CN112250865B - Modified maleimide resin prepolymer, preparation method thereof, resin composition, prepreg, laminated board and printed circuit board - Google Patents
Modified maleimide resin prepolymer, preparation method thereof, resin composition, prepreg, laminated board and printed circuit board Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/125—Unsaturated polyimide precursors the unsaturated precursors containing atoms other than carbon, hydrogen, oxygen or nitrogen in the main chain
-
- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
-
- 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
- B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
- B32B2379/08—Polyimides
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention provides a modified maleimide resin prepolymer, which is prepared by prepolymerization of at least a maleimide compound and an allyl compound, wherein the allyl compound comprises a siloxy allyl compound shown as a structural formula (1) and/or a siloxy propenyl compound shown as a structural formula (2). Compared with the prior art, the silicon-oxygen group is introduced into the maleimide resin system, the maleimide compound is modified mainly by the allyl compound with the silicon-oxygen group at the terminal, the silicon-oxygen bond has better flexibility and heat resistance, and plays a certain role in absorbing stress in the resin composition, so that the better heat resistance and high-temperature modulus value are maintained, and the water absorption, toughness and low CTE of the bismaleimide resin system are further improved; in addition, the steric effect of the group containing siloxane at the tail end is larger than that of hydroxyl, so that the room-temperature storage period of the modified resin, the resin composition and the prepared prepreg is greatly prolonged.
Description
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to a modified maleimide resin prepolymer and a preparation method thereof, a resin composition with the modified maleimide resin prepolymer, and a prepreg, a laminated board and a printed circuit board with the resin composition.
Background
In recent years, with the rapid development of mobile internet technology, high Density Interconnect (HDI) electronic products have been more demanding on their printed circuit board substrates, and in addition to their high heat resistance, peeling resistance and excellent flame retardancy, they are also demanding lower water absorption, dielectric constant/loss value and thermal expansion coefficient.
Bismaleimide resins have excellent heat resistance, peel resistance and high modulus, and are therefore widely used in high performance printed circuit boards. However, unmodified bismaleimides have poor solubility, high crosslinking density, and brittle curability, and are difficult to use alone, and thus, they are required to be modified with a modifier before use. The common modification method is to modify it with aromatic diamine compound (such as DDM, DDE, DDS, etc.) or allyl compound, to destroy the crystal structure, and to improve the solubility and toughness. The product modified by the aromatic diamine compound modified bismaleimide has a certain degree of improvement in the aspects of solubility and toughness, but the aromatic diamine has high toxicity, the modified product can only be dissolved in a polar solvent with a high boiling point (such as DMF, NMP and the like), and meanwhile, a large promotion space still exists in the aspects of toughness and cohesiveness. Furthermore, the solubility (easy to be dissolved in low-boiling point solvents such as PM, butanone, acetone, etc.) and the adhesiveness of the allyl compound bismaleimide compound are further improved compared with those of aromatic diamine compounds, but the allyl compound bismaleimide compound still has the defects in the aspects of heat resistance, toughness, low thermal expansion, water absorption rate, etc., and is difficult to meet the application requirements of high-performance packaging substrates and high-speed high-frequency substrates, and the modified resin or the prepared prepreg has the phenomenon of short storage period, and often does not exceed 30 days at normal temperature.
In order to solve the above-mentioned technical problems, the prior art has been to add polysiloxane (silicone oil), which can effectively reduce CTE, water absorption and flame retardancy of the substrate material. However, the compatibility of the polysiloxane having a large molecular weight with a compound such as bismaleimide resin is poor; low molecular weight polysiloxanes are very prone to bleed during curing due to their low viscosity, poor reactivity, or even little reactivity.
CN 100460431C discloses a hydrogen-containing terminated polysiloxane toughening modified allyl linear phenolic/bismaleimide resin, which plays a good toughening role, but does not mention the influence of the introduction of organic siloxane on the aspects of system flame retardant performance, water absorption and the like.
