CN109135647A - A kind of halogen-free resin composition, cover film prepared therefrom, copper-clad plate and printed wiring board - Google Patents
A kind of halogen-free resin composition, cover film prepared therefrom, copper-clad plate and printed wiring board Download PDFInfo
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- CN109135647A CN109135647A CN201811031204.6A CN201811031204A CN109135647A CN 109135647 A CN109135647 A CN 109135647A CN 201811031204 A CN201811031204 A CN 201811031204A CN 109135647 A CN109135647 A CN 109135647A
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
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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
- C09J11/06—Non-macromolecular additives organic
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- 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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
-
- 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
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of halogen-free resin composition, cover film prepared therefrom and copper-clad plate and printed circuit board, the halogen-free resin composition comprises the following components in parts by weight: 70~90 parts by weight of saturated polyester containing carboxyl, 5~20 parts by weight of polyacrylate, 3~15 parts by weight of epoxy resin, 0.5~5 parts by weight of blocked isocyanate.The present invention is using carboxyl saturated polyester and polyacrylate as matrix resin, and the transparency of resin combination is high, cementability is good；Using epoxy resin and blocked isocyanate as curing agent, the two collaboration solidification carboxyl saturated polyester and polyacrylate, the storage stability of resin combination is good, it is high to solidify crosslink density, cover that type is good, visible light transmittance is high, peel strength is high by the cover film that it is prepared, the copper-clad plate being prepared by it equally has high visible light transmittance and peel strength.
Description
Technical field
The invention belongs to printed-board technology field, it is related to a kind of halogen-free resin composition, cover film prepared therefrom
With copper-clad plate and printed circuit board.
Background technique
Under the promotion of the trend such as the lightening of electronic product, wearingization, flexible printed wiring board technology is quickly grown, right
Flexibility coat copper plate, the requirement for covering film properties are also more and more diversified.Wherein, the requirement of transparence is gradually convex in recent years
It is aobvious, the connection equipment of display screen and mainboard that backlight module, the CN203799313U being related to such as CN204513119U are related to and
The fields such as the display module that CN206207131U is related to have used transparent mulch film as its necessary component；
CN103898498A, CN103582304A etc. are then referred to the application of transparent copper-clad plate production opaque line plate.
An important technology for making transparent copper-clad plate and cover film is manufacture transparent adhesive, that is, is guaranteeing high heat resistance
Property, under conditions of flexibility and cohesive force, guarantee the high grade of transparency.Traditional adhesive of flexible printed wiring board materials'use is
Using rubber as toughening element.However rubber transparency itself is low, and easy to whiten and xanthochromia.
CN1294198C, which is disclosed, to be reacted with ethylene-vinyl alcohol copolymer with the monovalence epoxy resin below of molecular weight 500
Obtained modified ethylene vinyl alcohol copolymer can fly mountain barrier, transparent as the epoxy resin toughened of thermoplastic resin
Property；CN107400491A discloses a kind of transparent epoxy adhesive comprising cycloaliphatic epoxy resin, hexahydrophthalic anhydride, toughener
With light transmission powder, which combines epoxy systems and flexible polyester, gives full play to respective advantage, solve consistency problem and
Color inhibition problem, have high transparency, but heat resistance, in terms of still need to be further increased.
Therefore, in the art, it is still desirable to develop that transparency is high, caking property is good, heat resistance is high, storage stability is good
Copper-clad plate and cover film resin material.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of halogen-free resin compositions, prepared therefrom
Cover film and copper-clad plate and printed circuit board.
To achieve this purpose, the present invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of halogen-free resin composition, and the halogen-free resin composition includes following parts by weight
Component:
70~90 parts by weight of saturated polyester containing carboxyl, 5~20 parts by weight of polyacrylate, 3~15 parts by weight of epoxy resin,
0.5~5 parts by weight of blocked isocyanate.
In the present invention, using carboxyl saturated polyester and polyacrylate as matrix resin, the transparency of resin combination
Height, cementability are good；Using epoxy resin and blocked isocyanate as curing agent, the two collaboration solidifies carboxyl saturated polyester and gathers
The storage stability of acrylate, resin combination is good, and solidification crosslink density is high.
