CN108676533B - Resin composition and resin-coated copper foil made therefrom - Google Patents
Resin composition and resin-coated copper foil made therefrom Download PDFInfo
- Publication number
- CN108676533B CN108676533B CN201810413299.1A CN201810413299A CN108676533B CN 108676533 B CN108676533 B CN 108676533B CN 201810413299 A CN201810413299 A CN 201810413299A CN 108676533 B CN108676533 B CN 108676533B
- Authority
- CN
- China
- Prior art keywords
- resin
- parts
- epoxy resin
- copper foil
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- 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
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
本发明涉及一种树脂组合物及其制作的涂树脂铜箔。本发明的树脂组合物包含有机树脂组分和无机填料，其中，所述有机树脂组分包括：环氧树脂、相对于100重量份的环氧树脂为20‑100重量份的活性聚醚砜、相对于100重量份的环氧树脂为10‑20重量份的酚氧树脂；所述无机填料为纳米二氧化硅，相对于每100重量份的有机树脂组分，纳米二氧化硅的量为2‑10重量份。本发明通过采用聚醚砜、纳米二氧化硅和酚氧树脂共同增强增韧环氧树脂，使得由树脂组合物制成的涂树脂铜箔具有高Tg、高耐热性、高热分解温度、尺寸稳定性好、阻燃性优异、不掉粉，可满足更高性能高密度互连PCB使用要求。The invention relates to a resin composition and a resin-coated copper foil prepared therefrom. The resin composition of the present invention comprises an organic resin component and an inorganic filler, wherein the organic resin component comprises: epoxy resin, 20-100 parts by weight of active polyethersulfone relative to 100 parts by weight of epoxy resin, Relative to 100 parts by weight of epoxy resin, it is 10-20 parts by weight of phenolic resin; the inorganic filler is nano-silica, and relative to every 100 parts by weight of organic resin components, the amount of nano-silica is 2 ‑10 parts by weight. The present invention adopts polyethersulfone, nano-silica and phenolic resin to strengthen and toughen epoxy resin together, so that the resin-coated copper foil made of the resin composition has high Tg, high heat resistance, high thermal decomposition temperature, and size. Good stability, excellent flame retardancy, no powder drop, can meet the requirements of higher performance and high density interconnection PCB.
Description
Technical Field
The invention relates to the technical field of electronic products, in particular to a resin composition for a printed circuit board and a resin-coated copper foil manufactured by the same.
Background
With the miniaturization and multifunctionalization of electronic devices, Printed Circuit Boards (PCBs) are required to be high in density and performance, and high-density interconnection technologies are developing faster and faster, while resin-coated copper foils (RCCs) do not contain glass fibers, have lower dielectric constants and faster signal transmission compared with bonding sheets (prepreg), and are more suitable for laser drilling, thus being widely applied to high-density interconnection (HDI) printed circuit boards. At present, the Tg of the commonly used RCC is below 155 ℃, the heat resistance is insufficient, and the dimensional stability is also poor; and part of high Tg RCC is also brittle and has the problems of more powder falling and the like, so that the use requirement of the HDI PCB with higher performance is difficult to meet.
The Chinese patent application CN102311612A adopts a mode of phenol-oxygen and core-shell resin (CSR) toughened epoxy to manufacture RCC, although the Tg of the RCC is higher and the powder falling property is good, the heat resistance can also pass through the common lead-free reflow soldering (the maximum temperature is 260 ℃, and is less than 6 times), if the number of times of the original lead-free reflow soldering is increased to more than 10 times, or the maximum temperature of the lead-free reflow soldering is increased to 280 ℃, the number of times of reflow soldering is lower, and even the RCC can not pass through; meanwhile, the RCC of the patent application has lower modulus, the RCC modulus is reduced more obviously particularly at the high temperature of 100 ℃, and the defect exists in the manufacturing process of thinned HDI. In addition, the Coefficient of Thermal Expansion (CTE) of the RCC of this patent application is also relatively large and cannot meet the application requirements of any layer of high-density interconnected PCB.
Disclosure of Invention
In view of the disadvantages of the prior art, the present invention is directed to a resin composition having a high glass transition temperature (Tg), a high modulus, and a high heat resistance, and a resin-coated copper foil (RCC) made therefrom.