Therefore, in view of the problems in the prior art, there is a need to provide a modified maleimide prepolymer, a method for preparing the same, a resin composition prepared using the modified maleimide prepolymer, and a prepreg, a laminate and a printed circuit board having the same.
Disclosure of Invention
The invention aims to provide a modified maleimide prepolymer and a preparation method thereof, a resin composition prepared by using the modified maleimide prepolymer, and a prepreg, a laminated board and a printed circuit board with the resin composition.
In order to realize the purposes of the invention, the invention adopts the following technical scheme:
a modified maleimide resin prepolymer is prepared by prepolymerization of at least maleimide compound and allyl compound, wherein the allyl compound contains siloxy allyl compound shown in structural formula (1) and/or siloxy propenyl compound shown in structural formula (2),
structural formula (1)
Structural formula (2)
Wherein R is
、
、
、
Or
(ii) a R1, R2, R3 and R4 are the same or different and are selected from C1-C5 alkyl; x is selected from C1-C5 alkyl or a reactive group, and n is an integer of 1-10.
In a further improvement of the present invention, the reaction molar ratio of the maleimide compound to the allyl compound is from 100 to 10 to 100.
As a further improvement of the invention, the allyl compound also comprises at least one of diallyl bisphenol A, diallyl bisphenol S, allyl phenolic oxygen resin, allyl phenolic resin or diallyl diphenyl ether, and the content of the allyl compound is 10-90 parts by weight based on 100 parts by weight of the total allyl compound.
As a further improvement of the present invention, the maleimide compound is a compound containing at least 1 imide ring group represented by the structural formula (3) in one molecular structure:
wherein R5 is hydrogen or C1-C5 alkyl.
As a further improvement of the invention, the maleimide compound is a bismaleimide compound represented by the structural formula (4):
structural formula (4)
Wherein, R group is selected from one of the following structural formulas:
(a) 
、(b) 
、(c) 
、(d) 
、(e) 
、(f) 
、(g)
、（h）
、（i）
。
accordingly, the present invention provides a method for preparing a modified maleimide resin prepolymer, comprising the steps of:
prepolymerization is carried out on maleimide compound and 10-100 weight portions of allyl compound, wherein the allyl compound contains siloxy allyl compound shown as structural formula (1) and/or siloxy propenyl compound shown as structural formula (2),
structural formula (1)
Structural formula (2)
Wherein R is
、
、
、
Or
(ii) a R1, R2, R3 and R4 are the same or different and are selected from C1-C5 alkyl; x is selected from C1-C5 alkyl or a reactive group, and n is an integer of 1-10.
As a further improvement of the invention, the maleimide compound and the allyl compound are mixed, heated to 50-180 ℃, kept in a stirring condition for reaction for 20-180min, and cooled to room temperature to obtain the allyl compound modified maleimide resin prepolymer.
As a further improvement of the invention, the allyl compound also comprises at least one of diallyl bisphenol A, diallyl bisphenol S, allyl phenol-oxygen resin, allyl phenolic resin or diallyl diphenyl ether, and the content is 10-90 parts by weight based on 100 parts by weight of the total allyl compound.
As a further improvement of the present invention, the maleimide compound is a compound containing at least 1 imide ring group represented by the structural formula (3) in one molecular structure:
wherein R5 is hydrogen or C1-C5 alkyl;
or, the maleimide compound is a bismaleimide compound represented by structural formula (4):
structural formula (4)
Wherein, R group is selected from one of the following structural formulas:
(a) 
、(b) 
、(c) 
、(d) 
、(e) 
、(f) 
、(g)
、（h）
、（i）
。
accordingly, the present invention also provides a resin composition comprising, by weight:
the modified maleimide prepolymer of any one of the above: 10-100 parts;
additive: 1-100 parts; the additive comprises at least one of flame retardant, filler and elastomer.
Further, the filler is an organic filler or an inorganic filler, wherein the inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt or inorganic phosphorus; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
Further, the additive includes a filler in an amount of 0 to 200 parts by weight based on 100 parts by weight of the resin composition.
The flame retardant is at least one of a bromine flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organosilicon flame retardant, an organic metal salt flame retardant and an inorganic flame retardant.
Further, the elastomer is selected from at least one of styrene-butadiene copolymer, poly (meth) acrylate polymer, butadiene-acrylonitrile copolymer, polyurethane elastomer.
Further, the resin composition also comprises 0~5 parts of other auxiliary agents.
Correspondingly, the invention also provides a prepreg, which is prepared by adding a solvent into the resin composition to dissolve the resin composition to prepare a glue solution, dipping the reinforcing material into the glue solution, and heating and drying the dipped reinforcing material.
Correspondingly, the invention also provides a laminated plate, wherein the laminated plate can be obtained by coating metal foil on one side or two sides of at least one prepreg and performing hot press forming.
Correspondingly, the invention also provides a circuit board, which at least comprises the prepreg and/or the laminated board.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
in the invention, silicon oxygen group is introduced into the maleimide resin system, and the maleimide compound is modified mainly by the allyl compound with the silicon oxygen group at the terminal, so that the silicon oxygen bond has better flexibility and heat resistance and plays a certain role in absorbing stress in the resin composition, thereby keeping better heat resistance and high-temperature modulus value and further improving the water absorption, toughness and low CTE of the bismaleimide resin system; in addition, the steric effect of the group containing siloxane at the tail end is larger than that of hydroxyl, so that the room-temperature storage period of the modified resin, the resin composition and the prepared prepreg is greatly prolonged.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments. These embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to these embodiments are included in the scope of the present invention.
The term "comprising" or "containing" in the present specification means that other components capable of imparting different properties to the resin composition may be contained in addition to the components.
The modified maleimide resin prepolymer of the invention is prepared by pre-polymerizing at least a maleimide compound and an allyl compound, wherein the allyl compound comprises a siloxy-containing allyl compound shown as a structural formula (1) and/or a siloxy-containing propenyl compound shown as a structural formula (2),
structural formula (1)
Structural formula (2)
Wherein R is
、
、
、
Or
To biphenyl);
r1, R2, R3 and R4 are the same or different and are respectively selected from C1-C5 alkyl;
x is selected from C1-C5 alkyl or a reactive group, preferably, when X is C1-C5 alkyl, it is selected from methyl, ethyl, propyl or tert-butyl; when X is a reactive group, it is selected from a group containing an epoxy group, an amino group, a mercapto group, a hydroxyl group, a vinyl group or an allyl group; more preferably, X is methyl or ethyl;
n is an integer of 1 to 10.
The reaction molar ratio of the maleimide compound to the allyl compound is 100.
The allyl compound also comprises at least one of diallyl bisphenol A, diallyl bisphenol S, allyl phenol-oxygen resin, allyl phenol-formaldehyde resin or diallyl diphenyl ether, and the content is 10-90 parts by weight based on 100 parts by weight of the total allyl compound.
The maleimide compound is a compound containing at least 1 imide ring group represented by the structural formula (3) in one molecular structure:
wherein R5 is hydrogen or C1-C5 alkyl.
Preferably, the maleimide compound is a bismaleimide compound represented by the structural formula (4):
structural formula (4)
Wherein, R group is selected from one of the following structural formulas:
(a) 
、(b) 
、(c) 
、(d) 
、(e) 
、(f) 
、(g)
、（h）
、（i）
。
the modified maleimide resin prepolymer of the present invention is prepared by the following process, but is not limited thereto.
A method for preparing a modified maleimide resin prepolymer, comprising the steps of: prepolymerization is carried out on maleimide compound and 10-100 weight portions of allyl compound, wherein the allyl compound contains siloxy allyl compound shown as structural formula (1) and/or siloxy propenyl compound shown as structural formula (2).
Specifically, the maleimide compound and the allyl compound are mixed, heated to 50-180 ℃, kept under stirring conditions, reacted for 20-180min, and cooled to room temperature to obtain the allyl compound modified maleimide resin prepolymer.
The present invention also provides a resin composition comprising, by weight:
the above-described modified maleimide prepolymer: 10-100 parts;
additive: 1-100 parts.
Wherein, the additive is at least one of flame retardant, filler and elastomer.
The elastomer is selected from at least one of styrene-butadiene copolymer, poly (methyl) acrylate polymer, butadiene-acrylonitrile copolymer and polyurethane elastomer. By adding the elastomer, the toughness of the resin composition is improved, and the thermal expansion coefficient is lower.
The flame retardant is at least one of a bromine flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organosilicon flame retardant, an organic metal salt flame retardant and an inorganic flame retardant.
Wherein the bromine flame retardant can be decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalimide; the phosphorus-based flame retardant may be inorganic phosphorus, a phosphate compound, a phosphoric acid compound, a hypophosphorous acid compound, a phosphorus oxide compound, 9,10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10- (2,5 dihydroxyphenyl) -9,10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ),
(m is an integer of 1 to 5),
Organic phosphorus-containing compounds such as 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2,6 dimethylphenyl) phosphorus, phosphazene, and modified phosphazene; the nitrogen flame retardant may be a triazine compound, a cyanuric acid compound, an isocyanic acid compound, phenothiazine, or the like; the organic silicon flame retardant can be organic silicon oil, organic silicon rubber, organic silicon resin and the like; the organic metal flame retardant may be ferrocene, acetylacetone metal complex,Organometallic carbonyl compounds, and the like. The inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, or the like.
Of course, the type of flame retardant is not limited thereto, and it will be appreciated that the flame retardant to be added may be selected according to the particular application of the laminate, e.g. the application where halogen is required, preferably a non-halogen flame retardant, e.g. a phosphorus or nitrogen containing flame retardant, more preferably a phosphazene (e.g. trade mark SPB-100), DOPO or DOPO-HQ, a modified phosphazene (e.g. trade mark BP-PZ, PP-PZ, SPCN-100, SPV-100 and SPB-100L), or combinations thereof,
Or
。
Preferably, the flame retardant is a high melting point phosphorus-containing flame retardant,
such as
Or
。
The filler is an organic filler or an inorganic filler, wherein the inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt or inorganic phosphorus; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
Preferably, the inorganic filler is at least one selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
More preferably, the filler is silica, in particular, spherical silica which has been surface-treated, wherein the surface-treating agent is a silane coupling agent such as a silane coupling agent containing an epoxy group, an amino group, a vinyl group, an acrylate group or an allyl group.
When the additive includes a filler, the filler is contained in an amount of 0 to 200 parts by weight based on 100 parts by weight of the resin composition, i.e., the resin composition may or may not contain the filler.
When a filler is contained in the resin composition, the filler is preferably contained in an amount of 10 to 100 parts by weight, more preferably 30 to 70 parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, or 200 parts by weight, based on 100 parts by weight of the resin composition; and the particular points between the above numerical values, are not intended to be exhaustive or to be in a concise sense and the invention is not intended to be exhaustive of the particular points included in the range.
The filler has a median particle size value of 0.3 to 15 μm, for example 0.5 μm, 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, and the particular values therebetween are not exhaustive and are not intended to include the particular values in the ranges disclosed herein, limited to space and in the interest of brevity.
Preferably, the filler has a median particle size of from 1 to 5 μm.
In the invention, the resin composition also comprises 0~5 parts of other auxiliary agents according to different requirements of final products, and the other auxiliary agents comprise a coupling agent, a dispersing agent and a dye. The coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent; the dispersant is amino silane compound having amino group and having hydrolytic group or hydroxyl group such as gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, epoxy silane compound having epoxy group and having hydrolytic group or hydroxyl group such as 3-acryloxypropyltrimethoxysilane, vinyl silane compound having vinyl group and having hydrolytic group or hydroxyl group such as gamma-methacryloxypropyltrimethoxysilane, and cationic silane coupling agent, and the dispersant can be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, W903 (all product names) manufactured by BYK; the dye is a fluorescent dye and a black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is carbon black (liquid or powder), a pyridine complex, an azo complex, aniline black, black talcum powder, cobalt chromium metal oxide, azine, phthalocyanine and the like.
The invention also provides a prepreg, the resin composition is dissolved by a solvent, uniformly stirred and cured to prepare a resin composition glue solution, the reinforcing material is soaked in the resin composition glue solution, then the soaked reinforcing material is baked for 1-10min at the temperature of 50-170 ℃, and the prepreg can be obtained after drying.
Wherein the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric; preferably, the reinforcing material is glass fiber cloth, and open fiber cloth or flat cloth is preferably used in the glass fiber cloth. In addition, when the reinforcing material is a glass cloth, the glass cloth generally needs to be chemically treated to improve the interface between the resin composition and the glass cloth. The main method of the chemical treatment is a coupling agent treatment. The coupling agent used is preferably an epoxy silane, an aminosilane or the like to provide good water resistance and heat resistance.
The invention also provides a laminated board prepared by adopting the prepreg, which comprises the following preparation steps:
and covering a metal foil on one or two sides of one prepreg, or covering a metal foil on one or two sides of at least 2 prepregs after laminating, and carrying out hot press forming to obtain the metal foil laminated board.
The pressing conditions of the above laminate were: pressing for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
The number of prepregs may be determined according to the thickness of the laminate desired, and one or more prepregs may be used. The metal foil can be copper foil or aluminum foil, and the material is not limited; the thickness of the metal foil is also not particularly limited, and may be, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.
The invention also provides a circuit board, which at least comprises the prepreg and/or the laminated board.
Compared with the prior art, the invention has the following advantages:
according to the invention, a silicon-oxygen group is introduced into a maleimide resin system, and the maleimide compound is modified mainly by an allyl compound containing the silicon-oxygen group at the terminal, so that the silicon-oxygen bond has better flexibility and heat resistance, and plays a certain role in absorbing stress in a resin composition, thereby keeping better heat resistance and high-temperature modulus value, and further improving the water absorption, toughness and low CTE of the bismaleimide resin system; in addition, the steric effect of the group containing siloxane at the tail end is larger than that of hydroxyl, so that the room-temperature storage period of the modified resin, the resin composition and the prepared prepreg is greatly prolonged.
The present invention will be described in detail with reference to specific examples; and the embodiments of the present invention are not limited to these embodiments.
Modified maleimide prepolymer Synthesis example 1:
the modified maleimide prepolymer A is prepared by at least prepolymerizing a maleimide compound and an allyl compound, wherein the allyl compound is a siloxy-containing allyl compound, and the reaction mechanism for preparing the siloxy-containing allyl compound is as follows:
wherein X is methyl, Y is halogen, and n is an integer of 1-5.
Dissolving and dispersing the siloxy-containing allyl compound and maleimide resin in a proper amount of organic solvent, heating to 90-175 ℃ under the protection of nitrogen, and reacting for 20-120min under the condition of keeping stirring to obtain the allyl compound modified bismaleimide prepolymer A.
Modified maleimide prepolymer comparative example 1:
modified bismaleimide prepolymer C
Reacting an allyl bisphenol A compound with a diphenylmethane bismaleimide resin at a ratio of 50 to 100 at 130 to 170 ℃ for 30 to 120min to obtain a modified bismaleimide prepolymer C
The components and contents of the resin compositions of examples 1 to 5 and comparative examples 1 to 2 are shown in the following table 1:
TABLE 1
The detailed specification of the components is as follows:
TABLE 2
| Components | Detailed description of the invention |
| Silicon dioxide | Surface treated silica |
| Catalyst and process for preparing same | 2-methylimidazole |
Example (b):
according to the component contents in Table 1, the modified maleimide prepolymer, the filler, the catalyst and a proper amount of butanone solvent are stirred and mixed uniformly to obtain a glue solution with a solid content of 65 wt%.
The glue solution is dipped and coated on E glass fiber cloth (7628) and is dried in an oven at 160 ℃ for 5min to prepare a prepreg.
Preparation of performance evaluation sample laminates:
and (3) placing 18-micron metal copper foils on the upper prepreg and the lower prepreg respectively, and placing the prepregs in a vacuum hot press for pressing to obtain the laminated board. The specific pressing process is pressing for 4 hours under the pressure of 1.5MPa and the temperature of 180-220 ℃.
The performance evaluation method comprises the following steps:
(1) Glass transition temperature Tg (. Degree. C.): according to differential scanning calorimetry, the measurement was carried out by the DSC method defined by IPC-TM-650.4.25.
(2) Water absorption: the test was carried out according to IPC-TM-650.2.6.2.1.
(3) CTE (X/Y): : TMA test, in which the temperature was raised from room temperature 25 ℃ to 300 ℃ at a temperature raising rate of 10 ℃/min, and the in-plane thermal expansion coefficient was measured at 50 ℃ to 130 ℃.
(4) Semi-curing storage period: the storage is carried out at 25 ℃, the calculation is carried out from the preparation completion date of the prepreg, and the storage period is determined as the time when the substrate defects (white lines, dry flowers and other characteristics) appear on the pressing plate after the prepreg is stored.
The laminate properties obtained are shown in table 3.
TABLE 3
As can be seen from table 3, the resin composition obtained by the technical scheme of the present invention and the prepreg and the laminate prepared from the resin composition have excellent comprehensive properties such as high heat resistance, low water absorption, low thermal expansion coefficient, and the like, and the prepreg has a good shelf life.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (18)
1. A modified maleimide resin prepolymer is prepared by prepolymerization of at least maleimide compound and allyl compound, and is characterized in that the allyl compound comprises siloxy allyl compound shown as a structural formula (1) and/or siloxy propenyl compound shown as a structural formula (2),
structural formula (1)
Structural formula (2)
Wherein R is
、
、
、
Or
(ii) a R1, R2, R3 and R4 are the same or different and are respectively selected from C1-C5 alkyl; x is selected from C1-C5 alkyl, and n is an integer of 1-10.
2. The modified maleimide resin prepolymer according to claim 1, characterized in that: the reaction molar ratio of the maleimide compound to the allyl compound is 100.
3. The modified maleimide resin prepolymer according to claim 1, characterized in that: the allyl compound also comprises at least one of diallyl bisphenol A, diallyl bisphenol S, allyl phenol-oxygen resin, allyl phenolic resin or diallyl diphenyl ether, and the content is 10-90 parts by weight based on 100 parts by weight of the total allyl compound.
4. The modified maleimide resin prepolymer according to claim 1, characterized in that: the maleimide compound is a compound containing at least 1 imide ring group represented by the structural formula (3) in one molecular structure:
wherein R5 is hydrogen or C1-C5 alkyl;
or, the maleimide compound is a bismaleimide compound represented by structural formula (4):
structural formula (4)
Wherein, R group is selected from one of the following structural formulas:
(a) 
、(b) 
、(c) 
、(d) 
、(e) 
、(f) 
、(g) 
、（h）
、（i）
。
5. a method for preparing a modified maleimide resin prepolymer, which is characterized by comprising the following steps: the method comprises the following steps:
prepolymerization is carried out on maleimide compound and 10-100 parts by weight of allyl compound, wherein the allyl compound contains siloxy-containing allyl compound shown as structural formula (1) and/or siloxy-containing propenyl compound shown as structural formula (2),
structural formula (1)
Structural formula (2)
Wherein R is
、
、
、
Or
(ii) a R1, R2, R3 and R4 are the same or different and are selected from C1-C5 alkyl; x is selected from C1-C5 alkyl, and n is an integer of 1-10.
6. The method for producing a modified maleimide resin prepolymer according to claim 5, characterized in that: the method comprises the following steps: mixing maleimide compound and allyl compound, heating to 50-180 ℃, reacting for 20-180min under the condition of keeping stirring, and cooling to room temperature to obtain the allyl compound modified maleimide resin prepolymer.
7. The method for producing a modified maleimide resin prepolymer according to claim 5 or 6, characterized in that: the allyl compound also comprises at least one of diallyl bisphenol A, diallyl bisphenol S, allyl phenol-oxygen resin, allyl phenol-formaldehyde resin or diallyl diphenyl ether, and the content is 10-90 parts by weight based on 100 parts by weight of the total allyl compound.
8. The method for producing a modified maleimide resin prepolymer according to claim 5 or 6, characterized in that: the maleimide compound is a compound containing at least 1 imide ring group represented by the structural formula (3) in one molecular structure:
wherein R5 is hydrogen or C1-C5 alkyl;
or, the maleimide compound is a bismaleimide compound represented by structural formula (4):
structural formula (4)
Wherein, R group is selected from one of the following structural formulas:
(a) 
、(b) 
、(c) 
、(d) 
、(e) 
、(f) 
、(g) 
、（h）
、（i）
。
9. a resin composition characterized by comprising, by weight:
the modified maleimide prepolymer of any one of claims 1 to 4: 100 parts of a binder;
additive: 1-200 parts;
the additive comprises at least one of a flame retardant, a filler and an elastomer.
10. The resin composition according to claim 9, characterized in that: the filler is an organic filler or an inorganic filler, wherein the inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt or inorganic phosphorus; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
11. The resin composition according to claim 9, characterized in that: the additive comprises a filler, and the content of the filler is 20-180 parts by weight based on 100 parts by weight of the resin composition.
12. The resin composition according to claim 9, characterized in that: the flame retardant is at least one of a brominated flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organic silicon flame retardant, an organic metal salt flame retardant and an inorganic flame retardant.
13. The resin composition according to claim 9, characterized in that: the elastomer is selected from at least one of styrene-butadiene copolymer, poly (methyl) acrylate polymer, butadiene-acrylonitrile copolymer and polyurethane elastomer.
14. The resin composition according to claim 9, characterized in that: the resin composition also comprises 0~5 parts of other auxiliary agents.
15. A prepreg obtained by dissolving the resin composition according to any one of claims 9 to 14 in a solvent to prepare a liquid cement, immersing a reinforcing material in the liquid cement, and heating and drying the immersed reinforcing material.
16. A laminate which is obtained by coating at least one prepreg according to claim 15 on one or both sides with a metal foil and hot-pressing.
17. A wiring board comprising at least the prepreg according to claim 15.
18. A circuit board comprising at least the laminate of claim 16.
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| CN111978547A (en) * | 2020-08-21 | 2020-11-24 | 齐齐哈尔大学 | Imide-bridged polysiloxane gas separation membrane and preparation method thereof |
| CN113185751A (en) * | 2021-04-23 | 2021-07-30 | 艾蒙特成都新材料科技有限公司 | Halogen-free silicon flame-retardant vinyl resin, preparation method thereof and application thereof in copper-clad plate |
| CN113105498A (en) * | 2021-04-23 | 2021-07-13 | 艾蒙特成都新材料科技有限公司 | Halogen-free silicon flame-retardant allyl compound, preparation method thereof and application thereof in copper-clad plate |
| CN114230793B (en) * | 2021-12-30 | 2024-03-29 | 苏州生益科技有限公司 | Modified bismaleimide prepolymer and preparation method and application thereof |
| CN114561101A (en) * | 2022-04-01 | 2022-05-31 | 焦作市天益科技有限公司 | Diallyl bisphenol A modified bismaleimide resin capable of prolonging shelf life and preparation method thereof |
| CN115819458B (en) * | 2022-12-27 | 2023-10-20 | 苏州生益科技有限公司 | Phosphorus-containing epoxy resin, resin composition and application of resin composition |
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