In the present invention, saturated polyester containing carboxyl, polyacrylate, epoxy resin, blocked isocyanate these four at
Point indispensable, needing to work in coordination could make halogen-free resin composition obtain good performance, could ensure and be prepared by it
Cover film and copper-clad plate have the advantages that transparency is high, caking property is good, heat resistance is high, storage stability.
In the present invention, the dosage of the saturated polyester containing carboxyl can for 70 parts by weight, 71 parts by weight, 72 parts by weight,
73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight or 80 parts by weight.At this
In invention, if the dosage of saturated polyester containing carboxyl is too many, the crosslink density that will lead to the resin combination is lower, under heat resistance
Drop；If dosage is very little, the flexibility decline of the resin combination, and the cover film route fillibility made with it will lead to
It is deteriorated, usability is bad.
Preferably, the number-average molecular weight of the saturated polyester containing carboxyl be 5000~50000, such as 10000,13000,
15000、18000、20000、23000、25000、28000、30000、33000、35000、38000、40000、42000、
45000,48000 or 50000.
Preferably, the glass transition temperature of the saturated polyester containing carboxyl is -20~100 DEG C, such as -20 DEG C, -10
DEG C, 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C.
Preferably, the acid value of the saturated polyester containing carboxyl be 5mg KOH/g~50mg KOH/g, such as 5mg KOH/g,
10mg KOH/g、15mg KOH/g、20mg KOH/g、23mg KOH/g、25mg KOH/g、28mg KOH/g、30mg KOH/g、
33mg KOH/g、35mg KOH/g、38mg KOH/g、40mg KOH/g、43mg KOH/g、45mg KOH/g、48mg KOH/g
Or 50mg KOH/g.When the acid value of the saturated polyester containing carboxyl is lower than 5mgKOH/g, after halogen-free resin composition solidification
Crosslink density is low, poor mechanical property；When the acid value of the saturated polyester containing carboxyl is higher than 50mgKOH/g, Halogen resin combination
Object is fully cured that rear flexibility is low, poor to the fillibility of route.
In the present invention, the dosage of the polyacrylate can for 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight,
10 parts by weight, 12 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight or 20 parts by weight.In the present invention, such as
The dosage of fruit dosage polyacrylate is very few, then the transparency of resin combination is low, and bonding force is smaller；It, will if dosage is excessively high
The resin combination is caused to be deteriorated the fillibility of route in printed wiring board.
Preferably, the number-average molecular weight of the polyacrylate be 100000~1000000, such as 100000,200000,
300000,400000,500000,600000,700000,800000,900000 or 1000000.In the present invention, when described poly-
When the molecular weight of acrylate is lower than 100000, the cohesive force of resin combination is smaller；When molecular weight is higher than 1000000,
Viscosity is excessive, needs to dilute compared with multi-solvent, and the compatibility poor with the polyurethane containing carboxyl.
Preferably, the glass transition temperature of the polyacrylate be -50 DEG C~50 DEG C, such as -50 DEG C, -45 DEG C, -
40 DEG C, -30 DEG C, -20 DEG C, -10 DEG C, 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C or 50 DEG C.
Preferably, the polyacrylate is the polyacrylate containing hydroxyl, carboxyl or epoxy group.
In the present invention, the dosage of the epoxide can for 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight,
7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight or 15 weight
Part.In the present invention, when the dosage of the epoxy resin is very little, lead to the glue film formed by the resin combination, covering
Film and the crosslink density of copper-clad plate are lower；When the dosage of the epoxy resin is too many, cause to be formed by the resin combination
Glue film, cover film and the flexibility of copper-clad plate it is poor, the transparency be deteriorated.
Preferably, the epoxide equivalent of the epoxy resin be 100~500 grams/equivalent, such as 100 grams/equivalent, 120 grams/
Equivalent, 150 grams/equivalent, 200 grams/equivalent, 250 grams/equivalent, 300 grams/equivalent, 350 grams/equivalent, 400 grams/equivalent, 450 grams/
Equivalent or 500 grams/equivalent.When the epoxide equivalent of heretofore described epoxide is lower than 100 grams/equivalent, the friendship of formation
Connection density is excessively high, and the flexibility of cover film is poor；When the epoxide equivalent of heretofore described epoxide is higher than 500 grams/equivalent
When, reactivity is poor, and the adhesive gel time is long.
