CN105860896A - Adhesive with high glass transition temperature for flexible cover film - Google Patents
Adhesive with high glass transition temperature for flexible cover film Download PDFInfo
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- CN105860896A CN105860896A CN201610280635.0A CN201610280635A CN105860896A CN 105860896 A CN105860896 A CN 105860896A CN 201610280635 A CN201610280635 A CN 201610280635A CN 105860896 A CN105860896 A CN 105860896A
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- 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
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- 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
-
- 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
- C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
- C09J181/06—Polysulfones; Polyethersulfones
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- 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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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an adhesive with high glass transition temperature for a flexible cover film and a preparation method of the adhesive. The adhesive is prepared from, by weight, 30-50 parts of toughening material, 15-30 parts of polyfunctional epoxy resin, 2.5-15 parts of curing agent, 0-0.5 part of imidazole accelerant, 15-25 parts of filler, 5-15 parts of flame-retardant filler, 1-5 parts of other additives and 60-70 parts of organic solvent. According to the adhesive with the high glass transition temperature for the flexible cover film and the preparation method of the adhesive, toughening resin which is excellent in toughness and high in glass transition temperature and the polyfunctional epoxy resin are adopted to prepare the adhesive, insulating plastic film is coated with the adhesive, a semi-cured adhesive layer is obtained, press-fit of a circuit or copper foil is achieved under the high-temperature and high-pressure conditions, baking is conducted for 1 h to 2 h at the temperature ranging from 160 DEG C to 180 DEG C, after complete curing is achieved, the glass transition temperature of the adhesive layer can reach 90 DEG C to 100 DEG C, and the material can be used for a long time under the high temperature condition.
Description
Technical field
The present invention relates to the adhesive for flexible coverlay, particularly relate to a kind of high-vitrification that has for flexible coverlay and turn
Adhesive of temperature and preparation method thereof.
Background technology
Along with science and technology and the fast development of electronics industry, electronic circuit is more and more intensive, uses condition more and more harsher, right
Material requirements is more and more higher.The existing toughness reinforcing mode of FCCl adhesive mainly using CTBN (nbr carboxyl terminal) as toughness reinforcing,
Tg point (glass transition temperature) of CTBN is low, is only about 50 DEG C with tg after adhesive solidification toughness reinforcing for CTBN.Electronics
Material uses under higher temperature conditions or in use temperature can raise, when temperature is higher than adhesive layer tg point, and glue
Adhesive layer can deform under force and cause material property to decline, and affects product serviceability, limits coverlay at height
The application in temperature field.
Coverlay is widely used as route protection layer, in order to improve material property, expands materials'use scope, and the present invention carries
Having supplied a kind of adhesive high for the glass transition temperature of flexible coverlay, this adhesive is coated and is made on ambroin thin film
Standby one-tenth semi-solid preparation glue-line, pressing circuit or Copper Foil under high-temperature and high-pressure conditions, after solidification, its adhesive layer tg point can reach
90-100 DEG C, material life-time service under higher temperature conditions can be met.
Summary of the invention
It is an object of the invention to the shortcoming overcoming existing adhesive glass transition temperature low, it is provided that a kind of for flexible coverlay
The adhesive with high glass-transition temperature and preparation method thereof.
The technical solution used in the present invention is: a kind of adhesive with high glass-transition temperature for flexible coverlay,
Component including following parts by weight:
Preferably, described toughening material be rubber, thermal plastic high polymer engineering material and epoxy resin toughened in one or several
Kind.
Preferably, described rubber is butadiene, acrylonitrile and the nbr carboxyl terminal of organic acid mixing copolymerization and nanometer
At least one in rubber elastomer;Described thermal plastic high polymer engineering plastics are Polyetherimide, polyethersulfone resin, polyphenyl
One or more in ether and polyimides;Described epoxy resin toughened be poly phenol oxygen epoxy resin and rubber toughened bisphenol-A
At least one in type epoxy resin.
