CN107189347A - Resin combination, copper-clad plate, circuit board and manufacture method - Google Patents

Resin combination, copper-clad plate, circuit board and manufacture method Download PDF

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Publication number
CN107189347A
CN107189347A CN201710322664.3A CN201710322664A CN107189347A CN 107189347 A CN107189347 A CN 107189347A CN 201710322664 A CN201710322664 A CN 201710322664A CN 107189347 A CN107189347 A CN 107189347A
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China
Prior art keywords
resin
copper
resin combination
clad plate
glue
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Chinese (zh)
Inventor
张志勤
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Shuitian Kingboard Manufacturing Factory Co ltd
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Shuitian Kingboard Manufacturing Factory Co ltd
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Priority to CN201710322664.3A priority Critical patent/CN107189347A/en
Publication of CN107189347A publication Critical patent/CN107189347A/en
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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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • B32B15/092—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 comprising epoxy resins
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/096—Nitrogen 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
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of resin combination, copper-clad plate, circuit board and manufacture method.A kind of resin combination that the present invention is provided, wherein, count by weight, including following components：52~62 parts of low brominated epoxy；Without 35~45 parts of brominated eopxy resin；1.8~2.2 parts of curing agent；0.02~0.06 part of accelerator；20~60 parts of aluminum oxyhydroxide；20~40 parts of solvent.Above-mentioned resin combination, by adding aluminum oxyhydroxide inorganic filler, on the one hand the CTI values of copper-clad plate can be improved, heat resistance, resistance to acids and bases and the peel strength of copper-clad plate is on the other hand also substantially increased, has effectively expanded the application space of the copper-clad plate of the invention prepared.

Description

Resin combination, copper-clad plate, circuit board and manufacture method
Technical field
The present invention relates to printed circuit technique field, more particularly to a kind of resin combination, copper-clad plate, circuit board and Manufacture method.
Background technology
Copper-clad plate is widely used in various electronics, electric product as the insulating substrate of printed circuit board (PCB).In severe ring The printed wiring board used under border, its surface can accumulate dust, moisture condensation, in the presence of outer making alive, can be anti-between circuit Raw electric spark is reproduced, and then forms the vestige of charing conducting channel, the insulating properties of insulating substrate are destroyed.Weigh the resistance to leakage of copper-clad plate The good and bad index of electric marks rising property is phase ratio creepage tracking index (Comparative Tracking Index, CTI).Frequently with IEC-112 standard methods are tested, and CTI is defined sheet material (copper-clad plate surface etching off copper foil) and is subjected to the chlorination of 50 drop 0.1% by this method Maximum voltage value of the aqueous ammonium without forming tracking.CTI values are higher, and proof tracking is better, represents material Insulating properties is better.
The CTI of copper-clad plate is higher, is more suitable for line density height and the high occasion of dustiness；CTI is lower, and increase is used Danger.At present, its CTI of the common sheet material of industry only has 175V or so, is required far from the high CTI of elevated track density is met.
Traditionally, improve FR-4 CTI can by reducing system bromine content, could be used without or less aromatic ring structure Resin and curing agent, and reached using methods such as hydrated metal oxides.Due to needing to take into account fire-retardant and heat resistance Performances such as (Glass Transition Temperature, Tg), it is impossible to ceaselessly reduce bromine content, can not ceaselessly Aromatic ring structure in reduction system, current industry mostly realizes that sheet material reaches CTI using the scheme of high filler loading capacity aluminium hydroxide Value, especially prepares the copper-clad plate that CTI values are more than 600V.Although the CTI better performances of high filler loading capacity aluminium hydroxide, use Aluminium hydroxide prepare sheet material peel strength is relatively low, poor heat resistance.Due to the appearance of leadless process, CCL industries are to FR~4 The heat resistance of row is further improved, and the heat resistance of original aluminium hydroxide occurs in that significant limitation, especially for one A little high heat-resisting unleaded sheet material aluminium hydroxides typically can not all meet its requirement.Therefore, whole CCL industries are all finding high resistance to Hot, high CTI material new materials.