Preferably, the number-average molecular weight of the epoxy resin be less than or equal to 8000, such as 8000,7800,7500,7000,
6500,6000,5500,5000,4500,4000,3000,2400,2000,1000 etc..Preferably, the number of the epoxide
Average molecular weight is less than or equal to 6000.It is further preferred that the number-average molecular weight of the epoxide is 400~6000.
Preferably, the epoxy resin is selected from bisphenol-A epoxy, Bisphenol F epoxy, phenol type novolac epoxy resin, o-cresol
Type novolac epoxy resin, bisphenol A-type novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, naphthalene type ring
In oxygen resin and tetrafunctional epoxy resin any one or at least two combination.In the present invention, the epoxy resin can
To improve the solidification crosslink density of resin combination, and then improve the heat resistance of the cover film formed by the resin combination.
In the present invention, the dosage of the blocked isocyanate can for 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight,
1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight.At this
In invention, if the dosage of blocked isocyanate is very few, the crosslink density formed is lower；Dosage is excessive, will lead to solidification
The heat resistance of object is deteriorated.
Preferably, the blocked isocyanate is blocked diisocyanates and/or blocked polyisocyanate.It is preferred that
Ground, the sealer that the blocked isocyanate uses can be but not limited to the change of the types such as phenol, ketoxime, imidazoles, amide
Close object.Preferably, the blocked diisocyanates include but is not limited to enclosed type toluene di-isocyanate(TDI), enclosed type diphenyl
Methane diisocyanate, enclosed type 1,5- naphthalene diisocyanate, enclosed type hexamethylene diisocyanate or the different Fo Er of enclosed type
In ketone diisocyanate any one or at least two combination.Preferably, the blocked polyisocyanate includes but not
It is limited to enclosed type triphenylmethane triisocyanate, enclosed type trimerization toluene di-isocyanate(TDI), enclosed type thiophosphoric acid triphenyl
In triisocyanate any one or at least two combination.
Preferably, the blocked isocyanate is enclosed type aliphatic isocyanates, enclosed type aliphatic isocyanates
With preferably anti-yellowing property.
Preferably, the halogen-free resin composition further includes the antioxidant of 0.1~2.0 parts by weight, such as the antioxidant
Dosage can be 0.1 part, 0.5 part, 0.8 part, 1 part, 1.3 parts, 1.5 parts, 1.8 parts or 2 parts.
Preferably, the antioxidant includes but is not limited to 2,6- di-tert-butyl-4-methy phenol (BHT, abbreviation antioxidant
264), four (4- hydroxyl -3,5- tert-butyl-phenyl propionic acid) pentaerythritol esters (abbreviation antioxidant 1010), the tertiary butyl- 4- hydroxyl of 3,5- bis-
Base benzenpropanoic acid octadecyl ester (abbreviation antioxidant 1076), bis- (2,2,6,6- tetramethyl -4- piperidines) sebacates (Tinuvin770),
In triphenyl phosphite (TTP), phosphorous acid three (nonyl phenyl ester) (TNP) or phenthazine any one or at least two group
It closes.In the present invention, the antioxidant can restrain or delay curing agent and its cured resin combination manufacture, processing and
Oxidative degradation in use process.
Crosslink density for the halogen-free resin composition further increased, the halogen-free resin composition can be with
Preferably include in imidazoles curing accelerator or amine curing agent any one or at least two combination.
Preferably, the imidazoles curing accelerator is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl miaow
In azoles, undecyl imidazole or cyanoimidazole any one or at least two combination.
Preferably, the amine curing agent is in alicyclic ring amine compounds, aromatic amine compound or other types amine compounds
Any one or at least two combination.
Preferably, the amine curing agent is selected from diethylenetriamine, triethylene tetramine, tetraethylenepentamine, divinyl third
The fatty amines such as amine；Meng's alkane diamines, isophorone diamine, N- aminoethyl piperazine, m-xylene diamine, diaminodiphenylmethane, diamino
In base diphenyl sulfone, m-phenylene diamine (MPD), dicyandiamide (DICY) or adipic dihydrazide any one or at least two combination.
Preferably, content of the imidazoles curing accelerator in halogen-free resin composition is 0.1~2 parts by weight, example
Such as 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 weight
Part or 2 parts by weight.