The inventors of the present application have made extensive studies to achieve the above object, and as a result, have unexpectedly found that: polyether sulfone, nano silicon dioxide and phenoxy resin are used for jointly reinforcing and toughening epoxy resin, so that the high Tg (glass transition temperature) and RCC (resin controlled cracking) powder-free epoxy resin can be obtained, the heat resistance is high, the thermal shock (288 ℃/10S) is up to more than 20 times, the peeling strength of the copper foil is high, and the performance requirements and the processing process requirements of any HDI PCB can be met.
One aspect of the present invention provides a resin composition comprising an organic resin component and an inorganic filler, wherein the organic resin component comprises: epoxy resin, 20-100 parts by weight of active polyether sulfone relative to 100 parts by weight of epoxy resin, and 10-20 parts by weight of phenoxy resin relative to 100 parts by weight of epoxy resin; the inorganic filler is nano silica in an amount of 2 to 10 parts by weight per 100 parts by weight of the organic resin component.
In certain embodiments, the epoxy resin is one or a combination of bisphenol a type epoxy resin, phosphorous epoxy resin, novolac epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, cycloaliphatic epoxy resin, bromine-free epoxy resin.
In certain embodiments, the activated polyethersulfone has the following structure:
wherein R is1And R2Denotes a reactive end group, R1And R2May be the same or different, each independently selected from the group consisting of a hydroxyl group, an amine group, an allyl group and an epoxy group; n is an integer of 5 to 500.
In certain embodiments, the active polyethersulfone has active terminal hydroxyl groups and the active terminal hydroxyl groups are present in a range of 10 to 500 μ eq/g.
In certain embodiments, the phenoxy resin has the following structure:
wherein n is 50-150, and R1 and R2 may be the same or different and each independently represents a H atom, a Br atom or a P-containing group (e.g., DOPO, etc.).
In certain embodiments, the resin composition further comprises a curing agent and optionally a curing accelerator.
In some embodiments, the curing agent is one or a combination of dicyandiamide, 4' -diaminodiphenyl sulfone, bisphenol A phenolic aldehyde and phenol phenolic aldehyde, and the equivalent ratio of the amino equivalent or hydroxyl equivalent to the epoxy equivalent of the curing agent is 1: 1-2.
In certain embodiments, the cure accelerator is an imidazole-based cure accelerator.
In certain embodiments, the resin composition further comprises a solvent that is a mixture of one or more of Dimethylacetamide (DMAC), Methyl Ethyl Ketone (MEK), acetone, cyclohexanone, toluene solvents.
Another aspect of the present invention provides a resin-coated copper foil comprising a copper foil and a resin layer on a roughened surface of the copper foil, the resin layer being prepared from the above-described resin composition.
In certain embodiments, the resin-coated copper foil is used in a high-density interconnect printed circuit board.
The resin-coated copper foil (RCC) generally used at present has insufficient heat resistance and poor dimensional stability; the RCC prepared by the resin composition provided by the invention has high Tg (higher than 160 ℃), high heat resistance, high thermal decomposition temperature, good dimensional stability, excellent flame retardance and no powder falling, thereby meeting the use requirements of interconnected PCBs with higher performance and high density.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
One aspect of the present invention relates to a resin composition comprising an organic resin component (epoxy resin, active polyethersulfone, phenoxy resin) and an inorganic filler (nanosilica), and may further comprise the following optional components: curing agent, curing accelerator, solvent and other additives. The respective components of the resin composition of the present invention will be described in detail below.
-epoxy resins-
An epoxy resin is one of the main components of the resin composition of the present invention as a matrix resin. The epoxy resin of the present invention is not particularly limited, and it may be selected from organic compounds having a molecular structure containing at least two epoxy groups, for example, bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, tetramethylbisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol P type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthol novolac type epoxy resin, anthracene type epoxy resin, phenolphthalein type epoxy resin, phenoxy type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, Dicyclopentadiene phenol type epoxy resins, aralkyl phenol type epoxy resins, epoxy resins containing an arylene ether structure in the molecule, alicyclic epoxy resins, polyhydric alcohol type epoxy resins, silicon-containing epoxy resins, nitrogen-containing epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins, phosphorus-containing epoxy resins obtained by introducing a phosphorus compound into these resins, and the like.
Preferably, the epoxy resin can be one or a combination of more of bisphenol A epoxy resin, phosphorus-containing epoxy resin, novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, alicyclic epoxy resin and bromine-free epoxy resin.
The phosphorus-containing epoxy resin refers to an epoxy resin in which a reactive phosphorus compound is used and a phosphorus atom is absorbed by a chemical bond. Examples of the reactive phosphorus compound may include 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like. Commercially available phosphorous epoxy resins include XZ92530 (Dow chemical), YEP-250, YEP-300 (Guangshan chemical Co., Ltd.), and the like.