The content of the invention
Based on this, it is necessary to which for being carried by height filling aluminium hydroxide, peel strength caused by high CTI value is relatively low, heat resistance Poor the problem of, there is provided a kind of resin combination, copper-clad plate, circuit board and manufacture method.
A kind of resin combination that the present invention is provided, wherein, according to the mass fraction, including following components：
In one of the embodiments, the mass fraction of the aluminum oxyhydroxide is 40~60 parts.
In one of the embodiments, the low brominated epoxy is response type yellow glue resin, the low brominated epoxy Bromine content mass percent be 17%~19%；The epoxide equivalent of the low brominated epoxy is 2.2~2.4eq/kg.
In one of the embodiments, the bromine content mass percent of the low brominated epoxy is 17%~19%；Institute The epoxide equivalent for stating low brominated epoxy is 2.2~2.4eq/kg.
In one of the embodiments, the epoxide equivalent without brominated eopxy resin be 2.2~2.2eq/kg, hydrolysis chlorine≤ 500ppm。
In one of the embodiments, the curing agent is dicyandiamide, the accelerator be 2-methylimidazole or 2- ethyls- 4 methylimidazoles, the solvent is dimethylformamide.
In one of the embodiments, the D50 of the aluminum oxyhydroxide is 0.4~0.6 μm.
The present invention also provides a kind of copper-clad plate prepared using resin combination as described above.
The present invention also provides a kind of circuit board prepared using copper-clad plate as described above.
The present invention also provides a kind of preparation method of copper-clad plate, wherein, comprise the following steps：
With glue step, each component in resin combination as described above is well mixed by formula ratio, glue is made；
Gumming step, the glue is coated in enhancing base materials, baking, and prepreg is made；
It is folded to match somebody with somebody row's plate step, the prepreg by plate thickness requirement fold and matches somebody with somebody and covers copper, intermediate is made；
Step is pressed, the intermediate hot pressing is pressed, copper-clad plate is made.
In one of the embodiments, it is described to include with glue step：
Curing agent, which is dissolved in the solvent of part formulation amount, makes the curing agent dissolving complete, and curing agent solution is made；
In the solvent that accelerator is dissolved in remaining formula ratio, accelerator solution is made；
The curing agent solution is mixed with without brominated eopxy resin and low brominated epoxy stirring, resin solution is made；
Aluminum oxyhydroxide is added into the resin solution and mixing is stirred, resin-aluminum oxyhydroxide mixture is made；
The accelerator solution is added to the resin-aluminum oxyhydroxide mixture, is uniformly mixed, glue is made.
In one of the embodiments, temperature when preparing resin-aluminum oxyhydroxide mixture is not higher than 45 DEG C.
In one of the embodiments, the baking temperature of the gumming step is 180~230 DEG C.
Above-mentioned resin combination, by adding aluminum oxyhydroxide inorganic filler, on the one hand can make the CTI of raising copper-clad plate Value, on the other hand also substantially increases heat resistance, resistance to acids and bases and the peel strength of copper-clad plate, has effectively expanded the present invention The application space of the copper-clad plate of preparation.
Brief description of the drawings
, below will be to institute in embodiment in order to illustrate more clearly of the embodiment of the present application or technical scheme of the prior art The accompanying drawing needed to use is briefly described, it should be apparent that, drawings in the following description are only one described in the present invention A little embodiments, for those of ordinary skill in the art, can also obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is the preparation method flow chart of copper-clad plate of the present invention.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, by the following examples, to the present invention Resin combination, copper-clad plate, circuit board and manufacture method be further elaborated.It should be appreciated that described herein Specific embodiment only to explain the present invention, be not intended to limit the present invention.
A kind of resin combination that the present invention is provided, according to the mass fraction, including following components：
Inventor research find mainly due to aluminium hydroxide temperature of initial decomposition it is relatively low the reason for, aluminium hydroxide it is initial Decomposition temperature only has 230 DEG C, and this relatively low decomposition temperature not only reduces the heat resistance of copper-clad plate sheet material, also reduces copper The peel strength of paper tinsel, and the temperature of initial decomposition of aluminium hydroxide requires temperature also below PCB reflow soldering processes.Further, since Aluminium hydroxide is amphoteric compound, and its resistance to acids and bases is poor, through it is secondary take off wash when surface white point easily is presented because of acid and alkali corrosion Hickie.
In order to overcome it is traditional by add aluminium hydroxide carry high CTI value copper-clad plate heat resistance is low, antistripping is strong The poor defect of low, resistance to acids and bases is spent, present invention introduces aluminum oxyhydroxide, by adding aluminum oxyhydroxide to improve the CTI of copper-clad plate Value, overcomes the low caused defect that heat resistance is poor, peel strength is low of aluminium hydroxide heat decomposition temperature, carries high CTI value The heat resistance, peel strength and resistance to acids and bases of copper-clad plate can be improved simultaneously, in addition, also improving the unleaded suitable of copper-clad plate Sexuality is answered, makes to disclosure satisfy that making for high-density line and high pollution degree occasion using copper-clad plate prepared by the resin combination With requiring, the application space of copper-clad plate is improved.
Wherein, use, on the one hand ensure that enough by low brominated epoxy, without two kinds of mixed with resin of brominated eopxy resin Main body reacting resin consumption, on the other hand can control the bromine content in resin combination.If bromine content is too high, CTI can be made Value declines, if bromine content is too low, flame retardant rating can be reduced.By way of low brominated epoxy and without brominated eopxy mixed with resin, The bromine content for making resin combination is 4.43%~9.92%, so as to ensure that combination property is unaffected, is reached optimal.
As a kind of optional embodiment, the mass fraction for the aluminum oxyhydroxide that resin combination is included is 40~60 parts When, CTI values can be made to reach more than 600V.
As a kind of optional embodiment, low brominated epoxy can optionally have tetrabromobisphenol A with response type yellow glue resin Type low brominated epoxy.Alternatively, the bromine content mass percent of low brominated epoxy is 17%~19%, and epoxide equivalent is 2.2~2.4eq/kg.
As a kind of optional embodiment, no brominated eopxy resin can be E-20 resins, and the epoxy of no brominated eopxy resin is worked as Measure as 2.2~2.2eq/kg, hydrolysis chlorine≤500ppm.Hydrolysis chlorine can influence the reaction of epoxy resin and curing agent, and hydrolysis chlorine is not Its influence to resin combination of the invention can be reduced higher than 500ppm.
As a kind of optional embodiment, curing agent can be dicyandiamide, and dicyandiamide is latency amine curing agent, is used Dicyandiamide ensure that its condensate performance is unaffected as curing agent, it is to avoid panel stiffness increase, influence machining property Energy.
As a kind of optional embodiment, accelerator can be, any in 2-methylimidazole, the methylimidazole of 2- ethyls -4 It is a kind of.Compared to the methylimidazole of 2- ethyls -4, cost can be reduced using 2-methylimidazole as accelerator.
As a kind of optional embodiment, solvent can be dimethylformamide.The present invention is used as solidification using dicyandiamide Agent, because dissolving dicyandiamide need to use intensive polar solvent, therefore selection dimethylformamide is more beneficial for dicyandiamide as solvent Dissolving.
It is used as a kind of optional embodiment, the D of aluminum oxyhydroxide50For 0.4~0.6 μm, the size of aluminum oxyhydroxide particle diameter Dispersiveness of the aluminum oxyhydroxide in resin combination can be influenceed, particle diameter is excessive or too small is all likely to result in aluminum oxyhydroxide Deposited from resin combination, influence the combination property of resin combination.Alternatively, the oil absorption of aluminum oxyhydroxide be 12~ 20g/100g, aluminum oxyhydroxide and resin compatible are good in the range of the oil absorption.Alternatively, the whiteness of aluminum oxyhydroxide >= 98, colourity, the purity of aluminum oxyhydroxide of the whiteness higher than 98 can preferably meet aluminum oxyhydroxide of the present invention in resin combination In play a role.
Present invention also offers a kind of copper-clad plate, the copper-clad plate is prepared from using above-mentioned resin combination.
Refer to shown in Fig. 1, present invention also offers a kind of preparation method of above-mentioned copper-clad plate, the preparation method include with Lower step：
S100, with glue step, each component in resin combination is well mixed by formula ratio, and glue is made.