Described nbr carboxyl terminal, is formed by butadiene, acrylonitrile and organic acid mixing copolymerization.Wherein, end carboxyl butyronitrile
Rubber has splendid toughness, and the carboxyl of its molecular chain-end can be with epoxy radicals with the radical reaction such as epoxy radicals, hydroxyl, i.e. carboxyl
Reaction, thus is grafted on epoxy molecule, play toughness reinforcing while improve the physical property stability after adhesive solidification.Add suitable
Amount grafting rubbers, in PART EPOXY molecule, participates in cross-linking reaction, it is possible to increase the toughness after adhesive solidification will not drop again simultaneously
Low material tg value.Present invention nbr carboxyl terminal preferably is Nipol 1072 (Zeon Coporation), 1072CG
(Nantex industry Co.,Ltd)。
Described nano-rubber elastomer is XER-91 (JSR Corporation), and this rubber grain can be dispersed in asphalt mixtures modified by epoxy resin
In fat, the glass transition temperature of epoxy resin will not be reduced.As, 85 parts of epoxy resin add 15 parts of XER-91, its glass
Glass transition temperature is up to 120 DEG C;Toughness and the impact strength of epoxy resin can also be effectively improved simultaneously.
Tg own is higher for thermal plastic high polymer engineering plastics, and toughness is preferable, at high temperature still can have good after life-time service
Performance, the ehter bond in molecule imparts molecular flexibility simultaneously, is properly added toughness after can improving adhesive solidification and does not reduces simultaneously
Its glass transition temperature.
The described epoxy resin toughened macromole epoxy resin being to have certain toughness through toughening modifying or molecule itself, this
Invent at least one in preferred poly phenol oxygen epoxy resin and rubber toughened bisphenol A type epoxy resin.Bisphenol type epoxy tree is
Through rubber toughened modified bisphenol A type epoxy resin.Poly phenol oxygen epoxy resin is preferably JER1256 (Mitsubishi Chemical's strain formula meeting
Society, epoxide equivalent 9052g/eq), its molecular weight is at 10-45 about ten thousand, and its toughness is splendid, tg up to 98 DEG C, molecular backbone
On there is phenyl ring and propylidyne, therefore it has excellent mechanical strength and toughness, it is possible in adhesive system participate in reaction
Improve the toughness after adhesive solidification simultaneously.The high molecular weight bisphenol A epoxy resin of modified rubber is HyPox RK84L (CVC
Thermoset Specialties, its elastic scale of construction is 32%, and epoxide equivalent is 1350g/eq) epoxy resin toughness can be given
And pliability, the toughness that can improve adhesive system improves peel strength.
Preferably, described polyfunctional epoxy resin is at least one in phenol aldehyde type epoxy resin and bisphenol A type epoxy resin.
The bisphenol A type epoxy resin that the present invention uses belongs to the bisphenol A type epoxy resin of little molecule, preferably GESR128E (grand prosperous electricity
Sub-material limited company, epoxide equivalent 185g/eq) and GESR901 (HongChang Electronic Materials Co., Ltd, epoxy is worked as
Amount 475g/eq) resin;Phenol aldehyde type epoxy resin is preferably XD-1000 (Japan's chemical medicine, epoxide equivalent 253g/eq), these
Resin participate in adhesive system reaction can improve system solidification after crosslink density, thus improve adhesive adhesive strength,
Thermostability and tg etc..
Preferably, described firming agent is amine curing agent, acid anhydride type curing agent, blocked isocyanate curing agent and benzene oxazines
One or more in prepolymer.
Preferably, described amine curing agent is 4,4-diaminodiphenyl-methane, 4,4-DADPS, dicyanodiamine,
One or more in m-diaminobenzene. and modified polyamide solution, belong to many amine curing agents, and the present invention preferably 4,4-diamino
Base diphenyl sulphone (DPS), dicyanodiamine and modified polyamide solution;Described acid anhydride type curing agent is aromatic anhydride, selected from phthalic acid
At least one in acid anhydride, trimellitic anhydride, pyromellitic acid anhydride and Benzophenone carboxylic acid dianhydride, the present invention preferred benzophenone tetracarboxylic acid
Acid dianhydride;Described blocked isocyanate curing agent is polyisocyanate;Described benzene oxazines prepolymer be with phenolic compound,
Aminated compounds and the benzo 6-membered heterocyclic compound that formaldehyde is Material synthesis.
Amine curing agent can cured epoxy, the beneficially adhesive strength of raising adhesive;Anhydride curing agent can cured epoxy tree
Fat adhesive, can be effectively improved the high temperature resistant of system and acid-proof alkaline.
Blocked isocyanate curing agent is polyisocyanate, at 90 DEG C of deblockings and discharge free NCO group, and can be with system
In part amino, hydroxyl and epoxy reaction, curable epoxy or generate polyurethane and epoxy cross-linking System forming interpenetrating networks
Structure, improves thermostability and the toughness of material, and the blocked isocyanate that the present invention uses is Schneider TPA-B80X or MF-K60X.
Described benzene oxazines prepolymer is the benzo hexa-member heterocycle with phenolic compound, aminated compounds and formaldehyde as Material synthesis
Compound, the intermediate material of its open loop under the high temperature conditions can be as the firming agent of epoxy resin.
Preferably, described Imidizole accelerator is 2-methylimidazole, 2-ethyl-4 Methylimidazole. and 1-cyanoethyl-2-ethyl-4-
At least one in Methylimidazole., the present invention preferred 1-cyanoethyl-2-ethyl-4-methylimidazole, Imidizole accelerator can not only be used for room
Temperature firming agent also can add appropriate Imidizole accelerator can accelerate epoxy reaction speed as accelerator.Described filler is hydrogen-oxygen
Change one or more in aluminum, aluminium oxide and Pulvis Talci, preferably aluminium hydroxide.Aluminium hydroxide, aluminium oxide and talcum powder can
Improve the thermostability of adhesive system, dimensional stability and reduce cost, adhesive toughness can also be improved simultaneously, reducing harmomegathus.
Described fire-retardant filler is at least one in OP935 and FP110, and wherein, the phosphorus content of OP935 is high, is about
23-24%, it has special thin particle size, and (Laser Scattering Particle is distributed: D95 < 10um), gathers at various thermoplasticity, thermosetting
In polymer resin system (such as epoxy resin and organic solvent etc.), dispersive property is excellent;There is the resistance to height of brilliance
Warm nature energy, decomposition temperature, more than 300 DEG C, is a kind of halogen-free flameproof filler.
Preferably, other described auxiliary agent is one or more in resistance to ion migration agent, surfactant and age resister.Resistance to
Ion migration agent is IXE-100, and surfactant is 3M FC-4430, and age resister is EVERNOX-10.
Preferably, described organic solvent is one or more in methyl ethyl ketone, dimethyl fumarate and dimethylformamide,
The preferred methyl ethyl ketone of the present invention and dimethylformamide.
The preparation method of adhesive, puts into toughening material, polyfunctional epoxy resin by weight in dispersion cylinder respectively, fills out
Material, fire-retardant filler, firming agent, Imidizole accelerator, other auxiliary agent and organic solvent, by these material dissolutions, be configured to glue,
I.e. obtain adhesive.
The invention has the beneficial effects as follows, the present invention uses the toughened resin that toughness is splendid, glass transition temperature is high part or all of
Replace nitrile rubber, and select suitable curing system, prepare adhesive, it is achieved the raising of adhesive layer glass transition temperature,
This adhesive is coated and on ambroin thin film or Copper Foil, is prepared as semi-solid preparation glue-line, under high-temperature and high-pressure conditions, be pressed into circuit
Or Copper Foil, after solidification, its adhesive layer tg point can reach 90-100 DEG C, can meet material life-time service under higher temperature conditions.
Accompanying drawing explanation
Fig. 1 be comparative example 1 preparation toughness reinforcing for CTBN adhesive solidification after differential scanning calorimetry analyze collection of illustrative plates (DSC);
Fig. 2 is that the differential scanning calorimetry after the adhesive solidification of the embodiment of the present invention 1 preparation analyzes collection of illustrative plates (DSC).
Detailed description of the invention
Embodiment 1
A kind of adhesive with high glass-transition temperature for flexible coverlay, including the group of the parts by weight shown in table 1
Point:
Toughening material is nbr carboxyl terminal, poly phenol oxygen epoxy resin
Polyfunctional epoxy resin is bisphenol A type epoxy resin (GESR901 and GESR128E) and phenol novolak type epoxy
Firming agent is amine curing agent dicyanodiamine, acid anhydride type curing agent Benzophenone carboxylic acid dianhydride
Imidizole accelerator is 1-cyanoethyl-2-ethyl-4-methylimidazole
Filler is aluminium hydroxide
Fire-retardant filler is OP935 and FP110
Other auxiliary agents are resistance to ion migration agent IEX-100, surfactant 3M FC-4430, age resister EVERNOX-10
Organic solvent is dimethylformamide and methyl ethyl ketone
The components by weight percent of each raw material see table 1.
The preparation method of adhesive: put into toughening material, polyfunctional epoxy resin by weight in dispersion cylinder respectively, fill out
Material, fire-retardant filler, firming agent, Imidizole accelerator, other auxiliary agent and organic solvent, by these material dissolutions, be configured to glue,
I.e. obtain adhesive.
A kind of flexible coverlay, it includes bottom, intermediate layer and the top layer fit together, and bottom is electrical insulating film, and top layer is
Protective layer, intermediate layer is the adhesive layer that adhesive is formed.
The method of the flexible coverlay of preparation: the adhesive solvent present invention prepared is coated on electrical insulating film, in temperature is
Toast 5 minutes at 80-180 DEG C, remove organic solvent dry compositions, form intermediate adhesive layer, then by itself and protection
Lamination closes and forms an overall layer structure, in the constant temperature oven of 50 DEG C, toasts about 10 hours, makes adhesive layer shape
Become there is the semi-solid preparation glued membrane of certain state of cure, obtain the flexible coverlay of layer structure.
Adhesive and flexible coverlay to preparation carry out performance measurement, and the vitrification of adhesive turns table temperature measuring result such as table 2
Shown in, the performance indications that adhesive reaches are as shown in table 3, and the performance measurement result of flexible coverlay is as shown in table 4.
The prepared differential scanning calorimetry after adhesive solidification analyzes collection of illustrative plates as shown in Figure 2.
Embodiment 2
A kind of adhesive with high glass-transition temperature for flexible coverlay, including the group of the parts by weight shown in table 1
Point:
Toughening material is poly phenol oxygen epoxy resin and rubber toughened bisphenol A type epoxy resin
Polyfunctional epoxy resin is bisphenol A type epoxy resin (GESR901 and GESR128E) and phenol novolak type epoxy
Firming agent is amine curing agent dicyanodiamine and acid anhydride type curing agent Benzophenone carboxylic acid dianhydride
Imidizole accelerator is 1-cyanoethyl-2-ethyl-4-methylimidazole
Filler is aluminium hydroxide
Fire-retardant filler is OP935
Other auxiliary agents are resistance to ion migration agent IEX-100, surfactant 3M FC-4430, age resister EVERNOX-10
Organic solvent is dimethylformamide and methyl ethyl ketone
The components by weight percent of each raw material see table 1.
Adhesive is identical with embodiment 1 with the preparation method of flexible coverlay, and adhesive and flexible coverlay to preparation enter
Row performance measurement, it is as shown in table 2 that the vitrification of adhesive turns table temperature measuring result, the performance indications that adhesive reaches such as table 3
Shown in, the performance measurement result of flexible coverlay is as shown in table 4.
Embodiment 3
A kind of adhesive with high glass-transition temperature for flexible coverlay, including the group of the parts by weight shown in table 1
Point:
Toughening material is poly phenol oxygen epoxy resin and rubber toughened bisphenol A type epoxy resin
Polyfunctional epoxy resin is bisphenol A type epoxy resin (GESR901 and GESR128E)
Firming agent is amine curing agent dicyanodiamine and 4,4-DADPS
Imidizole accelerator is 1-cyanoethyl-2-ethyl-4-methylimidazole
Filler is aluminium hydroxide
Fire-retardant filler is OP935
Other auxiliary agents are resistance to ion migration agent IEX-100, surfactant 3M FC-4430, antiager EVERNOX-10
Organic solvent is dimethylformamide and methyl ethyl ketone
The components by weight percent of each raw material see table 1.
Adhesive is identical with embodiment 1 with the preparation method of flexible coverlay, and adhesive and flexible coverlay to preparation enter
Row performance measurement, it is as shown in table 2 that the vitrification of adhesive turns table temperature measuring result, the performance indications that adhesive reaches such as table 3
Shown in, the performance measurement result of flexible coverlay is as shown in table 4.
Embodiment 4
A kind of adhesive with high glass-transition temperature for flexible coverlay, including the group of the parts by weight shown in table 1
Point:
Toughening material is poly phenol oxygen epoxy resin and rubber toughened bisphenol A type epoxy resin
Polyfunctional epoxy resin is bisphenol A type epoxy resin (GESR901 and GESR128E)
Firming agent is amine curing agent dicyanodiamine, 4,4-DADPS and modified polyamide solution
Imidizole accelerator is 1-cyanoethyl-2-ethyl-4-methylimidazole
Filler is aluminium hydroxide
Fire-retardant filler is OP935
Other auxiliary agents are resistance to ion migration agent IEX-100, surfactant 3M FC-4430, antiager EVERNOX-10
Organic solvent is dimethylformamide and methyl ethyl ketone
The components by weight percent of each raw material see table 1.
Adhesive is identical with embodiment 1 with the preparation method of flexible coverlay, and adhesive and flexible coverlay to preparation enter
Row performance measurement, it is as shown in table 2 that the vitrification of adhesive turns table temperature measuring result, the performance indications that adhesive reaches such as table 3
Shown in, the performance measurement result of flexible coverlay is as shown in table 4.
Embodiment 5
A kind of adhesive with high glass-transition temperature for flexible coverlay, including the group of the parts by weight shown in table 1
Point:
Toughening material is poly phenol oxygen epoxy resin, rubber toughened bisphenol A type epoxy resin and polyphenylene oxide
Polyfunctional epoxy resin is bisphenol A type epoxy resin (GESR901 and GESR128E)
Firming agent is amine curing agent dicyanodiamine and acid anhydride type curing agent Benzophenone carboxylic acid dianhydride
Imidizole accelerator is 1-cyanoethyl-2-ethyl-4-methylimidazole
Filler is aluminium hydroxide
Fire-retardant filler is OP935
Other auxiliary agents are resistance to ion migration agent IEX-100, surfactant 3M FC-4430, antiager EVERNOX-10
Organic solvent is dimethylformamide and methyl ethyl ketone
The components by weight percent of each raw material see table 1.
Adhesive is identical with embodiment 1 with the preparation method of flexible coverlay, and adhesive and flexible coverlay to preparation enter
Row performance measurement, it is as shown in table 2 that the vitrification of adhesive turns table temperature measuring result, the performance indications that adhesive reaches such as table 3
Shown in, the performance measurement result of flexible coverlay is as shown in table 4.
Embodiment 6
A kind of adhesive with high glass-transition temperature for flexible coverlay, including the group of the parts by weight shown in table 1
Point:
Toughening material is poly phenol oxygen epoxy resin, rubber toughened bisphenol A type epoxy resin and polyimides
Polyfunctional epoxy resin is bisphenol A type epoxy resin (GESR901 and GESR128E)
Firming agent is amine curing agent dicyanodiamine and acid anhydride type curing agent Benzophenone carboxylic acid dianhydride
Imidizole accelerator is 1-cyanoethyl-2-ethyl-4-methylimidazole
Filler is aluminium hydroxide
Fire-retardant filler is OP935
Other auxiliary agents are resistance to ion migration agent IEX-100, surfactant 3M FC-4430 and antiager EVERNOX-10
Organic solvent is dimethylformamide and methyl ethyl ketone
Adhesive is identical with embodiment 1 with the preparation method of flexible coverlay, and adhesive and flexible coverlay to preparation enter
Row performance measurement, it is as shown in table 2 that the vitrification of adhesive turns table temperature measuring result, the performance indications that adhesive reaches such as table 3
Shown in, the performance measurement result of flexible coverlay is as shown in table 4.
Embodiment 7
A kind of adhesive with high glass-transition temperature for flexible coverlay, including the group of the parts by weight shown in table 1
Point:
Toughening material is nbr carboxyl terminal, poly phenol oxygen epoxy resin and rubber toughened bisphenol A type epoxy resin
Polyfunctional epoxy resin is bisphenol A type epoxy resin (GESR901 and GESR128E) and phenol novolak type epoxy
Firming agent is acid anhydride type curing agent Benzophenone carboxylic acid dianhydride and benzene oxazines
Imidizole accelerator is 1-cyanoethyl-2-ethyl-4-methylimidazole
Filler is aluminium hydroxide
Fire-retardant filler is OP935
Other auxiliary agents are resistance to ion migration agent IEX-100, surfactant 3M FC-4430 and antiager EVERNOX-10
Organic solvent is dimethylformamide and methyl ethyl ketone
The components by weight percent of each raw material see table 1.
Adhesive is identical with embodiment 1 with the preparation method of flexible coverlay, and adhesive and flexible coverlay to preparation enter
Row performance measurement, it is as shown in table 2 that the vitrification of adhesive turns table temperature measuring result, the performance indications that adhesive reaches such as table 3
Shown in, the performance measurement result of flexible coverlay is as shown in table 4.
Embodiment 8
A kind of adhesive with high glass-transition temperature for flexible coverlay, including the group of the parts by weight shown in table 1
Point:
Toughening material is poly phenol oxygen epoxy resin and rubber toughened bisphenol A type epoxy resin
Polyfunctional epoxy resin is bisphenol A type epoxy resin (GESR901 and GESR128E)
Firming agent is acid anhydride type curing agent Benzophenone carboxylic acid dianhydride, benzene oxazines and polyisocyanate
Imidizole accelerator is 1-cyanoethyl-2-ethyl-4-methylimidazole
Filler is aluminium hydroxide
Fire-retardant filler is OP935
Other auxiliary agents are resistance to ion migration agent IEX-100, surfactant 3M FC-4430 and antiager EVERNOX-10
Organic solvent is dimethylformamide and methyl ethyl ketone
The components by weight percent of each raw material see table 1.
Adhesive is identical with embodiment 1 with the preparation method of flexible coverlay, and adhesive and flexible coverlay to preparation enter
Row performance measurement, it is as shown in table 2 that the vitrification of adhesive turns table temperature measuring result, the performance indications that adhesive reaches such as table 3
Shown in, the performance measurement result of flexible coverlay is as shown in table 4.
Embodiment 9
A kind of adhesive with high glass-transition temperature for flexible coverlay, including the group of the parts by weight shown in table 1
Point:
Toughening material is polyether sulfone, rubber toughened bisphenol A type epoxy resin and reacting nano rubber elastomer
Polyfunctional epoxy resin is bisphenol A type epoxy resin (GESR901 and GESR128E)
Firming agent is acid anhydride type curing agent Benzophenone carboxylic acid dianhydride, benzene oxazines and polyisocyanate
Imidizole accelerator is 1-cyanoethyl-2-ethyl-4-methylimidazole
Filler is aluminium hydroxide
Fire-retardant filler is OP935
Other auxiliary agents are resistance to ion migration agent IEX-100, surfactant 3M FC-4430 and antiager EVERNOX-10
Organic solvent is dimethylformamide and methyl ethyl ketone
The components by weight percent of each raw material see table 1.
Adhesive is identical with embodiment 1 with the preparation method of flexible coverlay, and adhesive and flexible coverlay to preparation enter
Row performance measurement, it is as shown in table 2 that the vitrification of adhesive turns table temperature measuring result, the performance indications that adhesive reaches such as table 3
Shown in, the performance measurement result of flexible coverlay is as shown in table 4.
Comparative example 1
A kind of existing adhesive for flexible coverlay, including the component of the parts by weight shown in table 1:
Toughening material is nbr carboxyl terminal
Polyfunctional epoxy resin is bisphenol A type epoxy resin (GESR901) and phenol novolak type epoxy
Firming agent is amine curing agent dicyanodiamine, 4,4-DADPS and the polyamide solution of modification
Filler is aluminium hydroxide
Fire-retardant filler is OP935
Other auxiliary agents are resistance to ion migration agent IEX-100, surfactant 3M FC-4430 and antiager EVERNOX-10
Organic solvent is dimethyl acetylamide and methyl ethyl ketone
Adhesive is identical with embodiment 1 with the preparation method of flexible coverlay, and adhesive and flexible coverlay to preparation enter
Row performance measurement, it is as shown in table 2 that the vitrification of adhesive turns table temperature measuring result, and the performance measurement result of flexible coverlay is such as
Shown in table 4.
The prepared differential scanning calorimetry after adhesive solidification analyzes collection of illustrative plates as shown in Figure 1.
The parts by weight of table 1 adhesive
The glass transition temperature measurement result of the adhesive of table 2 preparation
As shown in Table 2, the present invention uses the toughened resin that toughness is splendid, glass transition temperature is high partly or entirely to replace butyronitrile
Rubber, prepares adhesive, and the glass transition temperature of prepared adhesive is the highest, and toughness reinforcing with CTBN in comparative example 1
Adhesive, after its solidification, glass transition temperature is only about 50 DEG C.
Simultaneously the present invention prepare adhesive also reached following index, as shown in table 3.
Table 3 present invention the method for testing of adhesive and index
Using the flexible coverlay of adhesive preparation of the present invention, the energy measurement result of gained flexibility coverlay is as shown in table 4.
The energy measurement result of the flexible coverlay of table 4
As shown in Table 4, the stripping performance of adhesive prepared by embodiment of the present invention 1-9 all can reach the index of quality of adhesive,
Its plate bursting performance is also qualified.
The above only lists the way of realization of the present invention, and protection scope of the present invention is not construed as being only limitted to embodiment
The concrete form stated, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made,
Should be included within the scope of the present invention.
Claims (10)
1. the adhesive with high glass-transition temperature for flexible coverlay, it is characterised in that include following parts by weight
Component:
Adhesive the most according to claim 1, it is characterised in that described toughening material is rubber, thermal plastic high polymer engineering
Material and epoxy resin toughened in one or more.
Adhesive the most according to claim 2, it is characterised in that described rubber is to be mixed by butadiene, acrylonitrile and organic acid
Amount at least one in poly-nbr carboxyl terminal and nano-rubber elastomer;Described thermal plastic high polymer engineering
Plastics are one or more in Polyetherimide, polyethersulfone resin, polyphenylene oxide and polyimides;Described flexibilizing epoxy tree
Fat is at least one in poly phenol oxygen epoxy resin and rubber toughened bisphenol A type epoxy resin.
Adhesive the most according to claim 1, it is characterised in that described polyfunctional epoxy resin is phenol aldehyde type epoxy resin
With at least one in bisphenol A type epoxy resin.
Adhesive the most according to claim 1, it is characterised in that described firming agent be amine curing agent, acid anhydride type curing agent,
One or more in blocked isocyanate curing agent and benzene oxazines prepolymer.
Adhesive the most according to claim 5, it is characterised in that described amine curing agent is 4,4-diamino-diphenyl first
One or more in alkane, 4,4-DADPS, dicyanodiamine, m-diaminobenzene. and modified polyamide solution;Described acid
Anhydride firming agent is aromatic anhydride, selected from phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride and Benzophenone
At least one in carboxylic acid dianhydride;Described blocked isocyanate curing agent is polyisocyanate;Described benzene oxazines prepolymer
It it is the benzo 6-membered heterocyclic compound with phenolic compound, aminated compounds and formaldehyde as Material synthesis.
Adhesive the most according to claim 1, it is characterised in that described Imidizole accelerator is 2-methylimidazole, 2-ethyl
At least one in-4 Methylimidazole .s and 1-cyanoethyl-2-ethyl-4-methylimidazole;Described filler is aluminium hydroxide, oxygen
Change one or more in aluminum and Pulvis Talci;Described fire-retardant filler is at least one in OP935 and FP110.
Adhesive the most according to claim 1, it is characterised in that other described auxiliary agent is resistance to ion migration agent, surface activity
One or more in agent and age resister.
Adhesive the most according to claim 1, it is characterised in that described organic solvent is methyl ethyl ketone, fumaric acid diformazan
One or more in ester and dimethylformamide.
10. the preparation method of the adhesive described in any one of claim 1-9, it is characterised in that by weight in dispersion cylinder respectively
Put into toughening material, polyfunctional epoxy resin, filler, fire-retardant filler, firming agent, Imidizole accelerator, other auxiliary agent and
Organic solvent, by these material dissolutions, is configured to glue, i.e. obtains adhesive.
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