Active polyethersulfone-
By activated polyethersulfone is meant polyethersulfones having reactive end groups, examples of which include, but are not limited to, hydroxyl, amine, allyl, and epoxy groups.
The activated polyethersulfones of the present invention may have the following structural formula:
wherein R is1And R2Denotes a reactive end group, R1And R2May be the same or different, each independently selected from the group consisting of a hydroxyl group, an amine group, an allyl group and an epoxy group; n is an integer of 5 to 500.
The molecular weight of the active polyethersulfone may be in the range of 1000-100000, and in this range, the active polyethersulfone may be dissolved in a solvent, easily mixed and reacted with an epoxy resin or the like, and there is no problem of brittleness (low toughness) caused by an excessively small molecular weight.
The reactive end group of the reactive polyethersulfone may preferably be a hydroxyl group because the affinity with the epoxy resin may be greatly improved. When the polyethersulfone has active terminal hydroxyl groups, the content of active terminal hydroxyl groups may be in the range of 10 to 500. mu. eq/g, preferably 100. mu. eq/g.
In the resin composition of the present invention, the active polyethersulfone may be used in an amount of 20 to 100 parts by weight relative to 100 parts by weight of the epoxy resin. Preferably, the weight ratio of active polyethersulfone to epoxy resin may be 1:1 to 4.5.
Phenoxy resin-
The phenoxy resin used in the resin composition of the present invention may have the following structure:
wherein n is 50-150, and R1 and R2 may be the same or different and each independently represents a H atom, a Br atom or a P-containing group (e.g., DOPO, etc.).
In the resin composition of the present invention, the phenoxy resin may be used in an amount of 10 to 20 parts by weight, relative to 100 parts by weight of the epoxy resin. In addition, the dosage ratio of the phenoxy resin to the active polyethersulfone can be 1: 1-10, preferably 1: 2 to 4.
In the resin composition of the present invention, both the phenoxy resin and the active polyethersulfone have a toughening effect on the epoxy resin, and sometimes both may be collectively referred to as a toughening resin.
-nano silica-
The nanosilica that can be used in the present invention has a particle size of 100nm or less, preferably 10 to 40 nm. The nano-scale silica as an inorganic filler, in combination with the above toughening resin, can improve Tg (> 160 ℃), heat resistance, thermal decomposition temperature and dimensional stability of the resin composition, particularly improve DMA modulus and reduce Coefficient of Thermal Expansion (CTE).
In the invention, the dosage of the nano silicon dioxide can be between 2 percent and 10 percent of the total amount of the epoxy resin and the toughening resin. Preferably, the nano silica may be used in an amount of 2 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin.
Curing agents
The resin composition of the present invention may contain a curing agent. The curing agent may be selected from curing agents for epoxy resins. In the present invention, amine-based curing agents and phenol resin curing agents are preferable. For example, the curing agent can be one or a combination of dicyandiamide, 4' -diaminodiphenyl sulfone, bisphenol a phenol formaldehyde and phenol formaldehyde.
In the present invention, the curing agent is used in an amount such that the equivalent ratio of the curing agent to the epoxy resin (equivalent ratio of amino group equivalent or hydroxyl group equivalent to epoxy equivalent) is 1:1 to 2.
Curing accelerators
The resin composition of the present invention may further contain a curing accelerator. In the case of an epoxy system using an amine or a phenol resin as a curing agent, the curing accelerator is preferably an imidazole compound, for example, imidazole (2-methylimidazole, 1-methylimidazole), etc., and derivatives thereof.
The curing accelerator may be used in an amount of 0.05 to 0.5 parts by weight, relative to 100 parts by weight of the organic resin component, to adjust gelation index of the resin composition and ensure stable process control.
-solvent-
The resin composition of the present invention may contain a solvent to dissolve the above epoxy resin, toughening resin, curing agent and the like together to form a glue solution. Preferably, the solvent may be one or a mixture of several of Dimethylacetamide (DMAC), Methyl Ethyl Ketone (MEK), acetone, cyclohexanone, and toluene. The mixed solvent may be, for example, a mixed solvent in which two or three of the above solvents are mixed at 1:1 or 1: 1.
In the present invention, the solvent is used in an appropriate amount to form a dope having a viscosity (e.g., 300-600 cPa. s) convenient for coating. For example, the solids content in the dope may be 40 wt% to 60 wt%.