Preferably, content of the amine curing agent in halogen-free resin composition is 0.1~2 parts by weight, such as 0.1 weight
Measure part, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight or 2 weights
Measure part.
On the other hand, the present invention provides a kind of resin adhesive liquid, and the resin adhesive liquid is by Halogen resin group as described above
Conjunction object, which is dissolved or dispersed in solvent, to be obtained.
In the present invention, solvent is added in halogen-free resin composition of the invention, to dissolve each component, and adjusts tree
The solid content of oil/fat composition, to adjust the viscosity of prepared resin adhesive liquid.Tool to the solvent that can be used in the present invention
Body type is not particularly limited, as long as it can dissolve or disperse each component and do not influence effect of the invention.It is excellent
Selection of land, the solvent are selected from acetone, butanone, cyclohexanone, toluene, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate
Any one in dimethylformamide or at least two combination.
Preferably, the solid content of the resin adhesive liquid be 20%~50%, such as 20%, 23%, 25%, 28%, 30%,
33%, 35%, 38%, 40%, 43%, 45%, 48% or 50%.
On the other hand, the present invention provides a kind of cover film, the cover film includes polymer film layer, the polymer
The release film layer on adhesive layer and the adhesive layer in film layer, the adhesive layer is by Halogen resin combination as described above
Object is formed.
Preferably, the polymer film layer is laminated polyester film or polyimide film layer.Polyester in the present invention
Film can choose the film that various petchems are formed, such as can choose poly- naphthalene ester film.
Preferably, the polymer film layer with a thickness of 5~100 μm, such as 5 μm, 10 μm, 15 μm, 20 μm, 25 μm,
30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm etc..
Preferably, the adhesive layer with a thickness of 5~50 μm, such as 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μ
M, 40 μm, 45 μm, 50 μm etc..
Preferably, the release film layer with a thickness of 50~200 μm, such as 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μ
m、35μm、40μm、45μm、50μm、55μm、60μm、70μm、80μm、90μm、100μm、120μm、140μm、160μm、180μm
Or 200 μm.
The production method of cover film of the present invention includes the following steps: to dissolve the halogen-free resin composition or divide
It dissipates and obtains resin adhesive liquid in a solvent, resin adhesive liquid is coated on the surface of the polymer film layer, then by the coating
There is the thin polymer film of resin combination to be placed in 120~160 DEG C of (such as 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145
DEG C, 150 DEG C, 155 DEG C or 160 DEG C) high-temperature test chamber toasts 2~6 minutes (such as 2 minutes, 3 minutes, 4 minutes, 5 minutes or 6 points
Clock) semi-solid preparation is carried out, then release film is laminating on the adhesive layer of semi-solid preparation.
On the other hand, the present invention provides a kind of copper-clad plate, the copper-clad plate includes polymer film layer, the polymer
Adhesive layer in film layer and laminating in the copper foil on the adhesive layer, the adhesive layer is by Halogen resin group as described above
Object is closed to be formed.
Preferably, the polymer film layer is laminated polyester film or polyimide film layer.Polyester in the present invention
Film can choose the film that various petchems are formed, such as can choose poly- naphthalene ester film.
Preferably, the adhesive layer with a thickness of 5~45 μm, such as 5 μm, 8 μm, 10 μm, 13 μm, 15 μm, 18 μm, 20 μ
M, 25 μm, 28 μm, 30 μm, 33 μm, 35 μm, 38 μm, 40 μm or 45 μm.
Preferably, the polymer film layer with a thickness of 10~100 μm, such as 5 μm, 10 μm, 15 μm, 20 μm, 25 μm,
30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm.
Preferably, the copper foil with a thickness of 6~70 μm, such as 6 μm, 8 μm, 10 μm, 14 μm, 18 μm, 20 μm, 25 μm,
30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm etc..
Preferably, the copper-clad plate is single-side coated copper plate or double face copper.
In the present invention, by taking single-side coated copper plate as an example, the copper-clad plate includes polymer film layer and by the Halogen tree
Oil/fat composition is formed in the adhesive layer of the polymer film layer side and laminating in the copper foil on the adhesive layer.
