CN114149658B - Resin composition and low-gummosis prepreg prepared from same - Google Patents

Resin composition and low-gummosis prepreg prepared from same Download PDF

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Publication number
CN114149658B
CN114149658B CN202111667600.XA CN202111667600A CN114149658B CN 114149658 B CN114149658 B CN 114149658B CN 202111667600 A CN202111667600 A CN 202111667600A CN 114149658 B CN114149658 B CN 114149658B
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curing agent
resin composition
resin
epoxy resin
aromatic amine
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CN114149658A (en
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何继亮
黄荣辉
陈诚
王宁
崔春梅
焦锋
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Changshu Shengyi Technology Co ltd
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Changshu Shengyi Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C08J2463/04—Epoxynovolacs
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • 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

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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)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention provides a resin composition and a low-flow glue prepreg manufactured by using the same, wherein the resin composition comprises the following components: epoxy resin: 100 parts by weight; an aromatic amine curing agent, wherein the ratio of the active hydrogen equivalent of the aromatic amine curing agent to the epoxy equivalent of the epoxy resin is 0.3-2.0; an imidazole curing agent, wherein the weight ratio of the imidazole curing agent to the aromatic amine curing agent is 0.03-1.0; the weight ratio of the toughness resin to the total weight of the epoxy resin, the aromatic amine curing agent and the imidazole curing agent is as follows: 0.01 to 0.5.

Description

Resin composition and low-gummosis prepreg prepared from same
Technical Field
The invention relates to the technical field of electronic materials, in particular to a resin composition and a low-flow glue prepreg manufactured by using the same.
Background
Currently, rigid-flex printed circuit boards are a type of printed circuit board that is currently in great demand and development. The rigid-flex printed circuit board is formed by combining a lamellar flexible bottom layer and a rigid bottom layer and laminating the lamellar flexible bottom layer and the rigid bottom layer into a single component, the rigid-flex printed circuit board changes the traditional planar design concept, expands the three-dimensional 3-dimensional space concept, and brings great convenience to product design and also brings great challenges. A typical (four layer) flex-rigid printed circuit board has a polyimide core with copper foil on both its upper and lower surfaces. The outer rigid layer consists of single sided FR-4 (fiberglass board) laminated to both sides of the flexible core, assembled into a multi-layer PCB. In the fabrication of a multi-layer flex-rigid board, the processing of the flex layer is in turn quite different from the external FR-4 layer. The layers of different materials must be gathered together by lamination, then drilled and electroplated. Thus, a typical four-layer flex-rigid printed circuit board may be fabricated 5 to 7 times longer than a standard four-layer flex-rigid printed circuit board. At present, the application range of the rigid-flex printed circuit board mainly comprises: aerospace, such as high-end aircraft mounted weapon navigation systems, advanced medical devices, digital cameras, portable cameras and high-quality MP3 players. Rigid-flex boards are most commonly used in the manufacture of military aircraft and medical equipment. The rigid-flex board provides great benefits to the design of a military aircraft because it reduces weight while improving connection reliability.
The rigid-flex printed circuit board needs to be bonded with a soft board and a hard board by using a bonding material when in processing and manufacturing, and the most common bonding material in the prior art is a low-fluidity prepreg. Compared with the conventional FR-4 prepreg, the low resin fluidity prepreg needs to have the characteristic of little or no gummosis under high temperature and high pressure, and also needs to have good adhesive force, excellent toughness and low powder falling property. Because of the minimal or little bleeding of low-flow prepregs at high temperatures and pressures, it is often desirable to increase the degree of reaction of the resin system, which can result in a reduction in the bonding ability of the adhesive sheet. Particularly, the bonding force between the low-flow glue prepreg and the polyimide surface of the soft board is one of factors which seriously influence the reliability of the soft and hard combined board. In addition, with the increase of product requirements, a higher proportion of filler needs to be added into the low-flow glue prepreg in some cases, which also leads to the obvious decrease of the bonding force between the low-flow glue prepreg and the polyimide surface of the flexible board.
In order to solve the problem of the bonding force between the low-flow prepreg and the polyimide surface of the flexible board, a thermosetting resin composition composed of allyl modified bismaleimide resin and epoxy resin with a special structure is used in the Chinese patent application No. CN104164087A, and the problem of the bonding force between the low-flow prepreg and the polyimide surface of the flexible board is mainly solved by using the epoxy resin with the special structure in the patent. However, the technical proposal in the patent has the problem of large powder dropping caused by insufficient toughness, and can seriously affect the processing performance of the printed circuit board. To improve the toughness problem of the low-flow prepregs, too much bisphenol a type epoxy resin is added, which in turn causes the problem of lower glass transition temperature.
In order to improve toughness and powder dropping performance of the low-flow prepreg, in the prior art, macromolecular polymers such as phenol-oxygen resin, nitrile rubber, polyacrylate resin and the like are generally added into a resin system, however, excessive addition of macromolecular polymers can cause the wettability of the resin system to glass fiber cloth to be reduced, and defects such as resin cavities are formed in the prepreg, which can cause the reliability to be reduced after the low-flow prepreg is pressed.
Therefore, a novel resin composition and a low-flow glue prepreg manufactured by using the same are developed, the bonding force between the low-flow glue prepreg and the polyimide surface of a soft board is improved, the low-flow glue prepreg is ensured to have excellent heat resistance, toughness and low powder dropping property, the problem of reduced wettability of a resin system to glass fiber cloth can be avoided, and the low-flow glue prepreg has positive practical significance obviously.
Disclosure of Invention
The invention aims to provide a resin composition and a low-gummosis prepreg prepared by using the same, wherein the low-gummosis prepreg has low gummosis quantity and excellent adhesive force, and particularly has excellent adhesive force with a polyimide surface of a soft board.
The technical scheme of the invention provides: a resin composition, the resin composition comprising: epoxy resin: 100 parts by weight; an aromatic amine curing agent, wherein the ratio of the active hydrogen equivalent of the aromatic amine curing agent to the epoxy equivalent of the epoxy resin is 0.3-2.0; an imidazole curing agent, wherein the weight ratio of the imidazole curing agent to the aromatic amine curing agent is 0.03-1.0; the weight ratio of the toughness resin to the total weight of the epoxy resin, the aromatic amine curing agent and the imidazole curing agent is as follows: 0.01 to 0.5.
As an alternative technical scheme, the ratio of the active hydrogen equivalent of the aromatic amine curing agent to the epoxy equivalent of the epoxy resin is 0.5-1.0.
As an alternative technical scheme, the weight ratio of the imidazole curing agent to the aromatic amine curing agent is 0.08-0.25.
As an alternative technical scheme, the weight ratio of the imidazole curing agent to the aromatic amine curing agent is 0.05-0.5.
As an alternative technical scheme, the epoxy resin is a polymer containing more than two epoxy groups in a molecular structure.
As an optional technical solution, the method further includes: and the filler accounts for 5-80 wt% of the total weight of the resin composition.
As an alternative technical solution, the filler accounts for 50 to 70wt% of the total weight of the resin composition.
As an alternative technical scheme, the resin composition further comprises a flame retardant, wherein the flame retardant accounts for 5-30% of the total weight of the resin composition by weight.
As an optional technical solution, the method further includes: and the boron-containing compound is selected from boric acid or borax, and the ratio of the weight of the boron-containing compound to the weight of the imidazole curing agent is 0.1-2.0.
The invention also provides a low-flow glue prepreg which is manufactured by using the resin composition.
In summary, the invention provides a resin composition and a low-flow prepreg manufactured by using the same, wherein in an epoxy resin system, the ratio of the active hydrogen equivalent of an aromatic amine curing agent to the epoxy equivalent of epoxy resin is 0.3-2.0; the weight ratio of the imidazole curing agent to the aromatic amine curing agent is 0.03-1, preferably 0.08-0.25; the weight ratio of the ductile resin to the total weight of other components (resin and curing agent) is 0.01-0.5; the low-gumming prepreg prepared based on the resin composition has excellent heat resistance, bonding performance, lower powder removal rate, lower gum overflow amount and excellent comprehensive performance.
Compared with the prior art, the resin composition and the low-gummosis prepreg prepared by using the same have the following beneficial effects:
the invention develops a novel resin composition for preparing a low-gumming prepreg, the aromatic amine curing agent and the imidazole curing agent are combined, and the low-gumming bonding sheet with excellent heat resistance, bonding performance, lower powder removal rate and lower gumming quantity is obtained by optimizing the weight ratio of the aromatic amine curing agent to the imidazole curing agent, and particularly, the bonding force between the low-gumming bonding sheet and a polyimide surface of a flexible board is remarkably improved.
The present invention will be described in detail with reference to specific examples, but is not limited thereto.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention aims to provide a resin composition and a low-flow glue prepreg prepared by using the same, wherein the weight ratio of an imidazole curing agent to an aromatic amine curing agent in the resin composition is regulated to be 0.03-2.0, preferably 0.08-0.25; the adhesive force between the low-flow glue prepreg manufactured based on the resin composition and the PI layer is improved.
The present invention provides a resin composition comprising:
epoxy resin: 100 parts by weight;
an aromatic amine curing agent, wherein the ratio of the active hydrogen equivalent of the aromatic amine curing agent to the epoxy equivalent of the epoxy resin is 0.03-2.0;
imidazole curing agent, imidazole curing agent and aromatic amine curing agent in the weight ratio of 0.03-1;
the weight ratio of the tough resin to the total weight of the epoxy resin, the aromatic amine curing agent and the imidazole curing agent is as follows: 0.01 to 0.5.
In the technical scheme, the ratio of the active hydrogen equivalent of the aromatic amine curing agent to the epoxy equivalent of the epoxy resin is 0.5-1.0.
In the technical scheme, the weight ratio of the imidazole curing agent to the aromatic amine curing agent is 0.05-0.5; more preferably, the weight ratio of the imidazole curing agent to the aromatic amine curing agent is 0.08 to 0.25.
In the technical scheme, the epoxy resin: 100 parts by weight; when the ratio of the active hydrogen equivalent of the aromatic amine curing agent to the epoxy equivalent of the epoxy resin is 0.5-1.0; the weight ratio of the imidazole curing agent to the aromatic amine curing agent is 0.08-0.25; and the weight ratio of the ductile resin to the total weight of the epoxy resin, the aromatic amine curing agent and the imidazole curing agent is as follows: 0.01 to 0.5; the low-gumming prepreg prepared from the resin composition in the proportion relation can obtain the maximum beneficial effect.
In the technical scheme, the epoxy resin is a polymer containing more than two epoxy groups in a molecular structure.
Specifically, the epoxy resin may be one or more selected from the group consisting of a phosphorus-containing epoxy resin, a nitrogen-containing epoxy resin, a multifunctional epoxy resin, a bisphenol a epoxy resin, a bisphenol F epoxy resin, a tetraphenylethane epoxy resin, a triphenylmethane epoxy resin, a biphenyl epoxy resin, a naphthalene ring type epoxy resin, a dicyclopentadiene type epoxy resin, an isocyanate type epoxy resin, a phenol epoxy resin, a methylphenol epoxy resin, a bisphenol type phenol epoxy resin, a polyphenylene ether modified epoxy resin, an alicyclic type epoxy resin, an allylglycidol type epoxy resin, a glycidylamine type epoxy resin, and a glycidylester type epoxy resin.
In order to ensure that the obtained low-flow prepreg and the soft board polyimide have good surface binding force, the epoxy resin preferably contains one or more of DOPO-HQ type phosphorus-containing epoxy resin, biphenyl type epoxy resin and bisphenol type phenolic epoxy resin; more preferably, the epoxy resin comprises bisphenol type novolac epoxy resin, and the bisphenol type novolac epoxy resin may be bisphenol a type novolac epoxy resin, bisphenol F type novolac epoxy resin, bisphenol S type novolac epoxy resin, or dihydroxydiphenyl ether type novolac epoxy resin.
In order to make the resin system in the obtained low-flow prepreg have good wettability to glass fiber cloth and avoid the defects of forming resin holes and the like in the prepreg, the epoxy resin preferably contains one or more small molecule epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, dihydroxydiphenyl ether epoxy resin, allyl glycidyl ether, N, N, N ', N ' -tetraepoxypropyl-4, 4' -diaminodiphenyl methane and the like.
Preferably, in order to make the obtained low-flow adhesive sheet have better anti-sticking property and heat resistance, when one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, dihydroxydiphenyl ether epoxy resin and allyl glycidyl ether is/are contained in the epoxy resin, the addition amount of the bisphenol a epoxy resin, bisphenol F epoxy resin, dihydroxydiphenyl ether epoxy resin and allyl glycidyl ether is 1-15% of the total solid weight of the total resin composition.
In the above technical scheme, the aromatic amine curing agent refers to an amine curing agent with an aromatic substituent in a molecular structure, and comprises aromatic amine and modified substances thereof. The aromatic amine curing agent can be selected from one or a mixture of any one of m-phenylenediamine and modified substances thereof, diaminodiphenyl methane and modified substances thereof, diaminodiphenyl sulfone and modified substances thereof, diaminodiphenyl ether and modified substances thereof, m-aminomethylamine and modified substances thereof, biphenyl diamine and modified substances thereof. Preferably, the aromatic amine curing agent is diaminodiphenyl methane, diaminodiphenyl sulfone and diaminodiphenyl ether. The amount of the aromatic amine curing agent added cannot be excessive, and after the amount of the aromatic amine curing agent added exceeds 2.0 in terms of the ratio of the active hydrogen equivalent of the aromatic amine curing agent to the epoxy equivalent of the epoxy resin, the problem of increased powder removal rate and the problem of deterioration of heat resistance such as decrease of Tg, deterioration of thermal stress and the like occur. Therefore, from the viewpoints of heat resistance and powder removal rate, the amount of the aromatic amine-based curing agent to be added is not more than 2.0 in terms of the ratio of the active hydrogen equivalent of the aromatic amine-based curing agent to the epoxy equivalent of the epoxy resin of the component (a).
In the above technical scheme, the imidazole curing agent refers to a five-membered aromatic heterocyclic compound curing agent containing two meta-position nitrogen atoms in a molecular structure, and comprises imidazole and modified substances thereof. The imidazole-based curing agent may be selected from one or a mixture of 2-methylimidazole (2-MZ), diethylimidazole (2-EI), 2-ethyl-4-methylimidazole (2E 4 MZ), 2-phenylimidazole (2-PZ), 2-phenyl-4-methylimidazole (2P 4 MZ), 2-undecylimidazole (C11Z), 2-heptadecylimidazole (C17Z), 2, 4-diamine-6- (2 ' -undecylimidazole- (1 ')) -ethyltriazine (C11Z-a), 1-cyanoethylundecylimidazole (C11Z-CN), 1-cyanoethyl-2-undecylimidazole-trimellitic acid adduct (C11Z-CNs), 2, 4-diamine-6- (2 ' -ethyl-4 ' -methylimidazole- (1 ')) -ethyltriazine (2E 4 MZ-a), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E 4 MZ-CN), 2, 4-diamine-6- (2 ' -methylimidazole- (1 ')) -ethyltriazine (2 a).
In the above technical solution, in order to obtain a low-flow prepreg with better storage stability, the imidazole curing agent is preferably one or any imidazole with relatively high reaction temperature, such as 2-undecylimidazole (C11Z), 2-heptadecylimidazole (C17Z), 2, 4-diamine-6- (2 ' -undecylimidazole- (1 ')) -ethyltriazine (C11Z-a), 1-cyanoethylundecylimidazole (C11Z-CN), 1-cyanoethyl-2-undecylimidazole-trimellitic acid adduct (C11Z-CNs), 2, 4-diamine-6- (2 ' -ethyl-4 ' -methylimidazole- (1 ')) -ethyltriazine (2E 4 MZ-a), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E 4 MZ-CN), 2, 4-diamine-6- (2 ' -methylimidazole- (1 ')) -ethyltriazine (2 MZ-a). In addition, when the imidazole reaction temperature is relatively low in view of the process operability and storage stability of the formulation, boron-containing compounds such as boric acid and borax can be added into the formulation to slow down the curing reaction of the imidazole curing agent, wherein the addition amount is that the weight ratio of the boron-containing compounds to the imidazole curing agent is 0.1-2.0. Other similar chemicals that slow down the reaction of the imidazole curing agent may also be added.
In the above technical solution, in order to obtain a low-flow prepreg and a PI film having more excellent adhesive strength, the imidazole curing agent is preferably one or any of 2, 4-diamine-6- (2 ' -undecylimidazolyl- (1 ')) -ethyltriazine (C11Z-a), 2, 4-diamine-6- (2 ' -ethyl-4 ' -methylimidazolyl- (1 ')) -ethyltriazine (2E 4 MZ-a), and 2, 4-diamine-6- (2 ' -methylimidazolyl- (1 ')) -ethyltriazine (2 MZ-a).
In the above technical scheme, the weight ratio of the imidazole curing agent to the aromatic amine curing agent is 0.03-1, more preferably 0.08-0.25.
In the technical scheme, the tough resin can be one or more selected from phenol-oxygen resin, nitrile rubber, core-shell rubber and polyacrylate resin.
The phenol oxygen resin can be selected from one or more of allyl phenol oxygen resin, phosphorus-containing phenol oxygen resin, sulfur-containing phenol oxygen resin, bisphenol A glycidyl ether type, bisphenol F glycidyl ether type or biphenyl type glycidyl ether type phenol oxygen resin; preferably, the weight average molecular weight is 5000-70000; more preferably, the weight average molecular weight thereof is 20000 to 50000.
The nitrile rubber may be selected from carboxylated nitrile rubber, aminonitrile rubber or other modified nitrile rubber, preferably a solid rubber or modified solid rubber of relatively high molecular weight, more preferably having a weight average molecular weight of 50000 to 300000.
The polyacrylate resin may be selected from acrylate homopolymers, other vinyl monomers and copolymers of acrylate esters. Preferably, the polyacrylate is an acrylate triblock copolymer. The acrylate triblock copolymer refers to a triblock copolymer comprising a middle flexible segment and hard segments at both ends. The middle flexible block can be a block with good flexibility such as polybutyl acrylate, polybutyl methacrylate, polyethyl acrylate, isooctyl polyacrylate, poly (2-ethylhexyl) acrylate, poly (2-ethylhexyl) methacrylate or polybutadiene; the hard segments at both ends may be blocks with better rigidity such as polymethacrylate and polystyrene. Preferably, the acrylate triblock copolymer is a polystyrene-polybutadiene-polymethacrylate triblock copolymer, a polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer. Preferably, the weight average molecular weight of the acrylate triblock copolymer is 10000 to 800000, more preferably, the weight average molecular weight of the acrylate triblock copolymer is 10000 to 300000. When the molecular weight is large, the toughness and heat resistance of the acrylic ester are good, but there may be a problem of compatibility with other resins. In order to improve the compatibility of the acrylic ester and other resins, the acrylic ester block copolymer may be modified by functionalization, and may be modified by hydroxyl functionalization, carboxyl functionalization, amino functionalization, or epoxy functionalization. The amount of the polyacrylate resin to be added is preferably 1 to 10 parts by weight based on 100 parts by weight of the epoxy resin. When the molecular weight of the acrylic acid ester is high, the addition amount of the acrylic acid ester may be appropriately reduced in order to improve the compatibility of the acrylic acid ester with other resins, and the addition amount is preferably 1 to 5 parts by weight.
The resin composition of the present invention may further include a flame retardant, and the flame retardant may be 5 to 30% by weight based on the total weight of the resin composition.
Specifically, the flame retardant may be a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, or the like. The phosphorus flame retardant may be an organic phosphorus-containing compound such as a phosphorus-containing phenolic resin, an inorganic phosphorus, a phosphate compound, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide, and tris (2, 6-dimethylphenyl) phosphazene. The nitrogen-based flame retardant may be a triazine compound, cyanuric acid compound, isocyanic acid compound, phenothiazine, or the like. The silicone flame retardant may be silicone oil, silicone rubber, silicone resin, or the like. The inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, or the like.
The resin composition of the present invention may further comprise a filler, and the proportion of the filler to the total weight of the resin composition may be 5 to 80% by weight.
Specifically, the filler can be one or more selected from crystalline silica, fused silica, spherical silica, alumina, aluminum hydroxide, aluminum nitride, boron nitride, titanium dioxide, strontium titanate, barium sulfate, talcum powder, calcium silicate, calcium carbonate, mica, polytetrafluoroethylene and graphene. The filler may be surface-treated with a silane coupling agent, and may be directly put into or pre-prepared into a filler dispersion or made into a paste to be put into a resin composition. The particle size of the filler is preferably 0.5 to 10 μm (particle size D50).
In order to give the resulting low-flow prepregs an excellent low powder removal rate, the filler content is preferably: the filler comprises 5 to 15 weight percent of the total weight of the resin composition.
In order to give the resulting low-flow prepregs excellent rigidity and thermal conductivity, the filler content is preferably 50 to 70% by weight. In order to obtain a low-flow prepreg which has excellent thermal conductivity and also has excellent interlayer adhesion and copper foil adhesion, the filler is preferably alumina.
In addition, the resin composition of the present invention may further contain special functional aids such as dispersants, coupling agents, defoamers, leveling agents, colorants, compatibilizers, UV blocking agents, and the like.
The invention also provides a low-flow glue prepreg which is manufactured by using the resin composition.
The manufacturing method of the low-flow glue prepreg comprises the following steps: adding the resin composition and the solvent into a glue mixing kettle, preparing reactants with the solid content of 40-70%, uniformly stirring, and curing for 4-8 hours to prepare resin composition glue solution; then the reinforcing material is immersed in the resin composition glue solution, and the immersed reinforcing material is reacted and dried in the environment of 100-200 ℃ according to the set procedure, thus obtaining the low-gummosis prepreg.
Wherein the reinforcing material can be natural fiber, organic synthetic fiber, organic fabric or inorganic fabric. The diluent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, acetone, butanone, propylene glycol methyl ether, ethylene glycol ethyl ether, methanol, ethanol, benzene, toluene, paraxylene, tetrahydrofuran, N-methylpyrrolidone and dimethyl sulfoxide.
The preparation process of the resin composition glue solutions in examples 1 to 9 is as follows:
the components were uniformly mixed in the amounts shown in Table 1 to prepare resin compositions 1 to 9 having a solid content of 50%, stirred uniformly, and cured for 4 to 8 hours to prepare resin composition dope 1 to 9;
TABLE 1 Components and contents of examples 1 to 9
The preparation process of the resin composition glue solution in comparative examples 1 to 8 is as follows:
the components were uniformly mixed in the amounts shown in Table 2 to prepare resin compositions 10-16 having a solid content of 50%, stirred uniformly, and cured for 4-8 hours to prepare resin composition dope 10-16;
TABLE 2 Components and contents of comparative examples 1 to 8
The preparation of the low-flow glue prepreg comprises the following steps:
the resin composition glue solution 1-9 in the above example and the resin composition glue solution 10-16 in the above comparative example were impregnated with electronic grade 2116 glass fiber cloth as a reinforcing material, and then the prepreg was heat-cured in an oven according to a certain temperature (100-200 ℃) and time (2-10 min) procedure to obtain a low-flow glue prepreg 1-16, a part of the prepreg was pressed into a laminate under the following conditions, and then the properties of the prepreg and laminate were evaluated by the following methods.
The manufacturing conditions of the plate are as follows: the stacking structure is 1/2OZ Cu+2x2116 bonding sheet+1/2 OZ Cu, the copper foil thickness is 1/2OZ, and the thickness of the plate after molding is as follows: 0.25mm, wherein the curing condition is that the temperature rises 3-5 ℃/min, and the material temperature is 200 ℃/1-2h;
the manufacturing conditions of the PI film bonding strength test board are as follows: the lamination is 1/2OZ Cu+25umPI film+1x2116+1/2 OZ Cu, the curing condition is that the temperature rises 3-5 ℃/min, and the material temperature is 200 ℃/1-2h.
The test items and test conditions were as follows:
< determination of glue overflow amount >: and (3) preparing PP into square samples with the size of 100mm and 100mm, punching a 1-inch round hole in the middle position, stacking the PP samples together in a stacking mode of steel plate, copper-clad plate, PP sample, release film, buffer material and steel plate, pressing by using a press with set temperature/pressure/time, and taking out the glue overflow quantity of the round hole position of the sample after the pressing is finished so as to evaluate the glue overflow quantity of the sample under the hot pressing condition.
< powder removal rate) >, measurement: the falling degree of the resin powder after the prepreg is subjected to punching/shearing treatment is taken as a judgment basis. The specific test method is that 4 prepregs with the size of 10cm x 10cm are taken, weighed and recorded as m1. A gap with the depth of 9cm is cut on one side of the sample by using scissors, 29 cutters are cut, each sample is made into 30 strips with the length of 9cm, and each strip is treated in the same way. The hand-held sample was vibrated up and down 30 times with the wrist as the center, and one back and forth was noted as one vibration. And weighing again after finishing, recording the weight as m2, and calculating the powder removal rate of the prepreg according to (m 1-m 2)/m 1x 100%.
< PI film adhesive strength > measurement: and simulating the stacking condition of the soft and hard combined plate, pressing the adhesive-free surfaces of the low-flow adhesive bonding sheet and the PI cover film together, and using a universal material testing machine to test the bonding strength between the low-flow adhesive bonding sheet and the PI cover film by 90-degree stripping.
< determination of glass transition temperature (Tg) >: the test was performed using the DMA method according to the method prescribed by IPC-TM-650.2.4.25.
< determination of copper foil peel Strength >: the peel strength of the metal cap layer was tested according to the "post thermal stress" experimental conditions in the IPC-TM-650.2.4.8 method.
< determination of 288 ℃ thermal stress >: measured according to the IPC-TM-650.2.6.8 method.
The product property test structures in examples 1 to 9 and comparative examples 1 to 8 described above are shown in Table 3
TABLE 3 Performance test of boards obtained from resin composition glue solutions in examples 1 to 9 and comparative examples 1 to 8
As can be seen from table 3, 1) compared with the resin compositions and the low-flow glue prepregs prepared therefrom in comparative examples 1 to 8, examples 1 to 9 are low-flow glue prepregs prepared by adopting the resin composition scheme provided by the invention, wherein the bonding strength of the lowest PI film is greater than 1.6 and is greater than 1.5 of the bonding strength of the largest PI film of the low-flow glue prepregs in comparative examples, that is, the resin composition provided by the invention can enable the low-flow glue prepregs to have more excellent PI film bonding strength by controlling the weight ratio of imidazole curing agent to aromatic amine curing agent to be 0.08 to 0.25;
2) Meanwhile, the low-gummosis prepreg prepared by the resin composition provided by the invention has excellent heat resistance, bonding performance, lower powder removal rate and lower gum overflow amount, so that the comprehensive performance is excellent.
In summary, the invention provides a resin composition and a low-flow prepreg manufactured by using the same, wherein in an epoxy resin system, the ratio of the active hydrogen equivalent of an aromatic amine curing agent to the epoxy equivalent of epoxy resin is 0.3-2.0; the weight ratio of the imidazole curing agent to the aromatic amine curing agent is 0.03-1, preferably 0.08-0.25; the weight ratio of the ductile resin to the total weight of other components (resin and curing agent) is 0.01-0.5; the low-gumming prepreg prepared based on the resin composition has excellent heat resistance, bonding performance, lower powder removal rate, lower gum overflow amount and excellent comprehensive performance.
Compared with the prior art, the resin composition and the low-gummosis prepreg prepared by using the same have the following beneficial effects:
the invention develops a novel resin composition for preparing a low-gumming prepreg, the aromatic amine curing agent and the imidazole curing agent are combined, and the low-gumming bonding sheet with excellent heat resistance, bonding performance, lower powder removal rate and lower gumming quantity is obtained by optimizing the weight ratio of the aromatic amine curing agent to the imidazole curing agent, and particularly, the bonding force between the low-gumming bonding sheet and a polyimide surface of a flexible board is remarkably improved.
The invention has been described with respect to the above-described embodiments, however, the above-described embodiments are merely examples of practicing the invention. In addition, the technical features described above in the different embodiments of the present invention may be combined with each other as long as they do not collide with each other. It is to be noted that the present invention is capable of other various embodiments and that various changes and modifications can be made herein by one skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. A resin composition, characterized in that the resin composition comprises:
epoxy resin: 100 parts by weight;
an aromatic amine curing agent, wherein the ratio of the active hydrogen equivalent of the aromatic amine curing agent to the epoxy equivalent of the epoxy resin is 0.3-2.0;
an imidazole curing agent, wherein the weight ratio of the imidazole curing agent to the aromatic amine curing agent is one of 0.04, 0.08, 0.2, 0.25, 0.5 and 1;
the weight ratio of the toughness resin to the total weight of the epoxy resin, the aromatic amine curing agent and the imidazole curing agent is as follows: 0.01 to 0.5;
the epoxy resin is selected from one or more of phosphorus-containing epoxy resin, biphenyl type epoxy resin, bisphenol type epoxy resin and bisphenol type phenolic epoxy resin;
the aromatic amine curing agent is selected from one or more of diaminodiphenyl methane, diaminodiphenyl sulfone and diaminodiphenyl ether;
the imidazole curing agent is one or two selected from 2-ethyl-4-methylimidazole and 2, 4-diamine-6- (2 '-undecylimidazole- (1')) -ethyltriazine;
the ductile resin is a phenolic resin.
2. The resin composition according to claim 1, wherein the ratio of the active hydrogen equivalent of the aromatic amine-based curing agent to the epoxy equivalent of the epoxy resin is 0.5 to 1.0.
3. The resin composition according to claim 1, wherein the epoxy resin is a polymer having two or more epoxy groups in a molecular structure.
4. The resin composition according to claim 1, further comprising: and the filler accounts for 5-80 wt% of the total weight of the resin composition.
5. The resin composition according to claim 4, wherein the filler is present in an amount of 50 to 70wt% based on the total weight of the resin composition.
6. The resin composition according to claim 1, further comprising a flame retardant in a proportion of 5 to 30% by weight based on the total weight of the resin composition.
7. The resin composition according to claim 1, further comprising: and the boron-containing compound is selected from boric acid or borax, and the ratio of the weight of the boron-containing compound to the weight of the imidazole curing agent is 0.1-2.0.
8. A low-flow prepreg manufactured using the resin composition according to any one of claims 1 to 7.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073844A (en) * 2013-01-05 2013-05-01 广东生益科技股份有限公司 Halogen-free flame-retardant epoxy resin composition and cover film produced by halogen-free flame-retardant epoxy resin composition
CN103589380A (en) * 2013-10-24 2014-02-19 苏州威仕科贸有限公司 Improved epoxy resin adhesive
CN103694631A (en) * 2013-11-14 2014-04-02 昆山珍实复合材料有限公司 Halogen-free epoxy resin composition and cover film prepared by using halogen-free epoxy resin composition
CN107163274A (en) * 2017-06-20 2017-09-15 苏州生益科技有限公司 A kind of low flow prepreg

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073844A (en) * 2013-01-05 2013-05-01 广东生益科技股份有限公司 Halogen-free flame-retardant epoxy resin composition and cover film produced by halogen-free flame-retardant epoxy resin composition
CN103589380A (en) * 2013-10-24 2014-02-19 苏州威仕科贸有限公司 Improved epoxy resin adhesive
CN103694631A (en) * 2013-11-14 2014-04-02 昆山珍实复合材料有限公司 Halogen-free epoxy resin composition and cover film prepared by using halogen-free epoxy resin composition
CN107163274A (en) * 2017-06-20 2017-09-15 苏州生益科技有限公司 A kind of low flow prepreg

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