
wherein n is a positive integer of 1-6, R1Is methyl or a hydrogen atom, Y is selected from
Figure BDA0002331864810000063
Polybutadiene chain, butadiene-styrene copolymer chain, straight-chain alkyl group having 6 to 18 carbon atoms,
Figure BDA0002331864810000064
Figure BDA0002331864810000065
Any one of the above;
n1 and n2 are positive integers, and n1+ n2 is 10-20;
r2 is
Figure BDA0002331864810000071
Figure BDA0002331864810000072
Figure BDA0002331864810000073
Represents the access position of the group.
As a preferable embodiment of the present invention, the thermosetting resin composition further comprises a component E: and (4) filling.
Preferably, the filler is added in an amount of 1 to 300 parts by weight, preferably 20 to 300 parts by weight, more preferably 20 to 200 parts by weight, and particularly preferably 30 to 100 parts by weight, based on 100 parts by weight of the total amount of the component a, the component B, the component C, and the component D.
Preferably, the filler is an inorganic filler and/or an organic filler.
Preferably, the inorganic filler is selected from any one or a mixture of at least two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate and inorganic phosphorus, preferably any one or a mixture of at least two of crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talc, calcium silicate, calcium carbonate and mica.
Preferably, the organic filler is selected from any one of polytetrafluoroethylene powder, polyphenylene sulfide, an organic phosphonium salt compound and polyether sulfone powder or a mixture of at least two of the foregoing.
Preferably, the median particle diameter of the filler is 0.01 to 50 μm, preferably 0.01 to 20 μm, and more preferably 0.1 to 10 μm.
As a preferable embodiment of the present invention, the thermosetting resin composition further comprises component F: a free radical initiator.
Preferably, the amount of the radical initiator added is 0.01 to 6 parts by weight, preferably 0.1 to 2 parts by weight, and more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total amount of the component a, the component B, the component C, and the component D.
Preferably, the radical initiator is selected from any one of organic peroxides, carbon-based radical initiators and azo-based radical initiators or a mixture of at least two of them.
Preferably, the thermosetting resin composition further comprises component G: and (3) a flame retardant.
Preferably, the flame retardant is added in an amount of 1 to 30 parts by weight, based on 100 parts by weight of the total amount of the component a, the component B, the component C and the component D.
Preferably, the flame retardant is a halogen-free flame retardant and/or a halogenated flame retardant.
Preferably, the halogen-free flame retardant is one or a mixture of at least two of phosphorus flame retardant, P-N flame retardant, nitrogen flame retardant, metal oxide, metal hydroxide, organosilicon flame retardant and halogen-free flame retardant synergist.
Preferably, the phosphorus-based flame retardant is selected from any one or a mixture of at least two of tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a phenoxyphosphazene compound, a phosphate ester, a polyphosphate ester, a polyphosphonate ester, and a phosphonate-carbonate copolymer.
Preferably, the P-N series flame retardant is selected from one or a mixture of at least two of melamine polyphosphate, melamine phosphonate, ammonium polyphosphate and polyphosphazene.
Preferably, the nitrogen-based flame retardant melamine cyanurate.
Preferably, the halogenated flame retardant is selected from one or a mixture of at least two of brominated triazine, brominated polystyrene, polybrominated styrene, brominated SBS, brominated styrene-butadiene resin, brominated polybutadiene, polydibromophenyl ether, decabromodiphenylethane, tetrabromophthalic anhydride and ethylenebistetrabromophthalimide.
The term "comprising" as used herein means that it may include, in addition to the components, other components which impart different characteristics to the resin composition. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" as closed.
For example, the thermosetting resin composition of the present invention may be added with a thermosetting resin, and specific examples thereof include polyphenylene ether resin, phenol resin, polyurethane resin, melamine resin, and the like, and a curing agent or a curing agent accelerator for these thermosetting resins may be added.
The thermosetting resin composition provided by the present invention may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like.
These thermosetting resins and various additives may be used alone or in combination of two or more.