Other additives
The resin composition of the present invention may further comprise other additives such as flame retardants, organic fillers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and the like. These various additives may be used alone or in combination of two or more. The amount of other additives may be arbitrarily adjusted within a range not to lose the effect of the present invention.
Another aspect of the invention relates to a resin-coated copper foil and a method of making the same.
The resin-coated copper foil of the present invention comprises a copper foil and a resin layer on a roughened surface of the copper foil, wherein the resin layer is formed by coating the resin composition.
The copper foil used for the resin-coated copper foil may be an electrolytic copper foil.
When the resin-coated copper foil is manufactured, all components of the resin composition are dissolved together into glue solution through a solvent, then the glue solution is uniformly coated on the roughened surface of the copper foil, and the copper foil is baked in an oven at the temperature of 150-.
The resin-coated copper foil manufactured by the above method can be used for a high-density interconnected printed circuit board.
The present invention may have at least one of the following advantages:
(1) the resin composition with higher Tg can be obtained by adopting the active polyether sulfone, the nano silicon dioxide and the phenoxy resin to jointly reinforce and toughen the epoxy resin, the RCC does not fall off powder, the heat resistance is higher, the thermal shock (288 ℃/10S) reaches more than 20 times, the peel strength of the copper foil is also higher, and the flame retardance is excellent.
(2) RCC can be laminated for many times, and can meet the performance requirement and the processing technology requirement of any HDI PCB.
(3) The active polyether sulfone (especially polyether sulfone with terminal hydroxyl groups) and the phenoxy resin are jointly used as the toughening resin, so that the high Tg, the thermal decomposition temperature (Td), the Coefficient of Thermal Expansion (CTE), the DMA modulus and the heat resistance of the resin composition are improved, the peel strength of the copper foil is improved, namely, the defects of the phenoxy resin in the aspects of Tg and heat resistance are overcome, and other performance advantages of the phenoxy resin are retained.
(4) The nano silicon dioxide and the toughening resin are combined for use, so that a better reinforcing and toughening effect is achieved, the powder dropping property is improved, and the using amount is reduced.
(5) The resin composition of the invention is easy to prepare into glue solution, greatly simplifies the production process and improves the production efficiency.
Examples
The technical solutions of the present invention are further illustrated below by examples, which, however, do not limit the scope of the present invention in any way.
In the following examples, parts by mass of the organic resin are based on parts by mass of organic solids unless otherwise indicated.
The first embodiment is as follows:
the resin composition comprises: 50 parts of epoxy resin (YEP-250, Guangdong Guangshan), 20 parts of active polyether sulfone (SOLVAY, 3000RP) and nano SiO2(winning company, Nanopol A710) 3.2 parts, phenoxy resin (Inchem, PKHH)5 parts, and amine curing agent (dicyandiamide) 1 part. 0.1 part of imidazole accelerator (2-methylimidazole (2-MI)) and a proper amount of solvent (DMAC: MEK 1:1) are added into the composition to prepare glue solution with the solid content of 40-60%, the glue solution is uniformly stirred and mixed and then coated on the roughened surface of the electrolytic copper foil, and the roughened surface is baked in an oven at the temperature of 150 ℃ and 160 ℃ for 3-6 minutes to obtain a resin-coated copper foil (RCC) product. Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Example two:
the resin composition comprises: 60 parts of epoxy resin (Hemson corporation, EPIKOTE 627-B-80), 30 parts of polyether sulfone (SOLVAY, 3600RP) and nano SiO2(winning company, Nanopol A710), 10 parts of phenoxy resin (Inchem company, PKHH), and 20 parts of phenolic resin curing agent (Resolution company, EPIKURE YLH129B 65). 0.15 part of imidazole accelerator (2-MI) and a proper amount of solvent (DMAC: MEK ═ 1:1) are added into the composition to prepare glue solution with the solid content of 40-60%, the glue solution is uniformly stirred and mixed, then the glue solution is coated on the roughened surface of the electrolytic copper foil, and the roughened surface is baked in an oven at 150-160 ℃ for 3-6 minutes to obtain a resin-coated copper foil (RCC) product. Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Example three:
the resin composition comprises: 70 parts of epoxy resin (YEP-250, Guangdong Guangshan), 30 parts of polyether sulfone (SOLVAY, 3000RP) and nano SiO2(Yingchuang company Nanopol A710) 5 parts, phenol-oxygen resin (Xinri iron chemical Co., Ltd.)Sherf-001) 14 parts, and amine curing agent (dicyandiamide) 3 parts. 0.25 part of imidazole accelerator (2-MI) and a proper amount of solvent (DMAC: MEK ═ 1:1) are added into the composition to prepare glue solution with the solid content of 40-60%, the glue solution is evenly stirred and mixed and then coated on the rough surface of the electrolytic copper foil, and the rough surface is baked in an oven at 155 ℃ for 5 minutes to obtain a resin-coated copper foil (RCC) product. Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Example four:
the resin composition comprises: 90 parts of epoxy resin (Hemson company, EPIKOTE 627-B-80), 40 parts of polyether sulfone (SOLVAY, 3600RP) and nano SiO27.5 parts of (Nanopol A710, Wingsho company), 18 parts of phenoxy resin (PKHH, Inchem company) and 5 parts of amine curing agent (dicyandiamide and DDS). 0.25 part of imidazole accelerator (2-MI) and a proper amount of solvent (DMAC: MEK ═ 1:1) are added into the composition to prepare glue solution with the solid content of 40-60%, the glue solution is evenly stirred and mixed and then coated on the rough surface of the electrolytic copper foil, and the rough surface is baked in an oven at 155 ℃ for 6 minutes to obtain a resin-coated copper foil (RCC) product. Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Example five:
the resin composition comprises: 50 parts of epoxy resin (YEP-250, Guangdong Guangshan), 50 parts of polyether sulfone (SOLVAY, 3000RP) and nano SiO24 parts of Nanopol A710 (winning company), 5 parts of phenoxy resin (PKHH (Inchem company) and 2 parts of amine curing agent (dicyandiamide). 0.1 part of imidazole accelerator (2-MI) and a proper amount of solvent (DMAC: MEK ═ 1:1) are added into the composition to prepare glue solution with the solid content of 40-60%, the glue solution is evenly stirred and mixed and then coated on the rough surface of the electrolytic copper foil, and the rough surface is baked in an oven at 155 ℃ for 6 minutes to obtain a resin-coated copper foil (RCC) product. Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Comparative example one:
first, 30 parts by weight of a phenol resin (Resolution, EPIKURE YLH129B65) and 0.10 part by weight of an accelerator (2-MI) were dissolved in an appropriate amount of a mixed solvent (1: 1) of PM and Methyl Ethyl Ketone (MEK), and the mixture was stirred for 60 minutes or longer.
Then, 100 parts by weight of an epoxy resin (YEP-250, Guangdong mountain), 10 parts by weight of a biphenyl epoxy resin (NC-3000H, Nippon chemical), 20 parts by weight of a phenoxy resin (PKHH, Inc.) and 25 parts by weight of a core shell rubber (Nippon Brillouin MX-392, Japan) were added in this order, stirred for 4 hours or more and mixed well to form a solution having a resin content of 50%.
And uniformly coating the solution on the roughened surface of 1/2OZ electrolytic copper foil, and baking in an oven at the temperature of 150-160 ℃ for 3-5 minutes to obtain the resin-coated copper foil.
Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Comparative example two:
3 parts by weight of a curing agent (dicyandiamide) and 0.2 part by weight of an accelerator (2-MI) were dissolved in an appropriate amount of a mixed solvent (1: 1) of Dimethylformamide (DMF) and Methyl Ethyl Ketone (MEK), and the mixture was stirred for 60 minutes or longer.
Then, 100 parts by weight of an epoxy resin (YEP-250, Guangdong mountain, Guangdong province), 50 parts by weight of a biphenyl epoxy resin (NC-3000H, Japan chemical), 60 parts by weight of a phenoxy resin (PKHH, Inc.) and 15 parts by weight of a core shell rubber (Nippon Brillouin MX-392, Japan) were added in this order, stirred for 4 hours or more, and sufficiently mixed to obtain a solution having a resin content of 50%.
And uniformly coating the solution on the roughened surface of 1/2OZ electrolytic copper foil, and baking in an oven at the temperature of 150-160 ℃ for 3-5 minutes to obtain the resin-coated copper foil.
Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Comparative example three:
the resin composition comprises: 70 parts of epoxy resin (YEP-250, Guangdong Guangshan), 30 parts of polyether sulfone (SOLVAY, 3000RP) and nano SiO2(winning company Na)nopol A710) 5 parts, and an amine curing agent (dicyandiamide) 3 parts. 0.2 part of imidazole accelerator (2-MI) and a proper amount of solvent (DMAC: MEK ═ 1:1) are added into the composition to prepare glue solution with the solid content of 40-60%, the glue solution is evenly stirred and mixed and then coated on the rough surface of the electrolytic copper foil, and the rough surface is baked in an oven at 155 ℃ for 6 minutes to obtain a resin coated copper foil (RCC) product. Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Comparative example four:
the resin composition comprises: 60 parts of epoxy resin (YEP-250, Guangdong mountains in Guangdong province), 30 parts of polyether sulfone (SOLVAY, 3600RP), 10 parts of phenoxy resin (Inchem company, PKHH) and 2 parts of amine curing agent (dicyandiamide). 0.2 part of imidazole accelerator (2-MI) and a proper amount of solvent (DMAC: MEK ═ 1:1) are added into the composition to prepare glue solution with the solid content of 40-60%, the glue solution is evenly stirred and mixed and then coated on the rough surface of the electrolytic copper foil, and the rough surface is baked in an oven at 155 ℃ for 6 minutes to obtain a resin coated copper foil (RCC) product. Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Comparative example five:
the resin composition comprises: 60 parts of epoxy resin (YEP-250, Guangdong Guangshan) and nano SiO2(winning company, Nanopol A710), phenoxy resin (Inchem, PKHH)10 parts, and amine curing agent (dicyandiamide) 2 parts. 0.5 part of imidazole accelerator (2-MI) and a solvent (DMAC: MEK 1:1) are added into the composition to prepare a glue solution, the glue solution is uniformly stirred and mixed, then the glue solution is coated on the rough surface of the electrolytic copper foil, and the rough surface is baked in an oven at 155 ℃ for 6 minutes to obtain a resin-coated copper foil (RCC) product. Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Comparative example six:
the resin composition comprises: 90 parts of epoxy resin (Hemson corporation, EPIKOTE 627-B-80), 15 parts of polyether sulfone (SOLVAY, 3600RP) and nano SiO2(winning company, Nanopol A710), 20 parts of phenoxy resin (Inchem company, PKHH) and 5 parts of amine curing agent (dicyandiamide). 0.2 part of imidazole accelerator (2-MI) and a proper amount of solvent (DMAC: MEK 1:1) are added into the composition to prepare glue solution with the solid content of 40-60%, the glue solution is uniformly stirred and mixed, then the glue solution is coated on the rough surface of the electrolytic copper foil, and the rough surface is baked in an oven at 155 ℃ for 6 minutes to obtain a resin-coated copper foil (RCC) product. Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Comparative example seven:
the resin composition comprises: 90 parts of epoxy resin (Hemson company, EPIKOTE 627-B-80), 60 parts of polyether sulfone (SOLVAY, 3600RP) and nano SiO2(winning company, Nanopol A710), 20 parts of phenoxy resin (Inchem company, PKHH) and 5 parts of amine curing agent (dicyandiamide). 0.3 part of imidazole accelerator (2-MI) and a proper amount of solvent (DMAC: MEK ═ 1:1) are added into the composition to prepare glue solution with the solid content of 40-60%, the glue solution is evenly stirred and mixed and then coated on the rough surface of the electrolytic copper foil, and the rough surface is baked in an oven at 155 ℃ for 6 minutes to obtain a resin coated copper foil (RCC) product. Two sheets of RCC resin were then stacked and laminated with the resin facing side, with the lamination ramp rate of 2-3 deg.C/min, and cured between 180 deg.C and 200 deg.C for 60-90 minutes, with the test properties shown in Table 1.
Comparative example eight:
the resin composition comprises: 60 parts of epoxy resin (Hemson corporation, EPIKOTE 627-B-80), 30 parts of polyether sulfone (SOLVAY, 3600RP) and nano SiO2(winning company, Nanopol A710), phenoxy resin (Inchem company, PKHH)10 parts, and phenolic resin curing agent (Resolution company, EPIKURE YLH129B65)10 parts. And adding 0.15 part of imidazole accelerator (2-MI) and 100 parts of solvent (DMAC: MEK ═ 1:1) into the composition to prepare a glue solution, uniformly stirring and mixing the glue solution, coating the glue solution on the roughened surface of the electrolytic copper foil, and baking the copper foil in an oven at 150-160 ℃ for 3-6 minutes to obtain a resin-coated copper foil (RCC) product. Then two sheets of RCC resin are stacked and laminated facing the resin surface, the heating rate of the lamination is 2-3 ℃/min, the lamination is cured for 60-90 min at the temperature of 180-200 ℃, and finally the detection performance is shown in Table 1.