Alternatively, S100, comprises the following steps with glue step：
Make the curing agent dissolving complete the solvent that curing agent is dissolved in part formulation amount, curing agent solution is made；
Accelerator is dissolved in the solvent of remaining formula ratio, accelerator solution is made；
Curing agent solution is mixed with low brominated epoxy and without brominated eopxy resin agitating, resin solution is made；
Aluminum oxyhydroxide is added into resin solution and mixing is stirred, resin-aluminum oxyhydroxide mixture is made.It is optional Ground, aluminum oxyhydroxide is added into resin solution by several times, for example, be divided into and add aluminum oxyhydroxide twice or more than twice, in favor of Aluminum oxyhydroxide it is well mixed.
The accelerator solution is added to resin-aluminum oxyhydroxide mixture, is uniformly mixed, glue is made.
As a kind of optional embodiment, temperature when preparing resin-aluminum oxyhydroxide mixture is not higher than 45 DEG C.
Glue is coated in enhancing base materials by S200, gumming step, baking, and prepreg is made.
Wherein, enhancing base materials can be the enhancing base materials such as glass fabric, synthetic fiber cloth, non-woven fabrics, paper.
Alternatively, the control parameter of gumming step is as follows：
Baking temperature：180~230 DEG C；
Prepreg speed of production：15~25m/min；
Prepreg resin content：40%~45%；
Prepreg gel time：(180±30s)/171℃；
Prepreg fluidity：20 ± 5%.
S300, is folded with row's plate step, and prepreg by plate thickness requirement fold and matches somebody with somebody and covers copper, intermediate is made.
Alternatively, electrolytic copper foil thickness specification can be H oz, 1oz, 1.5oz, 2oz, 3oz, and plate size can be 37mm*49mm, 41mm*49mm, 43mm*49mm, sheet thickness can be 0.5mm~4.0mm.
S400, presses step, intermediate hot pressing is pressed, and copper-clad plate is made.
Alternatively, the control parameter of pressing step is as follows：
Hot pressing temperature：130~230 DEG C；
Hot pressing pressure：8~30kgf/cm2；
Hot pressing time：120min；
The cold pressing time：50min.
It is further comprising the steps of as a kind of optional embodiment：
S500, cutting edge, detecting step will press the copper-clad plate that completes and carry out sharp processing with edge cutting machine, and carry out outward appearance, The detection of aspect of performance.
Embodiment one
2.0kg dicyandiamide is dissolved in 22kg dimethylformamide, makes dicyandiamide dissolving complete, curing agent is made molten Liquid.0.04kg 2-methylimidazole is dissolved in 10kg dimethylformamide, accelerator solution is made.By curing agent solution, The 39kg response type yellow glue resin without brominated eopxy resin, 55kg is added in high shear cylinder, mixed with the stirring of 1400r/min rotating speeds Close, resin solution is made.45kg aluminum oxyhydroxides are added into resin solution and are stirred with 1400r/min rotating speeds and are mixed, stirring When control temperature be not higher than 45 DEG C, persistently stir 1h, be made resin-aluminum oxyhydroxide mixture.It is mixed to resin-aluminum oxyhydroxide Accelerator solution is added in compound, is stirred and mixed with 1400r/min rotating speeds, persistently stir 1h, glue is made.
The viscosity of glue is determined, when viscosity is 25+/- 10s/4#During cup, ordinary cylinder is transferred to, is stirred with 30r/min rotating speeds It is stand-by.
Glue is coated on glass fabric, toasted with baking machine, prepreg is made.Specifically, prepreg control Parameter processed is as follows：
Drying machine baking temperature：210℃；
Prepreg speed of production：22m/min；
Prepreg resin content：43%；
Prepreg gel time：175s/171℃；
Prepreg fluidity：21%.
6 prepregs are folded and matched somebody with somebody, two-sided respectively coated with the thick copper foils of 1oz, double face copper is made in hot pressing pressing.Specifically Ground, hot pressing pressing control parameter is as follows：
Hot pressing temperature：228℃；
Hot pressing pressure：24kgf/cm2；
Hot pressing time：120min；
The cold pressing time：50min.