In the present invention, the three-layer process single-side coated copper plate the production method is as follows: by the resin composition in
In the wherein one side of the polymer film layer, which is placed in 120~160 DEG C
(such as 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C or 160 DEG C) high-temperature test chamber baking 2~
6 minutes (such as 2 minutes, 3 minutes, 4 minutes, 5 minutes or 6 minutes) progress semi-solid preparations, then by the laminating glue in semi-solid preparation of copper foil
Adhesion coating solidifies after carrying out this semi-solid preparation state composition by design program, obtains the single-side coated copper plate.
On the other hand, the present invention provides a kind of printed circuit board, the printed circuit board includes covering as described above
Film or copper-clad plate.
Compared with the existing technology, the invention has the following advantages:
For the present invention using carboxyl saturated polyester and polyacrylate as matrix resin, the transparency of resin combination is high, viscous
Connecing property is good；Using epoxy resin and blocked isocyanate as curing agent, the two collaboration solidifies carboxyl saturated polyester and polypropylene
The storage stability of acid esters, resin combination is good, and solidification crosslink density is high, and thermal decomposition temperature is up to 323 DEG C or more.By its preparation
It is good that obtained cover film covers type, it is seen that and light transmission rate reaches 88% or more, and peel strength reaches 1.1N/mm or more, by
The visible light transmittance of its copper-clad plate being prepared reaches 80% or more, and peel strength reaches 1.5N/mm or more.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1-6
It is diluted by group assignment system resin combination shown in table 1, and using toluene and butanone as solvent, obtains glue, according to
The production method production covering membrane sample of following cover film.
Halogen-free resin composition is coated in a thickness of on 25 μm of polyester film using coating machine, is controlled gluing (dry glue)
It with a thickness of 15 μm, is then toasted 2 minutes in 140 DEG C of high-temperature test chamber, to form part crosslinking curing on polyester film
Adhesive layer, then that release film and the adhesive layer is laminating, obtained flexible printed-circuit board cover film.
Embodiment 7-12
By group assignment system resin combination shown in table 1, (embodiment 7 uses the resin combination of embodiment 1, and embodiment 8 makes
With the resin combination of embodiment 2, embodiment 9 uses the resin combination of embodiment 3, and embodiment 10 uses the tree of embodiment 4
Oil/fat composition, embodiment 11 use the resin combination of embodiment 5, and embodiment 12 uses the resin combination of embodiment 6), and
It is diluted using toluene and butanone as solvent, obtains glue, make copper-clad plate sample according to the production method of following copper-clad plate.
By halogen-free resin composition coated on 25 μm of polyester film, control gluing (dry glue) is with a thickness of 15 μm.It should
Polyester film coated with halogen-free resin composition is placed in 140 DEG C of high-temperature test chambers and toasts 2 minutes progress semi-solid preparations, then by size
It is laminating for 40cm (length) × 25cm (width) × 18 μm (thickness) rolled copper foil (BHY-22B-T provided by Japanese Kuang company)
It on the adhesive layer of semi-solid preparation, crosses for 100 DEG C and moulds, 180 DEG C/100kg pressure presses 60s fastly, and 170 DEG C solidify 2 hours, to prepare flexibility
Single-side coated copper plate used for printed circuit board.
Comparative example 1-7
It is diluted by group assignment system resin combination shown in table 2, and using toluene and butanone as solvent, obtains glue, according to
The production method production covering membrane sample of cover film described in embodiment 1-7.
Comparative example 8-14
By group assignment system resin combination shown in table 2, (comparative example 8 uses the resin combination of comparative example 1, and comparative example 9 makes
With the resin combination of comparative example 2, comparative example 10 uses the resin combination of comparative example 3, and comparative example 11 uses the tree of comparative example 4
Oil/fat composition, comparative example 12 use the resin combination of comparative example 5, and comparative example 13 is compared using the resin combination of comparative example 6
Example 14 uses the resin combination of comparative example 7), and diluted using toluene and butanone as solvent, glue is obtained, according to embodiment 8-
The production method of copper-clad plate in 14 makes copper-clad plate sample.
The resin combination component of 1 embodiment 1-12 of table
The resin combination component of 2 comparative example 1-14 of table
It prepared by embodiment 1-6 and comparative example the 1-7 cover film being prepared and embodiment 7-12 and comparative example 8-14
Obtained single-side coated copper plate is tested for the property, and test method is as follows:
(1) glue-line thermal decomposition temperature
Resin combination is placed in high-temperature test chamber, 170 DEG C solidify 1 hour, and sampling carries out thermogravimetic analysis (TGA), nitrogen later
It is heated up under protection with the rate of 10 DEG C/min, temperature when sample thermal weight loss 5% is considered as the thermal decomposition temperature of glue-line.
(2) peel strength
Cover film: the release film stripping of each of the cover film that following example 1-6 and comparative example 1-7 are obtained, and
And respectively by the adhesive layer of the cover film with having a size of 20cm (length) × smooth surface of the copper foil of 20cm (width) × 18 μm (thickness)
It is laminating, with the fast press of EWEDO-KY04C after 180 DEG C, 100Kgf press 1 minute fastly, it is placed in 170 DEG C of common Homothermal Proof Box admittedly
Change 1 hour, solidifies according to the above method, to be pasted with the sample of the cover film corresponding to embodiment 1-6 and comparative example 1-7 respectively
Product.
According to IPC-TM-650 2.4.9 method, test is pasted with respectively according to what above method obtained corresponding to embodiment
The sample of the cover film of 1-6 and comparative example 1-7.
Copper-clad plate: it chooses having a size of 20cm (length) × 20cm (width) single-side coated copper plate sample, according to IPC-TM-650
2.4.9 the copper-clad plate sample of method, testing example 7-12 and comparative example 7-12.
(3) visible light transmittance rate
The cover film of embodiment 1-6 and comparative example 1-7: being made the sample of 5cm × 5cm by cover film, after tearing release film,
It is placed in spectrophotometric color measurement instrument and tests it in 360nm to the light penetration between 740nm.
Copper-clad plate:
The copper-clad plate of embodiment 7-12 and comparative example 8-14 are made to the sample of 5cm × 5cm, after etching away copper foil, are placed in
Spectrophotometric color measurement instrument tests it in 360nm to the light penetration between 740nm.
(4) cover film covers type
Covering type can qualitatively reflect cover film obtained in following example 1-6 and comparative example 1-7 to printing electricity
The filling capacity of route on the plate of road.
Cover film obtained in embodiment 1-6 and comparative example 1-7 is fitted in into measurement circuit respectively, uses EWEDO-KY04C
For fast press at 180 DEG C, 100Kgf presses 80s fastly, using 50 times or more of amplification sem observation, check between route with the presence or absence of starved,
Bubble, filling is bad, pressure is not firm or influences the other defects used.Measurement circuit include 100mm ± 10mm long straight line, semicircle and
The figure at right angle, route copper thickness are 25 μm, and line width and line-spacing are 100 μm.
From measurement result it is found that when there is no bubble starved, bubble, filling is bad, pressure is not firm or influences to use other
It is as qualified when defect, it is otherwise, as unqualified.
3 embodiment test result of table
4 comparative example test result of table
As can be seen from Table 3, thermal decomposition temperature with higher after resin combination of the invention solidification, with its production
It is good that cover film covers type, it is seen that light transmission rate is high, and peel strength is high, has same superiority with the copper-clad plate of its production
Energy.The performance table 4 of comparative example is reviewed as can be seen that lacking polyacrylate, epoxide or isocyanide in resin combination
Acid esters can heat resistance to product, cover type, light transmittance and peel strength and cause different degrees of adverse effect；According to not
Saturated polyester replaces saturated polyester, then the transparency of product is decreased obviously；Using non-close type isocyanates or cyanate is answered to change
Property epoxy resin replace blocked isocyanate, the heat resistance and peel strength of product decline.Moreover, can by comparing example 4
To find out, if the proportion of each component is improper, resin combination, cover film and the copper-clad plate that cannot equally have excellent performance.
The Applicant declares that the present invention is explained by the above embodiments halogen-free resin composition of the invention, by its preparation
Cover film and copper-clad plate and printed circuit board, but the present invention is not limited to the above embodiments, that is, does not mean that the present invention
Above-described embodiment, which must be relied on, to be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of halogen-free resin composition, which is characterized in that the halogen-free resin composition comprises the following components in parts by weight:
70~90 parts by weight of saturated polyester containing carboxyl, 5~20 parts by weight of polyacrylate, 3~15 parts by weight of epoxy resin, closing
0.5~5 parts by weight of type isocyanates.
2. halogen-free resin composition according to claim 1, which is characterized in that the number of the saturated polyester containing carboxyl is divided equally
Son amount is 5000~50000；
Preferably, the glass transition temperature of the saturated polyester containing carboxyl is -20 DEG C~100 DEG C；
Preferably, the acid value of the saturated polyester containing carboxyl is 5mg KOH/g~50mg KOH/g.
3. halogen-free resin composition according to claim 1 or 2, which is characterized in that the number of the polyacrylate is divided equally
Son amount is 100000~1000000；
Preferably, the glass transition temperature of the polyacrylate is -50 DEG C~50 DEG C；
Preferably, the polyacrylate is the polyacrylate containing hydroxyl, carboxyl or epoxy group.
4. halogen-free resin composition according to any one of claim 1-3, which is characterized in that the ring of the epoxy resin
Oxygen equivalent is 100~500 grams/equivalent；
Preferably, the number-average molecular weight of the epoxy resin is less than or equal to 8000, is preferably smaller than equal to 6000, further preferably
400~6000；
Preferably, the epoxy resin is selected from bisphenol-A epoxy, Bisphenol F epoxy, phenol type novolac epoxy resin, o-cresol type phenol
Formaldehyde epoxy resin, bisphenol A-type novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, naphthalene type asphalt mixtures modified by epoxy resin
In rouge and tetrafunctional epoxy resin any one or at least two combination.
5. halogen-free resin composition described in any one of -4 according to claim 1, which is characterized in that the enclosed type isocyanic acid
Ester is blocked diisocyanates and/or blocked polyisocyanate；
Preferably, the sealer that the blocked isocyanate uses is in the compound of phenol, ketoxime, imidazoles or amide type
Any one or at least two combination；
Preferably, the blocked diisocyanates include that enclosed type toluene di-isocyanate(TDI), enclosed type diphenyl methane two are different
Cyanate, two isocyanide of enclosed type 1,5- naphthalene diisocyanate, enclosed type hexamethylene diisocyanate or enclosed type isophorone
In acid esters any one or at least two combination；
Preferably, the blocked polyisocyanate includes enclosed type triphenylmethane triisocyanate, three polymethyl benzene of enclosed type
In diisocyanate, enclosed type thiophosphoric acid triphenyl triisocyanate any one or at least two combination.
6. halogen-free resin composition according to any one of claims 1-5, which is characterized in that the Halogen resin combination
Object further includes the antioxidant of 0.1~2.0 parts by weight；
Preferably, the antioxidant includes 2,6- di-tert-butyl-4-methy phenol, four (4- hydroxyl -3,5- tert-butyl-phenyls third
Acid) pentaerythritol ester, the tertiary butyl- 4- hydroxy phenylpropionic acid octadecyl ester of 3,5- bis-, bis- (2,2,6,6- tetramethyl -4- piperidines) decanedioic acid
In ester, triphenyl phosphite, phosphorous acid three (nonyl phenyl ester) or phenthazine any one or at least two combination；
Preferably, the halogen-free resin composition further include in imidazoles curing accelerator or amine curing agent any one or
At least two combination；
Preferably, the imidazoles curing accelerator is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, ten
In one alkyl imidazole or cyanoimidazole any one or at least two combination；
Preferably, the amine curing agent is appointing in alicyclic ring amine compounds, aromatic amine compound or other types amine compounds
It anticipates a kind of or at least two combinations；
Preferably, the amine curing agent is selected from diethylenetriamine, triethylene tetramine, tetraethylenepentamine, divinyl propylamine etc.
Fatty amine；Meng's alkane diamines, isophorone diamine, N- aminoethyl piperazine, m-xylene diamine, diaminodiphenylmethane, diamino two
In phenylsulfone, m-phenylene diamine (MPD), dicyandiamide or adipic dihydrazide any one or at least two combination；
Preferably, content of the imidazoles curing accelerator in halogen-free resin composition is 0.1~2 parts by weight；
Preferably, content of the amine curing agent in halogen-free resin composition is 0.1~2 parts by weight.
7. a kind of resin adhesive liquid, which is characterized in that the resin adhesive liquid is by Halogen such as of any of claims 1-6
Resin combination is dissolved or dispersed in solvent and obtains；
Preferably, the solid content of the resin adhesive liquid is 20%~50%.
8. a kind of cover film, which is characterized in that the cover film includes polymer film layer, the glue on the polymer film layer
Release film layer on adhesion coating and the adhesive layer, the adhesive layer is by Halogen tree such as of any of claims 1-6
Oil/fat composition is formed；
Preferably, the polymer film layer is laminated polyester film or polyimide film layer；
Preferably, the polymer film layer with a thickness of 5~100 μm；
Preferably, the adhesive layer with a thickness of 5~50 μm；
Preferably, the release film layer with a thickness of 50~200 μm.
9. a kind of copper-clad plate, which is characterized in that the copper-clad plate includes polymer film layer, the glue on the polymer film layer
Adhesion coating and laminating in the copper foil on the adhesive layer, the adhesive layer is formed by halogen-free resin composition as described above；
Preferably, the adhesive layer with a thickness of 5~45 μm；
Preferably, the polymer film layer with a thickness of 10~100 μm；
Preferably, the copper foil with a thickness of 6~70 μm；
Preferably, the copper-clad plate is single-side coated copper plate or double face copper.
10. a kind of printed circuit board, which is characterized in that the printed circuit board includes cover film according to any one of claims 8 or power
Benefit require 9 described in copper-clad plate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811031204.6A CN109135647A (en) | 2018-09-05 | 2018-09-05 | A kind of halogen-free resin composition, cover film prepared therefrom, copper-clad plate and printed wiring board |
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|---|---|---|---|
| CN201811031204.6A CN109135647A (en) | 2018-09-05 | 2018-09-05 | A kind of halogen-free resin composition, cover film prepared therefrom, copper-clad plate and printed wiring board |
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| CN109135647A true CN109135647A (en) | 2019-01-04 |
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| CN111117503A (en) * | 2019-12-26 | 2020-05-08 | 安徽明讯新材料科技股份有限公司 | Protective film with adhesive and PET (polyethylene terephthalate) base material capable of being granulated together and manufacturing method thereof |
| CN113999639A (en) * | 2021-11-17 | 2022-02-01 | 九江福莱克斯有限公司 | High-transparency temperature-resistant yellowing-resistant polyester adhesive and flexible covering film prepared from same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110591591A (en) * | 2019-09-05 | 2019-12-20 | 深圳市柳鑫实业股份有限公司 | Insulating medium adhesive film, preparation method thereof and multilayer printed circuit board |
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| KR20210030900A (en) * | 2019-09-05 | 2021-03-18 | 션전 뉴세스 인더스트리얼 컴퍼니 리미티드 | Insulating dielectric film, manufacturing method thereof, and multilayer printed circuit board |
| TWI750790B (en) * | 2019-09-05 | 2021-12-21 | 大陸商深圳市柳鑫實業股份有限公司 | Insulating medium adhesive film and preparation method thereof and multilayer printed circuit board |
| JP2022508986A (en) * | 2019-09-05 | 2022-01-20 | 深▲セン▼市柳▲キン▼実業股▲フン▼有限公司 | Insulation adhesive film and its manufacturing method, multi-layer printed wiring board |
| JP7146301B2 (en) | 2019-09-05 | 2022-10-04 | 深▲セン▼市柳▲キン▼実業股▲フン▼有限公司 | Insulating adhesive film and its manufacturing method, multilayer printed wiring board |
| KR102475222B1 (en) * | 2019-09-05 | 2022-12-06 | 션전 뉴세스 인더스트리얼 컴퍼니 리미티드 | Insulating dielectric film and its manufacturing method and multi-layer printed circuit board |
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| CN111117503A (en) * | 2019-12-26 | 2020-05-08 | 安徽明讯新材料科技股份有限公司 | Protective film with adhesive and PET (polyethylene terephthalate) base material capable of being granulated together and manufacturing method thereof |
| CN113999639A (en) * | 2021-11-17 | 2022-02-01 | 九江福莱克斯有限公司 | High-transparency temperature-resistant yellowing-resistant polyester adhesive and flexible covering film prepared from same |
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