Comparative example nine:
the resin composition comprises: 60 parts of epoxy resin (Hemson corporation, EPIKOTE 627-B-80), 30 parts of polyether sulfone (SOLVAY, 3600RP) and nano SiO2(winning company, Nanopol A710), 10 parts of phenoxy resin (Inchem company, PKHH), and 40 parts of phenolic resin curing agent (Resolution company, EPIKURE YLH129B 65). 0.15 part of imidazole accelerator (2-MI) and 100 parts of solvent (DMAC: MEK ═ 1:1) are added into the composition to prepare glue solution, the glue solution is uniformly stirred and mixed, then the glue solution is coated on the roughened surface of the electrolytic copper foil, and then the roughened surface is baked in an oven at 150-160 ℃ for 3-6 minutes to obtain a resin coated copper foil (RCC) product. Then two sheets of RCC resin are stacked and laminated facing the resin surface, the heating rate of the lamination is 2-3 ℃/min, the lamination is cured for 60-90 min at the temperature of 180-200 ℃, and finally the detection performance is shown in Table 1.
The test method of the above characteristics is as follows:
(1) glass transition temperature (Tg): the determination was carried out using the DMA (dynamic thermal analysis) test according to the DMA test method specified in IPC-TM-6502.4.24.
(2) Modulus (100 ℃): the determination was carried out using the DMA (dynamic thermal analysis) test according to the DMA test method specified in IPC-TM-6502.4.24.
(3) Coefficient of Thermal Expansion (CTE): the measurement was carried out by using a thermomechanical analyzer (TMA) test according to the TMA test method specified by IPC-TM-6502.4.24.1.
(4) Peel strength: the test is specified with reference to IPC-TM-650.
(5) Thermal decomposition temperature (Td 5% loss): the test is specified with reference to IPC-TM-650.
(6) Evaluation of Heat resistance: referring to IPC-TM-650 specified test, after etching the copper foil on the surface of the copper clad laminate, evaluating the substrate; the substrate was immersed in a tin furnace at 288 ℃ for 10s each, and the number of immersion times at which blistering or delamination occurred was measured.
(7) Reflow soldering: reference JEDEC Standard 22-A113D)
(1) The heating rate is as follows: 3 ℃/sec Max (recommended)
(2)150 ℃ and 260 ℃ for more than 150 sec.
(3) The maximum temperature is maintained at 260 ℃ for more than 20sec, and the maximum temperature is maintained at 25-260 ℃ for 3-5 min.
As can be seen from the test results, the glass transition temperature (Tg), the thermal decomposition temperature (Td), the Coefficient of Thermal Expansion (CTE), the DMA modulus at 100 ℃, and the heat resistance of the examples of the present invention are higher and the dusting property is improved, compared to the comparative example one and the comparative example two to which polyethersulfone and nano-silica are not added; compared with a third comparative example without the phenolic resin, the peel strength of the examples of the invention is higher; without adding nano SiO2Comparative example four, the inventive examples have higher modulus and lower CTE; compared with the fifth comparative example without polyether sulfone, the Tg, Td, CTE, modulus and heat resistance of the inventive example are all higher; compared with the sixth comparative example with less active polyether sulfone, the Tg, modulus and CTE of the embodiment of the invention are higher, and the heat resistance is improved; compared with the seventh comparative example in which the use amount of the active polyether sulfone exceeds the range required by the scheme, the peel strength of the embodiment of the invention is higher; compared with the eighth and ninth comparative examples in which the equivalent ratio of the curing agent to the epoxy resin does not satisfy the requirements of the present application, the examples of the present invention are better in peel strength, powder falling property and heat resistance. Therefore, all the performances of the embodiment of the invention are excellent, and the use requirements of any layer of high-density interconnection PCB with higher performance can be better met.