The copper-clad plate for pressing completion is subjected to sharp processing with edge cutting machine, and carries out outward appearance, the detection of aspect of performance.Determine As a result it is as shown in table 1.
The copper-clad plate basic performance measurement result of table 1
Project Index Representative value
CTI —— 600V
Peel strength 1/1oz ≥1.05N/mm 1.516/1.525N/mm
Floating/288 DEG C of weldering ≥60s 180s
Immersed solder/288 DEG C ≥60s 255s
It is fire-retardant UL94V0 UL94V0
Dielectric constant ≤5.4 4.79
Dielectric loss ≤0.035 0.011
Embodiment two
2.0kg dicyandiamide is dissolved in 22kg dimethylformamide, makes dicyandiamide dissolving complete, curing agent is made molten Liquid.0.04kg 2-methylimidazole is dissolved in 10kg dimethylformamide, accelerator solution is made.By curing agent solution, The 39kg response type yellow glue resin without brominated eopxy resin, 55kg is added in high shear cylinder, mixed with the stirring of 1400r/min rotating speeds Close, resin solution is made.Add 45kg aluminum oxyhydroxides by several times into resin solution and stirred with 1400r/min rotating speeds and mixed, Control temperature to be not higher than 45 DEG C during stirring, persistently stir 1h, resin-aluminum oxyhydroxide mixture is made.To resin-hydroxyl oxidation Accelerator solution is added in aluminium mixture, is stirred and mixed with 1400r/min rotating speeds, persistently stir 1h, glue is made.
The viscosity of glue is determined, when viscosity is 25+/- 10s/4#During cup, ordinary cylinder is transferred to, is stirred with 30r/min rotating speeds It is stand-by.
Glue is coated on glass fabric, toasted with baking machine, prepreg is made.Specifically, prepreg control Parameter processed is as follows：
Drying machine baking temperature：220℃；
Prepreg speed of production：21m/min；
Prepreg resin content：41%；
Prepreg gel time：173s/171℃；
Prepreg fluidity：20%.
8 prepregs are folded and matched somebody with somebody, two-sided respectively coated with the copper foil after 2oz, double face copper is made in hydrothermal solution pressing.Tool Body, hot pressing pressing control parameter is as follows：
Hot pressing temperature：228℃；
Hot pressing pressure：24kgf/cm2；
Hot pressing time：120min；
The cold pressing time：50min.
The copper-clad plate for pressing completion is subjected to sharp processing with edge cutting machine, and carries out outward appearance, the detection of aspect of performance.Determine As a result it is as shown in table 2.
The copper-clad plate basic performance measurement result of table 2
Project Index Representative value
CTI —— 600V
Peel strength 1/1oz ≥1.1N/mm 1.917/1.935N/mm
Floating/288 DEG C of weldering ≥60s 210s
Immersed solder/288 DEG C ≥60s 215s
It is fire-retardant UL94V0 UL94V0
Dielectric constant ≤5.4 4.67
Dielectric loss ≤0.035 0.012
Embodiment three
1.8kg dicyandiamide is dissolved in 13kg dimethylformamide, makes dicyandiamide dissolving complete, curing agent is made molten Liquid.0.02kg 2-methylimidazole is dissolved in 8kg dimethylformamide, accelerator solution is made.By curing agent solution, The 36kg response type yellow glue resin without brominated eopxy resin, 52kg is added in high shear cylinder, mixed with the stirring of 1400r/min rotating speeds Close, resin solution is made.Add 20kg aluminum oxyhydroxides in two times into resin solution and mixed with the stirring of 1400r/min rotating speeds Close, control temperature to be not higher than 45 DEG C during stirring, persistently stir 1h, resin-aluminum oxyhydroxide mixture is made.To resin-hydroxyl Accelerator solution is added in alumina mixture, is stirred and mixed with 1400r/min rotating speeds, persistently stir 1h, glue is made.
The viscosity of glue is determined, when viscosity is 25+/- 10s/4#During cup, ordinary cylinder is transferred to, is stirred with 30r/min rotating speeds It is stand-by.
Glue is coated on glass fabric, toasted with baking machine, prepreg is made.Specifically, prepreg control Parameter processed is as follows：
Drying machine baking temperature：210℃；
Prepreg speed of production：22m/min；
Prepreg resin content：43%；
Prepreg gel time：175s/171℃；
Prepreg fluidity：21%.
6 prepregs are folded and matched somebody with somebody, single-side coated copper plate is made coated with the thick copper foils of 1oz, hot pressing pressing in one side.Specifically, it is hot Pressure pressing control parameter is as follows：
Hot pressing temperature：228℃；
Hot pressing pressure：24kgf/cm2；
Hot pressing time：120min；
The cold pressing time：50min.
The copper-clad plate for pressing completion is subjected to sharp processing with edge cutting machine, and carries out outward appearance, the detection of aspect of performance.Determine As a result it is as shown in table 3.
The copper-clad plate basic performance measurement result of table 3
Project Index Representative value
CTI —— 300V
Peel strength 1/1oz ≥1.05N/mm 1.516/1.525N/mm
Floating/288 DEG C of weldering ≥60s 180s
Immersed solder/288 DEG C ≥60s 255s
It is fire-retardant UL94V0 UL94V0
Dielectric constant ≤5.4 4.79
Dielectric loss ≤0.035 0.011
Example IV
2.2kg dicyandiamide is dissolved in 28kg dimethylformamide, makes dicyandiamide dissolving complete, curing agent is made molten Liquid.0.06kg 2-methylimidazole is dissolved in 12kg dimethylformamide, accelerator solution is made.By curing agent solution, The 45kg response type yellow glue resin without brominated eopxy resin, 62kg is added in high shear cylinder, mixed with the stirring of 1400r/min rotating speeds Close, resin solution is made.Add 60kg aluminum oxyhydroxides in four times into resin solution and mixed with the stirring of 1400r/min rotating speeds Close, control temperature to be not higher than 45 DEG C during stirring, persistently stir 1h, resin-aluminum oxyhydroxide mixture is made.To resin-hydroxyl Accelerator solution is added in alumina mixture, is stirred and mixed with 1400r/min rotating speeds, persistently stir 1h, glue is made.
The viscosity of glue is determined, when viscosity is 25+/- 10s/4#During cup, ordinary cylinder is transferred to, is stirred with 30r/min rotating speeds It is stand-by.
Glue is coated on glass fabric, toasted with baking machine, prepreg is made.Specifically, prepreg control Parameter processed is as follows：
Drying machine baking temperature：220℃；
Prepreg speed of production：21m/min；
Prepreg resin content：41%；
Prepreg gel time：173s/171℃；
Prepreg fluidity：20%.
8 prepregs are folded and matched somebody with somebody, single-side coated copper plate is made coated with the copper foil after 2oz, hydrothermal solution pressing in one side.Specifically, Hot pressing pressing control parameter is as follows：
Hot pressing temperature：228℃；
Hot pressing pressure：24kgf/cm2；
Hot pressing time：120min；
The cold pressing time：50min.
The copper-clad plate for pressing completion is subjected to sharp processing with edge cutting machine, and carries out outward appearance, the detection of aspect of performance.Determine As a result it is as shown in table 4.
The copper-clad plate basic performance measurement result of table 4
Project Index Representative value
CTI —— 600V
Peel strength 1/1oz ≥1.1N/mm 1.917/1.935N/mm
Floating/288 DEG C of weldering ≥60s 210s
Immersed solder/288 DEG C ≥60s 215s
It is fire-retardant UL94V0 UL94V0
Dielectric constant ≤5.4 4.67
Dielectric loss ≤0.035 0.012
Reference examples one
By 50kg low brominated epoxy, 35kg without brominated eopxy resin, 4kg polyfunctional group resin, 2.0kg double cyanogen Amine, 0.04kg 2-methylimidazole, 50kg aluminium hydroxide, 32kg dimethylformamide are according to existing method prepare glue.
Glue is coated on glass fabric, toasted with baking machine, prepreg is made.Prepreg control parameter is such as Under：
Drying machine baking temperature：210℃；
Prepreg speed of production：22m/min；
Prepreg resin content：43%；
Prepreg gel time：175s/171℃；
Prepreg fluidity：21%.
6 prepregs are folded and matched somebody with somebody, two-sided respectively coated with the thick copper foils of 1oz, double face copper is made in hot pressing pressing.Specifically Ground, hot pressing pressing control parameter is as follows：
Hot pressing temperature：228℃；
Hot pressing pressure：24kgf/cm2；
Hot pressing time：120min；
The cold pressing time：50min.
The copper-clad plate for pressing completion is subjected to sharp processing with edge cutting machine, and carries out outward appearance, the detection of aspect of performance.Determine As a result it is as shown in table 5.
The copper-clad plate basic performance measurement result of table 5
Project Index Representative value
CTI —— 600V
Peel strength 1/1oz ≥1.05N/mm 1.413/1.427N/mm
Floating/288 DEG C of weldering ≥60s 80s
Immersed solder/288 DEG C ≥60s 90s
It is fire-retardant UL94V0 UL94V0
Dielectric constant ≤5.4 4.8
Dielectric loss ≤0.035 0.011
Material composition that the embodiment of the present invention is used, performance standard is as shown in table 6~11.
Table 6E grade fiberglass cloth ingredient standards
Composition Content
B2O3 5%~10%
CaO 16%~25%
Al203 12%~16%
SiO2 52%~56%
MgO 0%~5%
Na2O、K20 0%~2%
TiO2 0%~0.8%
Fe203 0.05%~0.4%
F2 0%~1.0%
Table 7E grade fiberglass cloth performance standards
Project Index
Thickness 0.18±0.018mm
Indicated weight 203±5g/m2
Warp-wise tensile strength ≥295N/25mm
Weft tension intensity ≥250N/25mm
Warp-wise yarn density 44 ± 2 pieces/inch
Broadwise yarn density 31 ± 2 pieces/inch
Outward appearance Performed by IPC-4412
The response type yellow glue resin property standard of table 8
Project Index
Outward appearance Amber transparent liquid
Viscosity 1000~2000mPa
Epoxide number 2.2~2.4eq/kg
Solids content 80 ± 1%
Bromine content 17~19%
Table 9 is without brominated eopxy resin property standard
Project Index
Outward appearance Light yellow transparent liquid
Epoxide number 2.0~2.2eq/kg
Solids content 70 ± 1%
Hydrolyze chlorine ≤500ppm
The aluminum oxyhydroxide performance standard of table 10
Project Index
Moisture ≤ 0.3%
D50 0.4~0.6 μm
Oil absorption 16+/-4g/100g
Whiteness ≥98
The copper foil performance standard of table 11
Project Index
Copper foil type Electrolytic copper foil
Tension intensity (N/cm2) ≥28000
Indicated weight (g/m2) 305 ± 10%
Surface roughness (μm) ≤10
Elongation percentage >=3%
Outward appearance Performed by IPC-4101D
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (13)

1. a kind of resin combination, it is characterised in that according to the mass fraction, including following components：
2. resin combination according to claim 1, it is characterised in that the mass fraction of the aluminum oxyhydroxide is 40~ 60 parts.
3. resin combination according to claim 1, it is characterised in that the low brominated epoxy is response type yellow glue tree Fat.
4. resin combination according to claim 1, it is characterised in that the bromine content quality hundred of the low brominated epoxy Fraction is 17%~19%；The epoxide equivalent of the low brominated epoxy is 2.2~2.4eq/kg.
5. resin combination according to claim 1, it is characterised in that the epoxide equivalent without brominated eopxy resin is 2.2~2.2eq/kg, hydrolyzes chlorine≤500ppm.
6. resin combination according to claim 1, it is characterised in that the curing agent is dicyandiamide, the accelerator For 2-methylimidazole or the methylimidazole of 2- ethyls -4, the solvent is dimethylformamide.
7. the resin combination according to claim 1 to 6 any one, it is characterised in that the D of the aluminum oxyhydroxide50 For 0.4~0.6 μm.
8. copper-clad plate prepared by a kind of resin combination using as described in claim 1 to 7 any one.
9. a kind of circuit board prepared using copper-clad plate as claimed in claim 8.
10. a kind of preparation method of copper-clad plate, it is characterised in that comprise the following steps：
With glue step, each component in the resin combination as described in claim 1 to 7 any one is mixed equal by formula ratio It is even, glue is made；
Gumming step, the glue is coated in enhancing base materials, baking, and prepreg is made；
It is folded to match somebody with somebody row's plate step, the prepreg by plate thickness requirement fold and matches somebody with somebody and covers copper, intermediate is made；
Step is pressed, the intermediate hot pressing is pressed, copper-clad plate is made.
11. preparation method according to claim 10, it is characterised in that described to include with glue step：
Curing agent, which is dissolved in the solvent of part formulation amount, makes the curing agent dissolving complete, and curing agent solution is made；
In the solvent that accelerator is dissolved in remaining formula ratio, accelerator solution is made；
The curing agent solution is mixed with without brominated eopxy resin and low brominated epoxy stirring, resin solution is made；
Aluminum oxyhydroxide is added into the resin solution and mixing is stirred, resin-aluminum oxyhydroxide mixture is made；
The accelerator solution is added to the resin-aluminum oxyhydroxide mixture, is uniformly mixed, glue is made.
12. preparation method according to claim 11, it is characterised in that described to prepare resin-aluminum oxyhydroxide mixture When temperature be not higher than 45 DEG C.
13. the preparation method according to claim 10 to 12 any one, it is characterised in that the gumming step it is described Baking temperature is 180~230 DEG C.
CN201710322664.3A 2017-05-09 2017-05-09 Resin combination, copper-clad plate, circuit board and manufacture method Pending CN107189347A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110328914A (en) * 2019-06-17 2019-10-15 吉安市宏瑞兴科技有限公司 A kind of copper-clad plate and preparation method thereof suitable for PCB processing procedure with good flame-retardance
CN113263796A (en) * 2021-04-27 2021-08-17 建滔电子材料（江阴）有限公司 Copper-clad plate with low thermal expansion coefficient and preparation process thereof
CN113263797A (en) * 2021-05-06 2021-08-17 建滔电子材料（江阴）有限公司 Low-cost copper-clad plate with stable size and preparation process thereof
CN113307993A (en) * 2021-04-27 2021-08-27 建滔电子材料（江阴）有限公司 Glass yarn and glass fiber cloth and preparation process thereof
CN117229596A (en) * 2023-09-04 2023-12-15 忠信世纪电子材料(始兴)有限公司 High heat-resistant copper-clad plate and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1871300A (en) * 2003-10-01 2006-11-29 阿尔伯麦尔公司 Flame retardant epoxy prepregs, laminates, and printed wiring boards of enhanced thermal stability
CN101654004A (en) * 2008-08-22 2010-02-24 金安国纪科技股份有限公司 Method for manufacturing CTI copper-clad laminate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1871300A (en) * 2003-10-01 2006-11-29 阿尔伯麦尔公司 Flame retardant epoxy prepregs, laminates, and printed wiring boards of enhanced thermal stability
CN101654004A (en) * 2008-08-22 2010-02-24 金安国纪科技股份有限公司 Method for manufacturing CTI copper-clad laminate

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110328914A (en) * 2019-06-17 2019-10-15 吉安市宏瑞兴科技有限公司 A kind of copper-clad plate and preparation method thereof suitable for PCB processing procedure with good flame-retardance
CN113263796A (en) * 2021-04-27 2021-08-17 建滔电子材料（江阴）有限公司 Copper-clad plate with low thermal expansion coefficient and preparation process thereof
CN113307993A (en) * 2021-04-27 2021-08-27 建滔电子材料（江阴）有限公司 Glass yarn and glass fiber cloth and preparation process thereof
CN113263797A (en) * 2021-05-06 2021-08-17 建滔电子材料（江阴）有限公司 Low-cost copper-clad plate with stable size and preparation process thereof
CN117229596A (en) * 2023-09-04 2023-12-15 忠信世纪电子材料(始兴)有限公司 High heat-resistant copper-clad plate and preparation method thereof

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