The method for preparing the thermosetting resin composition of the present invention is not particularly limited, and the thermosetting resin composition can be prepared by blending, stirring and mixing the component A, the component B, the component C, the component D, the initiator, the filler, the flame retardant, various thermosetting resins and various additives by a known method.
In a second aspect, the present invention provides a prepreg comprising a reinforcing material and the thermosetting resin composition of the first aspect attached to the reinforcing material by impregnation drying.
The preparation method of the prepreg is not particularly limited, and for example, the thermosetting resin composition described in the first aspect may be dissolved or dispersed in a solvent to obtain a resin glue solution; and then infiltrating the reinforcing material with resin glue solution, and drying to obtain the prepreg.
The solvent is not particularly limited in the present invention, and specific examples thereof include alcohols such as methanol, ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol and butyl carbitol, ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and mesitylene, esters such as ethoxyethyl acetate and ethyl acetate, and nitrogen-containing solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone. The solvent may be used singly or in combination of two or more, and preferably an aromatic hydrocarbon solvent such as toluene, xylene or mesitylene is used in combination with a ketone solvent such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone. The amount of the solvent to be used can be selected by those skilled in the art according to their own experience, so that the obtained resin glue solution has a viscosity suitable for use.
In the process of dissolving or dispersing the thermosetting resin composition in a solvent as described above, an emulsifier may be added. The powder filler and the like can be uniformly dispersed in the glue solution by dispersing through the emulsifier.
The reinforcing material is not particularly limited, and organic fibers, inorganic fiber woven cloth or non-woven fabric can be selected, the organic fibers can be aramid fiber non-woven fabric, and the inorganic fiber woven cloth can be E-glass fibers, D-glass fibers, S-glass fibers, T-glass fibers, NE-glass fibers or quartz cloth. The thickness of the reinforcing material is not particularly limited, and the woven or nonwoven fabric is preferably 0.01 to 0.2mm thick, and is preferably subjected to a fiber-opening treatment and a silane surface treatment, from the viewpoint of good dimensional stability in the application to a laminate. In order to provide good water and heat resistance, the silane is preferably any one of epoxy silane, amino silane or vinyl silane or a mixture of at least two thereof.
The drying method after the reinforcing material is soaked is not particularly limited, and for example, the reinforcing material can be baked for 2-10 minutes at the temperature of 100-200 ℃ for drying.
In a third aspect, the present invention provides a resin film obtained by post-curing the resin composition of the first aspect after baking and heating.
In a fourth aspect, the present invention provides an adhesive-backed copper foil obtained by applying the resin composition of the first aspect to a copper foil or a PI film of a PI film-coated copper foil and forming a semi-cured state by heating.
In a fifth aspect, the present invention provides a laminate comprising one or at least two stacked prepregs according to the second aspect.
In a sixth aspect, the present invention provides a metal-clad laminate comprising one or at least two stacked prepregs according to the second aspect, and a metal foil clad to one or both sides of one prepreg or the stacked prepregs.
And (2) overlapping one or more prepregs according to the second aspect in a certain sequence, respectively covering copper foils on one side or two sides of the mutually overlapped prepregs, and curing in a hot press to obtain the copper clad laminate. Or one or more prepregs according to the second aspect are stacked together in a certain order, a release film is respectively coated on one side or two sides of the stacked prepregs, and the prepregs are cured in a hot press, so that the insulating board or the single panel can be manufactured. The curing temperature can be 150-250 ℃, and the curing pressure can be 25-60 kg/cm2。
The prepreg and the laminated board prepared by the method have excellent dielectric property and damp-heat resistance, high glass transition temperature and low water absorption rate.
Compared with the prior art, the invention has the following beneficial effects:
the thermosetting resin composition provided by the invention can provide good dielectric properties and glass transition temperature required by a laminated board; and the thermosetting resin composition contains amino silane, amino groups of the amino silane are easy to generate Michael addition reaction with electron-deficient C ═ C double bonds in maleimide, and part of the electron-deficient C ═ C double bonds in the maleimide are consumed, so that the reaction speed of the composition can be reduced, the phenomenon that gel is too early caused by excessive reaction of bonding sheets in the pre-curing process is avoided, the phase separation phenomenon is improved and even eliminated, and the PCB delamination and board explosion are prevented.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources of the raw materials used in the examples of the present invention are shown in table 1 below:
TABLE 1
Figure BDA0002331864810000111
Figure BDA0002331864810000121
Example 1
The embodiment provides a copper clad laminate, and a preparation method thereof is as follows:
(1) preparation of resin glue solution
Taking a container, adding 5 parts by weight of BDM type bismaleimide resin and 24 parts by weight of styrene-butadiene resin (Cleavrili RICON 100), then adding 70 parts by weight of polyphenylene ether resin SA9000 and 60 parts by weight of acetone, uniformly stirring, then adding 1 part by weight of aminosilane (Nanda-42) and 0.5 part by weight of BIPB, and continuously uniformly stirring to obtain the resin glue solution.
(2) Preparation of prepregs
Impregnating glass fiber cloth (model 2116, thickness 0.08mm) with the above resin glue solution, baking at 150 deg.C for 10min, and removing solvent to obtain prepreg.
(3) Preparation of copper clad laminate
Laminating 6 sheets of the prepared prepreg, respectively laminating 18 mu RTF copper foils on the two outermost sides of the prepreg, and curing in a hot press to obtain the copper-clad laminate, wherein the curing temperature is 200 ℃ and the curing pressure is 40kg/cm2The curing time was 120 min.
Example 2
This example provides a copper clad laminate, which is different from example 1 in that the resin adhesive solution is prepared as follows:
taking a container, adding 50 parts by weight of BDM type bismaleimide and 20 parts by weight of styrene-butadiene resin (Krevillicon 181), then adding 28 parts by weight of methacrylic resin (Sadoma CD535) and 170 parts by weight of toluene, uniformly stirring, then adding 2 parts by weight of aminosilane KBM-903 (Happy chemical) and 0.5 part by weight of BIPB, continuously uniformly stirring, then adding 20 parts by weight of OP935, 10 parts by weight of MELAPUR200 and 200 parts by weight of spherical silica powder (DQ-1028L, Jiangsu Liori), and uniformly mixing and stirring to obtain a resin glue solution.
Example 3
This example provides a copper clad laminate, which is different from example 1 in that the resin adhesive solution is prepared as follows:
taking a container, adding 23 parts by weight of BMI-E type bismaleimide, 20 parts by weight of styrene-butadiene resin (Clrowland RICON 100), 20 parts by weight of styrene-butadiene resin (Clrowland RICON 181), 20 parts by weight of polybutadiene resin (Caoda B3000) and 10 parts by weight of polybutadiene resin (Caoda B2000), then adding 5 parts by weight of methacrylic resin (Clrowland RICACRYL 3500) and 75 parts by weight of toluene, stirring uniformly, then adding 2 parts by weight of aminosilane KBM-903 (Happy chemical) and 0.1 part by weight of BIPB, continuing stirring uniformly, then adding 25 parts by weight of XP7866 and 50 parts by weight of spherical silicon powder (DQ-1028L, Jiangsu alli), mixing and stirring uniformly to obtain a resin glue solution.
Example 4
This example provides a copper clad laminate, which is different from example 1 in that the resin adhesive solution is prepared as follows:
taking a container, adding 37 parts by weight of BMI-E type bismaleimide, 55 parts by weight of styrene-butadiene resin (Cleavrili RICON 100) and 100 parts by weight of dimethylbenzene, uniformly stirring, adding 8 parts by weight of aminosilane KBM-603 (Happy chemistry) and 0.2 part by weight of BIPB, continuously uniformly stirring, adding 30 parts by weight of Uniplex FRP-64P and 100 parts by weight of spherical silica powder (DQ-1028L, Jiangsu Biry), uniformly mixing and stirring to obtain a resin glue solution.
Example 5
This example provides a copper clad laminate, which is different from example 1 in that the resin adhesive solution is prepared as follows:
taking a container, adding 20 parts by weight of BMI-E type bismaleimide and 4 parts by weight of KBM-573, pre-reacting for 120min at 120 ℃ under the protection of nitrogen, then adding 100 parts by weight of xylene to dissolve and cooling to room temperature, then adding 30 parts by weight of styrene-butadiene resin (Cleviland RICON 100), 40 parts by weight of polyphenylene ether resin SA9000, 6 parts by weight of methacrylic resin SR368NS, then adding 0.1 part by weight of BIPB to continue stirring uniformly, then adding 20 parts by weight of SAYTEX 8010 and 100 parts by weight of spherical silicon micropowder (DQ-1028L, Jiangsu alli), and mixing and stirring uniformly to obtain a resin glue solution.
Example 6
This example provides a copper clad laminate, which is different from example 1 in that the resin adhesive solution is prepared as follows:
taking a container, adding 40 parts by weight of BDM bismaleimide and 3 parts by weight of aminosilane A-1170, pre-reacting for 120min at 120 ℃ under the protection of nitrogen, then adding 150 parts by weight of butanone to dissolve, cooling to room temperature, then adding 35 parts by weight of polybutadiene resin B3000, then adding 11 parts by weight of methacrylic resin (sartomera CD535) and 11 parts by weight of polyphenylene ether resin SA9000, then adding 0.4 part by weight of BIPB to continue stirring uniformly, then adding 30 parts by weight of BT-93W and 200 parts by weight of spherical silicon micropowder (DQ-1028L, Jiangsu birui) to mix and stir uniformly to obtain a resin glue solution.
Example 7
This example provides a copper clad laminate, which is different from example 1 in that the resin adhesive solution is prepared as follows:
taking a container, adding 40 parts by weight of BMI-E type bismaleimide and 6 parts by weight of aminosilane A-1130, pre-reacting for 120min at 120 ℃ under the protection of nitrogen, then adding 200 parts by weight of butanone to dissolve, cooling to room temperature, then adding 50 parts by weight of polybutadiene resin B2000, then adding 4 parts by weight of methacrylic resin SR295NS, then adding 1 part by weight of BIPB, continuously stirring uniformly, then adding 30 parts by weight of E3000 and 300 parts by weight of spherical silica powder (DQ-1028L, Jiangsu Murray), and mixing and stirring uniformly to obtain a resin glue solution.
Example 8
This example provides a copper clad laminate, which is different from example 4 in that the resin adhesive solution is prepared as follows:
taking a container, adding 37 parts by weight of BMI-E type bismaleimide and 8 parts by weight of aminosilane KBM-603 (Happy chemical), pre-reacting for 120min at 120 ℃ under the protection of nitrogen, then adding 100 parts by weight of toluene to dissolve and cooling to room temperature, then adding 55 parts by weight of styrene-butadiene resin (Cleviland RICON 100), then adding 0.2 part by weight of BIPB to continue stirring uniformly, then adding 30 parts by weight of Uniplex FRP-64P and 100 parts by weight of spherical silica powder (DQ-1028L, Jiangsu Lifei) to mix and stir uniformly to obtain a resin glue solution.
The copper clad laminates provided in examples 1-8 above were tested for their performance and the results are shown in table 2 below:
TABLE 2
Figure BDA0002331864810000161
Figure BDA0002331864810000171
The test method for the above properties is as follows:
(1) phase separation:
size of phase separation: observed by SEM, the maximum size of the resin agglomeration or phase separation is marked as the size of phase separation.
Figure BDA0002331864810000172
Figure BDA0002331864810000181
(2) Glass transition temperature (T)g): measured according to the DMA test method specified by IPC-TM-6502.4.24;
(3) dielectric constant (D)k) And dielectric dissipation factor (D)f): testing according to the SPDR method;
(4) t300 (with copper): the copper clad laminate is provided with copper on two sides to prepare a sample of 6.35mm multiplied by 6.35mm, the sample is measured according to the test method specified by IPC-TM-6502.4.24.1, and the time of layering and board explosion is recorded. When the time is more than 120min, stopping the test, and recording that T300 (with copper) is more than 120 min;
(5) t330 (with copper): copper is carried on two sides of the copper-clad plate to prepare a sample of 6.35mm multiplied by 6.35mm, the sample is processed according to the testing method specified by IPC-TM-6502.4.24.1, the temperature is increased to 330 ℃ for measurement according to the method, the temperature is kept, the time for layering and plate explosion is recorded, when the time is more than 120min, the test is stopped, and T330 (with copper) is recorded for more than 120 min.
Examples 9 to 15
Examples 9 to 15 each provide a copper clad laminate, differing from example 5 only in the kind and amount of raw materials in the resin paste. The raw material types, amounts (parts by weight) and performance data for examples 9-15 are shown in Table 3 below:
TABLE 3
Figure BDA0002331864810000182
Figure BDA0002331864810000191
Comparative examples 1 to 7
Comparative examples 1 to 7 each provide a copper clad laminate differing from examples 9 to 15 only in that aminosilane is replaced with another kind of silane. The raw material types, amounts (parts by weight) and performance data of comparative examples 1 to 7 are shown in table 4 below:
TABLE 4
Figure BDA0002331864810000201
Figure BDA0002331864810000211
Comparative example 8
There is provided a copper clad laminate, which is different from example 9 in that a resin having at least two maleimide functional groups is not added as component C.
Comparative example 9
There is provided a copper clad laminate, which is different from example 12 in that a resin having at least two maleimide functional groups is not added as component C.
Comparative example 10
There is provided a copper clad laminate, which is different from example 11 in that the modified or unmodified polyolefin resin of component B is added in an amount of 10 parts by weight.
Comparative example 11
A copper clad laminate was provided which differs from example 14 in that no aminosilane, component a, was added.
Comparative example 12
A copper clad laminate was provided, which was different from example 14 in that the aminosilane of component a was added in an amount of 0.5 part by weight.
Comparative example 13
A copper clad laminate was provided, which was different from example 14 in that the aminosilane of component a was added in an amount of 10 parts by weight.
Comparative example 14
The difference between the copper-clad laminate and the embodiment 13 is that in the resin glue solution preparation process, the component A aminosilane does not pre-react with the component C resin containing at least two maleimide functional groups, but is firstly mixed with the filler in a high-speed mixer at the rotating speed of 300r/min at the temperature of 90 ℃ for 1h, the surface of the filler is activated, and then the surface-activated filler is mixed with other components to prepare the resin glue solution.
Comparative example 15
The copper-clad laminate is different from the copper-clad laminate in example 14 in that the addition amount of component A aminosilane is 0.5 part by weight, and in the preparation process of a resin glue solution, the component A aminosilane does not pre-react with the component C resin containing at least two maleimide functional groups, but is firstly mixed with a filler in a high-speed mixer at the rotating speed of 300r/min at the temperature of 90 ℃ for 1 hour, the surface of the filler is activated, and then the filler after surface activation is mixed with other components to prepare the resin glue solution.
The types of raw materials, amounts (parts by weight) and performance data of comparative examples 8-14 are shown in table 5 below:
TABLE 5
Figure BDA0002331864810000221
Figure BDA0002331864810000231
As can be seen from the test results of the above tables 2 and 3, copper-clad laminates prepared using the thermosetting resin compositions provided by the present inventionThe foil laminate has good dielectric properties and a high glass transition temperature without phase separation. The glass transition temperature of the copper clad laminate prepared by the thermosetting resin composition reaches 205-275 ℃, and the dielectric constant D isk(10G) 3.5-4.2, dielectric loss factor Df(10G) 0.0038 to 0.0053, no blistering delamination and popping phenomenon occurs in a T300 (with copper) test, and the aminosilane of the component A and the resin of the component C containing at least two maleimide functional groups are pre-reacted first, so that the prepared copper clad laminate has no blistering delamination and popping phenomenon in a T330 (with copper) test, wherein the T330 is obviously larger than that without pre-reaction, and the phase separation overall performance is better than that without pre-reaction.
As can be seen from the test results in Table 4, compared to examples 9 to 15, comparative examples 1 to 7 employ other types of silanes instead of aminosilane, so that the resulting copper clad laminates still have significant phase separation and are prone to delamination and board explosion.
As can be seen from the test results of Table 5, comparative examples 8 and 9 resulted in a copper clad laminate T having no addition of component C containing a resin having at least two maleimide functional groups, as compared with examples 9 and 12gLow, insufficient heat resistance, and phase separation, resulting in significant decreases in T300 (with copper) and T330 (with copper).
In comparative example 10, the dielectric loss of the resulting copper clad laminate was significantly increased compared to example 11 because the amount of the modified or unmodified polyolefin resin of component B was too small.
Compared with example 14, in comparative example 11, because the component A amino silane is not added, and in comparative example 12, because the addition amount of the component A amino silane is too small, the obtained copper clad laminate has obvious phase separation, and delamination and board explosion are easy to occur. Comparative example 13 since the aminosilane as component A was added in an excessive amount, T of the resulting copper clad laminate wasgThe heat resistance is remarkably insufficient although almost no phase separation is caused.
In comparison with example 13, comparative example 14, although aminosilane was added, the resulting copper clad laminate still had a weak phase separation, with T330 much lower than that after pre-reaction, because it was used for surface activation of the filler, not for reaction with the resin having at least two maleimide functional groups of component C. In comparison with example 14, comparative example 15, which contains aminosilane, still has significant phase separation and is prone to delamination and board explosion because of its use in surface activation of the filler and its small amount.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The thermosetting resin composition is characterized by comprising the following components in parts by weight:
and (2) component A: 1-8 parts of aminosilane;
and (B) component: 20-70 parts by weight of modified or unmodified polyolefin resin;
and (3) component C: 5-50 parts by weight of a resin containing at least two maleimide functional groups;
and a component D: 0-70 parts by weight of an acrylic or methacrylic end-capped resin;
and the total amount of the component A, the component B, the component C and the component D is 100 parts by weight.
2. The thermosetting resin composition according to claim 1, wherein the aminosilane is contained in an amount of 2 to 6 parts by weight based on 100 parts by weight of the total amount of the component a, the component B, the component C, and the component D;
preferably, the preparation method of the thermosetting resin composition is as follows: the aminosilane is pre-reacted with the resin containing at least two maleimide functional groups, and then is mixed with other components;
preferably, the temperature of the pre-reaction is 100-150 ℃, and the time is 30-180 min;
preferably, the modified or unmodified polyolefin resin is selected from one or a combination of at least two of polybutadiene, butadiene-styrene copolymer, epoxidized polybutadiene resin, hydroxyl-modified polybutadiene resin, maleic anhydride-modified polybutadiene, maleic anhydride-modified styrene-butadiene copolymer, and olefin-modified polyphenylene ether resin.
3. The thermosetting resin composition according to claim 1 or 2, wherein the resin containing at least two maleimide functional groups has a structure represented by the following formula I:
Figure FDA0002331864800000011
wherein m is a positive integer greater than 1, and X is selected from
Figure FDA0002331864800000021
Figure FDA0002331864800000022
Figure FDA0002331864800000031
Figure FDA0002331864800000032
Any one of the above;
wherein a is a positive integer of 1-20, R4Is phenyl or alkyl with 1-4 carbon atoms, and represents the access position of the group.
4. The thermosetting resin composition of any of claims 1-3, wherein the acrylic or methacrylic terminated resin has the structure of formula II:
Figure FDA0002331864800000033
wherein n is a positive integer of 1-6, R1Is methyl or a hydrogen atom, Y is selected from
Figure FDA0002331864800000034
Polybutadiene chain, butadiene-styrene copolymer chain, straight-chain alkyl group having 6 to 18 carbon atoms,
Figure FDA0002331864800000035
Figure FDA0002331864800000041
Any one of the above;
n1 and n2 are positive integers, and n1+ n2 is 10-20;
r2 is
Figure FDA0002331864800000042
Figure FDA0002331864800000043
Figure FDA0002331864800000044
Represents the access position of the group.
5. The thermosetting resin composition according to any one of claims 1 to 4, further comprising a component E: a filler;
preferably, the filler is added in an amount of 1 to 300 parts by weight, preferably 20 to 300 parts by weight, more preferably 20 to 200 parts by weight, and particularly preferably 30 to 100 parts by weight, based on 100 parts by weight of the total amount of the component a, the component B, the component C, and the component D;
preferably, the filler is an inorganic filler and/or an organic filler;
preferably, the inorganic filler is selected from any one or a mixture of at least two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate and inorganic phosphorus, preferably any one or a mixture of at least two of crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talc, calcium silicate, calcium carbonate and mica;
preferably, the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, an organic phosphonium salt compound and polyether sulfone powder;
preferably, the median particle size of the filler is 0.01-50 μm, preferably 0.01-20 μm, and more preferably 0.1-10 μm;
preferably, the thermosetting resin composition further comprises component F: a free radical initiator;
preferably, the addition amount of the radical initiator is 0.01 to 6 parts by weight, preferably 0.1 to 2 parts by weight, and further preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the total amount of the component A, the component B, the component C and the component D;
preferably, the free radical initiator is selected from any one of organic peroxide, carbon-based free radical initiator and azo free radical initiator or a mixture of at least two of the organic peroxide, the carbon-based free radical initiator and the azo free radical initiator;
preferably, the thermosetting resin composition further comprises component G: a flame retardant;
preferably, the flame retardant is added in an amount of 1 to 30 parts by weight, based on 100 parts by weight of the total amount of the component A, the component B, the component C and the component D;
preferably, the flame retardant is a halogen-free flame retardant and/or a halogenated flame retardant;
preferably, the halogen-free flame retardant is one or a mixture of at least two of phosphorus flame retardant, P-N flame retardant, nitrogen flame retardant, metal oxide, metal hydroxide, organosilicon flame retardant and halogen-free flame retardant synergist;
preferably, the phosphorus-based flame retardant is selected from any one or a mixture of at least two of tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a phenoxyphosphazene compound, a phosphate ester, a polyphosphate ester, a polyphosphonate ester, and a phosphonate-carbonate copolymer;
preferably, the P-N series flame retardant is selected from one or a mixture of at least two of melamine polyphosphate, melamine phosphonate, ammonium polyphosphate and polyphosphazene;
preferably, the nitrogen-based flame retardant melamine cyanurate;
preferably, the halogenated flame retardant is selected from one or a mixture of at least two of brominated triazine, brominated polystyrene, polybrominated styrene, brominated SBS, brominated styrene-butadiene resin, brominated polybutadiene, polydibromophenyl ether, decabromodiphenylethane, tetrabromophthalic anhydride and ethylenebistetrabromophthalimide.
6. A prepreg comprising a reinforcing material and the thermosetting resin composition according to any one of claims 1 to 5 attached to the reinforcing material after drying by impregnation.
7. A resin film obtained by post-curing the resin composition according to any one of claims 1 to 5 after baking and heating.
8. An adhesive-backed copper foil, which is obtained by applying the resin composition according to any one of claims 1 to 5 to a copper foil or a PI film of a PI film-coated copper foil and forming a semi-cured state by heating.
9. A laminate comprising one or at least two superimposed prepregs according to claim 6.
10. A metal-clad laminate comprising one or at least two stacked prepregs according to claim 6, and a metal foil clad to one or both sides of the one prepreg or the stacked prepregs.
CN201911342697.XA 2019-12-23 2019-12-23 Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same Active CN113088061B (en)

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