The foregoing merely illustrates some preferred embodiments of the invention. Although the present invention has been described in detail by way of the above-described embodiments, the present invention is not limited to the above-described details, i.e., it is not intended that the present invention be implemented by relying on the above-described details. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810413299.1A CN108676533B (en) | 2018-05-03 | 2018-05-03 | Resin composition and resin-coated copper foil made therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810413299.1A CN108676533B (en) | 2018-05-03 | 2018-05-03 | Resin composition and resin-coated copper foil made therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108676533A CN108676533A (en) | 2018-10-19 |
| CN108676533B true CN108676533B (en) | 2021-05-11 |
Family
ID=63801782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810413299.1A Active CN108676533B (en) | 2018-05-03 | 2018-05-03 | Resin composition and resin-coated copper foil made therefrom |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108676533B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102752625B1 (en) | 2019-02-15 | 2025-01-10 | 엘지이노텍 주식회사 | Circuit board |
| CN112662132B (en) * | 2020-12-22 | 2023-08-22 | 广东盈骅新材料科技有限公司 | Modified resin composition and preparation method and application thereof |
| CN114591708B (en) * | 2020-12-30 | 2023-04-07 | 广东生益科技股份有限公司 | Resin composition, resin adhesive film and application thereof |
| CN112745782B (en) * | 2020-12-31 | 2022-09-30 | 苏州赛伍应用技术股份有限公司 | Hot-pressing insulating film and bus bar |
| CN116285231B (en) * | 2023-05-18 | 2023-08-29 | 东方飞源(山东)电子材料有限公司 | Electronic-grade copper-clad plate resin and preparation method thereof |
| CN116985411A (en) * | 2023-09-21 | 2023-11-03 | 江苏生益特种材料有限公司 | Preparation method of high-peel strength high-heat-conductivity high-frequency copper-clad plate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6447915B1 (en) * | 1999-03-11 | 2002-09-10 | Sumitomo Bakelite Company Limited | Interlaminar insulating adhesive for multilayer printed circuit board |
| MY121156A (en) * | 1999-07-02 | 2005-12-30 | Sumitomo Chemical Co | Thermosetting resin composition for build-up method |
| JP5471423B2 (en) * | 2009-03-31 | 2014-04-16 | 東レ株式会社 | Underfill agent and semiconductor device using the same |
| CN104629342A (en) * | 2014-12-10 | 2015-05-20 | 广东生益科技股份有限公司 | A kind of resin composition and cover film prepared with the resin composition |
| CN108350253A (en) * | 2015-12-17 | 2018-07-31 | 东丽株式会社 | Preform adhesive resin composition, binder particles, reinforcing-fiber substrate, preform and fibre reinforced composites |
-
2018
- 2018-05-03 CN CN201810413299.1A patent/CN108676533B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 聚醚砜/纳米二氧化硅改性环氧树脂胶黏剂的制备及性能研究;白孟瑶;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120515(第5期);B016-460 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108676533A (en) | 2018-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108676533B (en) | Resin composition and resin-coated copper foil made therefrom | |
| CN102633990A (en) | Epoxy resin composition and prepreg and copper-clad laminate manufactured using it | |
| CN107868399A (en) | A kind of resin combination and product containing the resin combination and preparation method thereof | |
| KR20070089053A (en) | Thermosetting Resin Compositions, Wet-Stage Resin Films, and Multi-Layer Build-up Substrates | |
| CN101104727B (en) | Halogen-free resin composition and resin-coated copper foil for high-density interconnection | |
| CN111635616B (en) | Halogen-free flame-retardant thermosetting resin composition, prepreg for printed circuit, and metal-clad laminate | |
| KR101044114B1 (en) | Resin composition for printed circuit board and printed circuit board using same | |
| CN104804377A (en) | A kind of halogen-free resin composition and its prepreg and laminate | |
| JP3821728B2 (en) | Prepreg | |
| CN103740055B (en) | A kind of compositions of thermosetting resin and application thereof | |
| JP2014105332A (en) | Resin composition for printed circuit board, insulating film, prepreg, and printed circuit board | |
| JP4322463B2 (en) | Copper-clad laminate prepreg and copper-clad laminate | |
| JP5303826B2 (en) | Resin composition, prepreg and printed wiring board using the same | |
| CN102260402A (en) | Epoxy resin composition and prepreg and printed circuit board made therefrom | |
| JP4132755B2 (en) | Resin composition, prepreg and printed wiring board using the same | |
| JP2003213019A (en) | Prepreg and printed wiring board using the same | |
| JP2004277671A (en) | Prepreg and printed circuit board using the same | |
| JP5428212B2 (en) | Resin composition, prepreg and printed wiring board using the same | |
| KR20220077993A (en) | Resin composition for high frequency, prepreg, metal clad laminate, laminate sheet and printed circuit board using the same | |
| CN115181395B (en) | Thermosetting resin composition and application thereof | |
| CN1198875C (en) | Thermosetting resin composite for assembling process | |
| JP3821797B2 (en) | Resin composition, resin-coated metal foil and multilayer printed wiring board | |
| JP2005209489A (en) | Insulation sheet | |
| CN102838842A (en) | Epoxy resin composition and prepreg and copper-clad laminate produced therefrom | |
| JP4150178B2 (en) | Resin composition, prepreg and printed wiring board using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |