CN114085436A - Glue solution, prepreg, circuit substrate and printed circuit board - Google Patents

Glue solution, prepreg, circuit substrate and printed circuit board Download PDF

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CN114085436A
CN114085436A CN202111471357.4A CN202111471357A CN114085436A CN 114085436 A CN114085436 A CN 114085436A CN 202111471357 A CN202111471357 A CN 202111471357A CN 114085436 A CN114085436 A CN 114085436A
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glue solution
surfactant
weight
parts
reactive group
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CN114085436B (en
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韩梦娜
任英杰
卢悦群
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Hangzhou Wazam New Materials Co ltd
Zhejiang Huazheng New Material Group Co ltd
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Hangzhou Wazam New Materials Co ltd
Zhejiang Huazheng New Material Group 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
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a glue solution, which comprises resin, a filler, a surfactant, a curing agent and an organic solvent, wherein the resin has a first reactive group, and the structural formula of the surfactant is shown as a formula (1):

Description

Glue solution, prepreg, circuit substrate and printed circuit board
Technical Field
The invention relates to the technical field of electronic industry, in particular to glue solution, a prepreg, a circuit substrate and a printed circuit board.
Background
Based on the requirement of a 5G communication application scene on the dielectric property of a circuit substrate, some surfactants are usually added into glue solution in the traditional method to optimize the interfacial tension so as to improve the bonding force, the dispersibility or the compatibility of each phase in the glue solution to improve the dielectric property of the circuit substrate.
However, when the aqueous glue solution is adopted, the temperature is up to over 380 ℃ when the reinforcing materials such as glass fiber cloth and the like are dipped and glued, the surfactant can be decomposed and volatilized, and finally no surfactant residue exists in the circuit substrate synthesized by pressing; however, when an organic solvent system is used, the temperature of the prepreg when the reinforcing material such as glass fiber cloth is dipped and sized is not higher than 200 ℃ and does not reach the decomposition temperature of the surfactant, so that the surfactant remains in the prepreg, and the free surfactant exists in the circuit board to be laminated, thereby affecting the thermal stability and reliability of the circuit board.
Disclosure of Invention
In view of the above, it is necessary to provide a glue solution, a prepreg, a circuit board, and a printed circuit board, wherein the circuit board made of the glue solution has excellent thermal stability and reliability.
A glue solution comprises resin, filler, a surfactant, a curing agent and an organic solvent, wherein a molecular chain of the resin has a first reaction group, and the structural formula of the surfactant is shown as a formula (1):
Figure BDA0003392533710000021
in the formula (1), R is a second reactive group, and the molecular weight of the surfactant is 2000-3500;
wherein the first reactive group is selected from vinyl, epoxy, cyanate ester, amino or acid anhydride, and the second reactive group is selected from vinyl or epoxy.
In one embodiment, in formula (1), m is 12 to 17, n is 4 or 5, x is 1 to 5, y is 6 to 20, and z is 4 to 7.
In one embodiment, the first reactive group and the second reactive group are the same cure system reactive group.
In one embodiment, the contact angle of the glue solution on a molded plate is 0-50 ℃ at 25 +/-1 ℃, wherein the molded plate is made of the filler.
In one embodiment, the resin comprises at least one of polybutadiene, a copolymer of polybutadiene and styrene, polyisoprene, modified polybutadiene, polyphenylene ether, modified polyphenylene ether, polyimide, epoxy resin, modified epoxy resin, cyanate ester, and isocyanate.
In one embodiment, the filler is used in an amount of 150 parts by weight to 350 parts by weight, the surfactant is used in an amount of 0.5 parts by weight to 3 parts by weight, and the curing agent is used in an amount of 1 part by weight to 20 parts by weight, based on 100 parts by weight of the resin.
In one embodiment, the glue solution further comprises a flame retardant.
The prepreg comprises a reinforcing material and the dried glue solution attached to the reinforcing material.
The circuit substrate comprises an insulating layer and a conducting layer arranged on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or at least two overlapped prepregs.
A printed circuit board is made of the circuit substrate.
The glue solution disclosed by the invention adopts the surfactant with the structural formula shown in the formula (1), and the surfactant has a hydrophilic end and a lipophilic end, so that the surfactant can be combined with the filler through the hydrophilic end, and the good compatibility of the lipophilic end with resin and an organic solvent is utilized to uniformly disperse the filler in the glue solution, and meanwhile, the surfactant can provide electrostatic repulsion and steric hindrance and effectively prevent collision and agglomeration among the fillers. Furthermore, the surface tension of the glue solution can be adjusted by the surfactant with the structural formula shown in the formula (1), so that the components in the glue solution can quickly reach a uniformly distributed and stable state in the mixing process, and the glue solution has better gluing manufacturability.
In addition, in the glue solution, the molecular chain of the resin has a first reaction group, and the surfactant with the structural formula shown in formula (1) has a second reaction group, so that the second reaction group in the molecular chain of the surfactant can react with the first reaction group in the molecular chain of the resin in the process of laminating and curing the prepreg into an insulating layer, so that the second reaction group and the first reaction group form chemical combination, and the surfactant can be locked in a cured molecular network in a chemical combination manner to avoid dissociating in a circuit substrate, so that the thermal stability and reliability of the circuit substrate can be effectively improved.
Detailed Description
The glue solution, prepreg, circuit board and printed circuit board provided by the invention will be further explained below.
The glue solution provided by the invention comprises resin, a filler, a surfactant, a curing agent and an organic solvent.
Wherein the resin has a first reactive group selected from a vinyl group, an epoxy group, a cyanate group, an amino group, or an acid anhydride.
Optionally, the resin includes at least one of polybutadiene, copolymer of polybutadiene and styrene, polyisoprene, modified polybutadiene, polyphenylene oxide, modified polyphenylene oxide, polyimide, epoxy resin, modified epoxy resin, cyanate ester, and isocyanate.
Optionally, the filler comprises at least one of titanium dioxide, barium titanate, strontium titanate, silica, corundum, wollastonite, solid glass microspheres, synthetic glass, quartz, boron nitride, aluminum nitride, silicon carbide, aluminum carbide, beryllium oxide, aluminum hydroxide, magnesium oxide, mica, talc, or magnesium hydroxide.
The structural formula of the surfactant is shown as a formula (1):
Figure BDA0003392533710000041
in the formula (1), R is a second reactive group selected from a vinyl group or an epoxy group.
In order to make the surfactant have better compatibility in the glue solution, the molecular weight of the surfactant shown in the formula (1) is preferably 2000-3500.
In the surfactant represented by the formula (1), m, n, x, y and z are not limited, and the effect of the surfactant in use is not affected.
Since the more x and m, the better the lipophilicity of the surfactant, the more z and n, the better the hydrophilicity of the surfactant, the larger m and n, the longer the branch, the higher the degree of freedom of the surfactant, but also the lower the thermal stability and compatibility, and the more y, the better the reactivity of the surfactant, but too large also the lower the compatibility. Therefore, in the formula (1), m is preferably an integer of 12 to 17, n is preferably 4 or 5, x is preferably an integer of 1 to 5, y is preferably an integer of 6 to 20, and z is preferably an integer of 4 to 7, so that the molecular weight of the surfactant is in the range of 2000-3500, and at the same time, excellent thermal stability and compatibility are exhibited.
Taking the second reactive group as vinyl as an example, the surfactant can be prepared by reacting octadecyl methacrylate, polyethylene glycol methacrylate and 1, 4-pentadiene, and the structural formula is shown as the formula (1-1),
Figure BDA0003392533710000051
it should be noted that when the second reactive group is an epoxy group, the epoxy group can be obtained by directly epoxidizing a vinyl group, for example, the surfactant with the structural formula shown in formula (1-1) is epoxidized to obtain the surfactant with the structural formula shown in formula (1-2).
Figure BDA0003392533710000052
Of course, when the second reactive group is an epoxy group, the surfactant can also be synthesized by a polymerization method.
Optionally, the curing agent comprises at least one of dicyandiamide, diaminodiphenyl sulfone, diaminodiphenylmethane, styrene-maleic anhydride copolymer, phenolic resin, active ester, benzoxazine, 2, 5-dimethyl-2, 5-di (phenylmethyl peroxide) hexane, di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne, dicumyl peroxide.
Optionally, the organic solvent includes at least one of toluene, xylene, butanone, acetone, dichloromethane, N-dimethylformamide, and propylene glycol monomethyl ether.
Optionally, the glue solution further comprises a flame retardant to make the circuit substrate have flame retardant performance, wherein the flame retardant comprises at least one of tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-chloroethyl) phosphate, tris (2, 3-dichloropropyl) phosphate, tris (2, 3-dibromopropyl) phosphate, Pyrol99, tolylene diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, 2-ethylhexyl) diphenyl phosphate, chlordane anhydride, dibromomethane, trichlorobromomethane, dichlorobromomethane, octabromodiphenyl oxide, pentabromoethylbenzene, tetrabromobisphenol a, tris (dibromopropyl) phosphate, halogenated cyclohexane and its derivatives, decabromodiphenyl ether and its derivatives.
Optionally, based on 100 parts by weight of the resin, the filler is used in an amount of 150 to 350 parts by weight, the surfactant is used in an amount of 0.5 to 3 parts by weight, and the curing agent is used in an amount of 1 to 20 parts by weight.
As shown in formula (1), the surfactant adopted in the glue solution disclosed by the invention has a hydrophilic end and a lipophilic end, so that the surfactant can be combined with the filler through the hydrophilic end, and the filler is uniformly dispersed in the glue solution by utilizing the good compatibility of the lipophilic end with resin and an organic solvent, and meanwhile, the surfactant can also provide electrostatic repulsion and steric hindrance, so that collision and agglomeration among the fillers are effectively prevented. Furthermore, the surface tension of the glue solution can be adjusted through the surfactant, so that the components in the glue solution can rapidly reach a uniformly distributed and stable state in the mixing process, and therefore, the glue solution has better manufacturability, and the prepared circuit substrate has excellent thermal stability and reliability.
Optionally, through the selection and the control of the amount of the surfactant, the contact angle of the glue solution on a mould pressing plate is 0-50 degrees, preferably 0-30 degrees at 25 +/-1 ℃, so that the components in the glue solution can be in a uniformly distributed and stable state.
It should be noted that the method for testing the contact angle of the glue solution on the molded plate comprises the following steps: pressing the filler into a mould pressing plate by using a precision press, dripping the glue on the mould pressing plate, and measuring the contact angle at the temperature of 25 +/-1 ℃ by using a contact angle measuring device.
Most importantly, the adhesive solution is an organic solvent system adhesive solution, a first reaction group is arranged in a molecular chain of resin in the adhesive solution, and a second reaction group is arranged in a molecular chain of a surfactant, so that the temperature is below 200 ℃ when reinforcing materials such as glass fiber cloth and the like are dipped and glued in the preparation process of a prepreg, the surfactant cannot be decomposed in the prepreg, and the second reaction group in the molecular chain of the surfactant can react with the first reaction group in the molecular chain of the resin in the process of laminating and curing the prepreg into an insulating layer, so that the second reaction group and the first reaction group form chemical bonding, the surfactant can be locked in a cured molecular network in a chemical bonding mode, and the surfactant is prevented from dissociating in a circuit substrate, and therefore, the thermal stability and the reliability of the circuit substrate can be effectively improved.
In order to make the second reactive group in the molecular chain of the surfactant react with the first reactive group in the molecular chain of the resin better, the first reactive group and the second reactive group are preferably the same curable group of the curing system.
For example, the first reactive group and the second reactive group are both selected from vinyl groups, and in this case, the resin is preferably at least one selected from polybutadiene, a copolymer of polybutadiene and styrene, polyisoprene, and modified polybutadiene.
When the second reactive group is selected from epoxy group, the first reactive group is selected from cyanate group, amino group, acid anhydride or epoxy group, in this case, the resin includes at least one of polyphenylene ether, modified polyphenylene ether, polyimide, epoxy resin, modified epoxy resin, cyanate ester and isocyanate.
The invention also provides a prepreg, which comprises a reinforcing material and the dried glue solution attached to the reinforcing material.
Namely, the glue solution is formed on the reinforcing material in a coating, dipping and other modes, and the organic solvent in the glue solution is removed through drying, so that the prepreg is obtained.
The reinforcing material is used for controlling the curing shrinkage of the circuit substrate in manufacturing and endowing the circuit substrate with certain mechanical strength, and the reinforcing material is preferably glass fiber cloth, including non-woven fabrics or woven fabrics, such as natural fibers, organic synthetic fibers and inorganic fibers, and is preferably electronic grade glass fiber cloth.
The invention also provides a circuit substrate which comprises an insulating layer and a conducting layer arranged on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or at least two overlapped prepregs.
Wherein in the step of pressing, the temperature is 120-250 ℃, and the pressure is 10kg/cm2-80kg/cm2And in the pressing step, the second reaction group in the molecular chain of the surfactant and the first reaction group in the molecular chain of the resin are subjected to chemical reaction, so that the surfactant is locked in a cured molecular network in a chemically combined mode.
It should be noted that the surfactant and the resin in the prepreg partially react, and are completely cured and reacted in the pressing step.
Optionally, the conductive layer is a copper foil, and the circuit substrate is a copper-clad plate.
The invention also provides a printed circuit board which is mainly manufactured by the circuit substrate through the processes of drilling, hole trimming, microetching, presoaking, activating, accelerating, chemical copper, copper thickening and the like.
The glue, prepreg, circuit board, and printed circuit board will be further described with reference to the following specific examples.
In the following examples, the surfactants used are represented by the following formulae (1-1) to (1-2).
Figure BDA0003392533710000091
In formula (1-1), n is 4, x is 2, y is 10, z is 4, and the molecular weight is 2404.
Figure BDA0003392533710000092
In formula (1-2), n is 4, x is 2, y is 10, z is 4, and the molecular weight is 2564.
Example 1
Mixing 100 parts by weight of polybutadiene, 250 parts by weight of silicon dioxide filler, 3 parts by weight of surfactant with a structural formula shown in a formula (1-1) and 5 parts by weight of dicumyl peroxide curing agent, and diluting with a xylene organic solvent to obtain a glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 31 degrees by using a contact angle measuring device at the temperature of 25 ℃.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Example 2
100 parts by weight of polybutadiene and styrene copolymer, 250 parts by weight of silica filler, 2.5 parts by weight of surfactant with a structural formula shown as a formula (1-1) and 4 parts by weight of dicumyl peroxide curing agent are mixed and diluted by a xylene organic solvent to obtain a glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 36 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Example 3
Mixing 100 parts by weight of epoxy resin, 200 parts by weight of silicon dioxide filler, 1.5 parts by weight of surfactant with a structural formula shown as a formula (1-2) and 12 parts by weight of diaminodiphenyl sulfone curing agent, and diluting with butanone organic solvent to obtain glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 40 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Overlapping 4 prepregs, covering copper foils on the upper and lower parts respectively, andat 40kg/cm2Pressing at 200 deg.C for 3 hr to obtain the circuit substrate.
Example 4
Mixing 100 parts by weight of polybutadiene, 320 parts by weight of silicon dioxide filler, 3 parts by weight of surfactant with a structural formula shown in a formula (1-1) and 5 parts by weight of dicumyl peroxide curing agent, and diluting with a xylene organic solvent to obtain a glue solution. Pressing the silica filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 34 degrees by using a contact angle measuring device at the temperature of 25 ℃.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Example 5
Mixing 100 parts by weight of polybutadiene, 150 parts by weight of silicon dioxide filler, 2 parts by weight of surfactant with a structural formula shown in a formula (1-1) and 5 parts by weight of dicumyl peroxide curing agent, and diluting with a xylene organic solvent to obtain a glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 25 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Example 6
Mixing 100 parts by weight of epoxy resin, 180 parts by weight of silicon dioxide filler, 2 parts by weight of surfactant with a structural formula shown as a formula (1-2) and 12 parts by weight of diaminodiphenyl sulfone curing agent, and diluting with butanone organic solvent to obtain glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 30 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 40kg/cm2Pressing at 200 deg.C for 3 hr to obtain the circuit substrate.
Example 7
Mixing 50 parts by weight of epoxy resin, 50 parts by weight of epoxy modified polyphenyl ether, 180 parts by weight of silicon dioxide filler, 2.5 parts by weight of surfactant with a structural formula shown as a formula (1-2) and 8 parts by weight of diaminodiphenyl sulfone curing agent, and diluting with butanone organic solvent to obtain glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 24 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 40kg/cm2Pressing at 200 deg.C for 3 hr to obtain the circuit substrate.
Example 8
70 parts by weight of cyanate ester, 30 parts by weight of epoxy resin, 170 parts by weight of silicon dioxide filler and 2 parts by weight of surfactant with a structural formula shown as a formula (1-2) are diluted by DMF organic solvent to obtain glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 33 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and heating at 50kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Example 9
100 parts by weight of polybutadiene, 250 parts by weight of silica filler, 3 parts by weight of a surfactant (R is vinyl, m is 14, n is 4, x is 2, y is 6, z is 7, and the molecular weight is 2834) having a structural formula shown in formula (1), and 5 parts by weight of dicumyl peroxide curing agent are mixed and diluted with a xylene organic solvent to obtain a glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 32 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Example 10
100 parts by weight of polybutadiene, 250 parts by weight of silica filler, 3 parts by weight of a surfactant having a structural formula shown in formula (1) (wherein R is vinyl, m is 12, n is 5, x is 4, y is 17, z is 4, and the molecular weight is 3452), and 5 parts by weight of dicumyl peroxide curing agent are mixed and diluted with a xylene organic solvent to obtain a glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 31 degrees by using a contact angle measuring device at the temperature of 25 ℃.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
In the following comparative examples, the surfactants used are represented by the following formulae (2) to (3).
Figure BDA0003392533710000131
In formula (2), n is 4, x is 2, y is 10, z is 4, and the molecular weight is 2134.
Figure BDA0003392533710000132
In formula (3), n is 4, x is 2, y is 10, z is 4, and the molecular weight is 2464.
Comparative example 1
100 parts by weight of polybutadiene, 200 parts by weight of silica filler, 2 parts by weight of surfactant with a structural formula shown in formula (2), and 5 parts by weight of dicumyl peroxide curing agent are diluted by a xylene organic solvent to obtain a glue solution. Pressing the silica filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 34 degrees by using a contact angle measuring device at the temperature of 25 ℃.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Comparative example 2
100 parts by weight of polybutadiene and styrene copolymer, 210 parts by weight of silicon dioxide filler, 2.5 parts by weight of surfactant with a structural formula shown in formula (2), and 5 parts by weight of dicumyl peroxide curing agent are diluted by a xylene organic solvent to obtain a glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 32 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Comparative example 3
100 parts by weight of epoxy resin, 200 parts by weight of silicon dioxide filler, 1.5 parts by weight of surfactant with a structural formula shown in a formula (2), 12 parts by weight of diamino diphenyl sulfone curing agent and butanone organic solvent are diluted to obtain glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 41 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 40kg/cm2Pressing at 200 deg.C for 3 hr to obtain the circuit substrate.
Comparative example 4
100 parts by weight of epoxy resin, 180 parts by weight of silicon dioxide filler, 2.5 parts by weight of surfactant with a structural formula shown in a formula (3), 12 parts by weight of diamino diphenyl sulfone curing agent and butanone organic solvent are diluted to obtain glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 24 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 40kg/cm2Pressing at 200 deg.C for 3 hr to obtain the circuit substrate.
Comparative example 5
100 parts by weight of polybutadiene, 250 parts by weight of silica filler and 5 parts by weight of dicumyl peroxide curing agent are diluted by a xylene organic solvent to obtain a glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 68 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Comparative example 6
100 parts by weight of epoxy resin, 180 parts by weight of silicon dioxide filler and 12 parts by weight of diaminodiphenyl sulfone curing agent are diluted by butanone organic solvent to obtain glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 63 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 40kg/cm2Pressing at 200 deg.C for 3 hr to obtain the circuit substrate.
Comparative example 7
100 parts by weight of polybutadiene, 220 parts by weight of silica filler, 1.5 parts by weight of a surfactant having a structural formula shown by formula (1-1) (n-4, x-2, y-2, z-2, molecular weight of 1336) and 5 parts by weight of dicumyl peroxide curing agent were mixed and diluted with xylene organic solvent to obtain a dope. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 52 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Comparative example 8
100 parts by weight of polybutadiene, 220 parts by weight of silica filler, 1.5 parts by weight of a surfactant (n-4, x-2, y-20, z-8, molecular weight 4132) having a structural formula shown in formula (1-1) and 5 parts by weight of dicumyl peroxide curing agent were diluted with a xylene organic solvent to obtain a glue solution. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 48 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Overlapping 4 prepregs one above the otherSpreading the copper foil at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Figure BDA0003392533710000171
Comparative example 9
100 parts by weight of polybutadiene, 220 parts by weight of silica filler, 1.5 parts by weight of a surfactant having a structural formula shown in formula (1) (wherein R is vinyl, m is 20, n is 7, x is 2, y is 10, z is 6, and the molecular weight is 4564), and 5 parts by weight of dicumyl peroxide curing agent were mixed and diluted with a xylene organic solvent to obtain a dope. Pressing the silicon dioxide filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 45 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
Comparative example 10
100 parts by weight of polybutadiene, 220 parts by weight of silica filler, 1.5 parts by weight of a surfactant (R is vinyl, m is 12, n is 4, x is 6, y is 10, z is 8, and the molecular weight is 4384) having a structural formula shown in formula (1), and 5 parts by weight of dicumyl peroxide curing agent are mixed and diluted with a xylene organic solvent to obtain a glue solution. Pressing the silica filler into a mould pressing plate by using a precision press, dripping the obtained glue solution on the mould pressing plate, and measuring the contact angle to be 43 degrees at the temperature of 25 ℃ by using a contact angle measuring device.
And (4) dipping the glue solution by using glass fiber cloth, and removing the organic solvent to obtain the prepreg.
Laminating 4 prepregs, covering copper foils on the upper and lower parts respectively, and keeping the thickness at 60kg/cm2And press-bonding at 230 ℃ for 3 hours to obtain a circuit board.
The glue solutions of examples 1-10 and comparative examples 1-10 and the performance of the prepared circuit substrates were tested, the specific test contents and standards are shown below, and the test results are shown in table 1.
The viscosity was measured using a # 3 zeitne cup and the viscosity of all examples and comparative examples was measured with stirring at the same solids for the same time.
Thermal stability Td the temperature at which the substrate loses 5 wt% weight was tested using a thermogravimetric analyzer according to ASTM D3850.
The peel strength was measured according to IPC-TM-6502.4.8 standard.
TABLE 1
Figure BDA0003392533710000181
Comparing example 1 with comparative example 5, and example 6 with comparative example 6 in table 1, it can be seen that, when the surfactant of the present invention is added to the same system, the contact angle is greatly reduced, and the viscosity of the glue solution is also reduced, which indicates that the filler can rapidly reach a stable dispersion state in the glue solution, and the Td and the peel strength of the substrate are not greatly affected after the surfactant is added in a proper amount due to the reactivity of the surfactant.
Comparing examples 1, 2, 4 and 5 with comparative examples 1 and 2, and examples 3 and 6 with comparative examples 3 and 4 in table 1, it can be seen that the surfactants with or without reactive groups can effectively reduce the contact angle, help the filler to disperse stably, and reduce the viscosity of the glue solution, but after further pressing, the surfactants of comparative examples 1 to 4 are free in the system because the surfactants have no reactive groups, and thus the thermal stability of the circuit substrate and the peeling reliability of the copper foil can be reduced.
In addition, as can be seen from table 1, the smaller the contact angle of the paste on the molded board at 25 ± 1 ℃, the better the grammage stability of the circuit board, which indicates that the smaller the contact angle, the more uniform the distribution of the components in the paste and the better the stability.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The glue solution is characterized by comprising resin, filler, a surfactant, a curing agent and an organic solvent, wherein a molecular chain of the resin is provided with a first reaction group, and the structural formula of the surfactant is shown as a formula (1):
Figure FDA0003392533700000011
in the formula (1), R is a second reactive group, and the molecular weight of the surfactant is 2000-3500;
wherein the first reactive group is selected from vinyl, epoxy, cyanate ester, amino or acid anhydride, and the second reactive group is selected from vinyl or epoxy.
2. The glue solution of claim 1, wherein in formula (1), m is 12-17, n is 4 or 5, x is 1-5, y is 6-20, and z is 4-7.
3. The glue solution of claim 1, wherein the first reactive group and the second reactive group are the same curable system reactive group.
4. The glue of claim 1, wherein the contact angle of the glue on a molded plate is 0-50 ° at 25 ± 1 ℃, wherein the molded plate is made of the filler.
5. The glue solution of any one of claims 1 to 4, wherein the resin comprises at least one of polybutadiene, a copolymer of polybutadiene and styrene, polyisoprene, modified polybutadiene, polyphenylene oxide, modified polyphenylene oxide, polyimide, epoxy resin, modified epoxy resin, cyanate ester and isocyanate.
6. The glue solution of any one of claims 1 to 4, wherein the filler is used in an amount of 150 to 350 parts by weight, the surfactant is used in an amount of 0.5 to 3 parts by weight, and the curing agent is used in an amount of 1 to 20 parts by weight, based on 100 parts by weight of the resin.
7. The glue solution according to any one of claims 1 to 4, wherein a flame retardant is further included in the glue solution.
8. Prepreg, characterized in that it comprises a reinforcing material and a dried glue according to any one of claims 1 to 7 attached to said reinforcing material.
9. A circuit board comprising an insulating layer and a conductive layer provided on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or at least two prepregs which are stacked as set forth in claim 8.
10. A printed circuit board made from the circuit substrate of claim 9.
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Denomination of invention: Glue, semi cured film, circuit substrate, printed circuit board

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