CN101486883A - Adhesive composition used for non-halogen coating and coating using the same - Google Patents

Adhesive composition used for non-halogen coating and coating using the same Download PDF

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Publication number
CN101486883A
CN101486883A CNA2008100823427A CN200810082342A CN101486883A CN 101486883 A CN101486883 A CN 101486883A CN A2008100823427 A CNA2008100823427 A CN A2008100823427A CN 200810082342 A CN200810082342 A CN 200810082342A CN 101486883 A CN101486883 A CN 101486883A
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halogen
binder composition
weight
mulch film
equal
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CN101486883B (en
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金佑锡
全海尚
文基祯
金志赫
金度均
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Toray Advanced Materials Korea Inc
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Toray Saehan Inc
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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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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

Abstract

The invention relates to an adhesive composite for halogen free covering films, which is used for preparing covering films for protecting flexible printed circuit board, and further relates to covering films comprising such adhesive composite. Move specially, the invention relates to an adhesive composite for halogen free covering films and covering films using the same which meets all requirements in fire resistance, binding property, heat resistance, permeability, and fluidity. To this end, the adhesive composite of the halogen free covering film is characterized in comprising (1) a nitrile butadiene rubber (NBR) including carboxyl with molecular weight from 10,000 to 200,000 and having 20 to 40 weight parts of acrylonitrile content, (2) a non-halogen multifunctional epoxide resin with two or more epoxide group on each molecule thereof and having molecular weight from 200 to 1,000, (3) a hardening agent, (4) a curing accelerant, (5) a non-halogen phosphorus fire resistor with content of phosphorus fire resistor larger than 10% by weight and thermal cracking temperature higher than 300 DEG C., and (6) inorganic particles, such as aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, antimony trioxide, silica or the like.

Description

Be used for the binder composition of halogen mulch film and the mulch film of the described binder composition of use
Technical field
The present invention relates to be used to protect the halogen mulch film binder composition of flexible printed circuit board, and relate to the mulch film that uses described binder composition.More specifically, the present invention relates to be used for the binder composition of halogen mulch film, described mulch film meets all requirements such as flame retardant resistance, binding property, thermotolerance, exudative, flowability, and relates to the mulch film that uses described binder composition.
Background technology
Recently, the consumer electronics that obviously more and more the flexible printing battery lead plate is used for compactness, frivolous and Highgrade integration.Therefore, also use the mulch film holding circuit more and more, thereby need to improve performances such as binding property, thermotolerance, flame retardant resistance, flowability really.
And in Europe, WEEE and RoHS etc. requires development environment close friend's material.Yet, be used for the tackiness agent that electronic material for example is used for conventional mulch film or semiconductor-encapsulating material, be to comprise halogen atom such as bromine compound as fire retardant.Therefore, when tackiness agent burns, its toxigenicity gas, for example dioxin-like compound.Therefore, require electronic product to use the halogen tackiness agent at present.
Usually, mulch film is by making and comprise that barrier sheet protects tackiness agent in the side coating of heat-resistant film with the tackiness agent of semicure.Owing to the mulch film that so produces will be bonded to flexible printed circuit board (PCB) with the protection printed wiring, so need physicalies such as thermotolerance, binding property, flame retardant resistance, flowability.Mulch film must have the physicals of all requirements, even also requires its halogen feature to keep environment.
The conventional tackiness agent that is used for mulch film is generally based on epoxide, acrylic resin, phenol resins, polyester etc., but all these uses halogen-based flame retardants such as bromine, and this is unfavorable for environment.For the reason of protection environment, avoid halogen-based flame retardants, therefore developed the mulch film that uses halogen-free flame-retardant, but they do not meet above-mentioned all physicals requirements.
Summary of the invention
The present invention expection is provided for the binder composition of halogen mulch film and comprises described binder composition, meets the mulch film that all above-mentioned physicalies require.The purpose of this invention is to provide the binder composition that is used for the halogen mulch film and comprise described binder composition and meet the mulch film of performance requriementss such as desired all flame retardant resistances of mulch film, binding property, thermotolerance, exudative and flowability.
Realize above-mentioned purpose of the present invention by the binder composition that is used for the halogen mulch film, described halogen mulch film is characterised in that and comprises: (1) comprises carboxyl and has 10,000 to 200,000 molecular weight, and acrylonitrile content is the paracril (NBR) of 20 to 40 weight parts, (2) per molecule has two or more epoxide groups and molecular weight is 200 to 1,000 non-halogen polyfunctional epoxy resin, (3) stiffening agent, (4) curing catalyst, (5) phosphorus content is equal to or greater than the phosphorus fire retardant that 10 quality % and thermo-cracking temperature are equal to or higher than 300 ℃ non-halogen, (6) inorganic particulate, for example aluminium hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, or silica etc.
Here, the phosphorus fire retardant of described non-halogen and the ratio of described inorganic particulate in described binding compositions meet following condition: (1) Y be less than or equal to [X+30] (Y≤-X+30), in this case, X is 6 to 25 and comprises end value (6≤X≤25); (2) if X be 6 to 8 and comprise end value (6≤X≤8), then Y more than or equal to [2X+22] (Y 〉=-2X+22); If X is 8 to 12 and comprises end value (8≤X≤12), then Y more than or equal to [X+14] (Y 〉=-X+14); If perhaps X is 12 to 25 and comprises end value (12≤X≤25), then Y is more than or equal to 2 (Y 〉=2), wherein " X " is the phosphorus fire retardant weight based on the non-halogen of 100 weight part binder composition gross weights, and " Y " is the inorganic particulate weight based on 100 weight part binder composition gross weights.
Preferably, the phosphorus fire retardant of described non-halogen is an organic secondary phosphine acid salt compound fire retardant, and described inorganic particulate is an aluminium hydroxide.
Realize above-mentioned purpose of the present invention by mulch film, it is characterized in that the binder composition that will be used for the halogen mulch film is applied to the polyimide basilar membrane as binder layer with the binder composition that is used for the halogen mulch film.
Description of drawings
The features and advantages of the present invention will be become obviously by the as detailed below of illustrative its preferred implementation with reference to the accompanying drawings, wherein:
Fig. 1 is the side-view that is bonded to the mulch film of electrolysis copper film;
What Fig. 2 schematically represented to meet relevant criterion oozes out performance (by zero expression);
What Fig. 3 schematically represented not meet relevant criterion oozes out performance (being represented by X); With
Fig. 4 represents that schematically wherein flexible copper film forms the plate of pattern.
Embodiment
Below, reference implementation mode and invention accompanying drawing are described the present invention in more detail.
It will be apparent to one skilled in the art that these embodiments are used for illustration the present invention in more detail, scope of the present invention should not be subjected to the restriction of these embodiments.
At the binder composition that is used for halogen mulch film of the present invention, the paracril (hereinafter being also referred to as " NBR ") that comprises carboxyl has 2,000 to 200,000, preferred 10,000 to 200,000 weight-average molecular weight, the acrylonitrile content of 10 to 60 weight %, preferred 20 to 40 weight % and the carboxyl-content of 5 to 20 weight %.
In this case, if weight-average molecular weight is less than 10,000, its poor heat stability then is if weight-average molecular weight is higher than 200,000, its poorly soluble in solvent then, and its viscosity rises and causes the processibility of difference and the binding property of reduction when preparation solution.If the content of vinyl cyanide is less than 20 weight %, then its solvability in solvent reduces.The content of vinyl cyanide is higher than the electrical insulation capability that 40 weight % cause difference.If the content of carboxyl is 5 to 20 weight %, then is easy to adhere to NBR, other resin and adhesive substrate and rises to cause binding property.
And, at the binder composition that is used for halogen mulch film of the present invention, Resins, epoxy is the multifunctional non-halogen Resins, epoxy that per molecule has 2 or a plurality of epoxide groups, for example bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic resin varnish type epoxy resin, cresols type Resins, epoxy etc.Described Resins, epoxy can independently use or wherein two or more type combination uses.Based on 100 weight part NBR, the amount of multifunctional non-halogen Resins, epoxy is 50 to 200 weight parts among the present invention, and wherein the equivalent of epoxy (g/eq) is 200 to 1000.The content of multifunctional non-halogen Resins, epoxy causes reducing binding property less than 50 weight parts, also significantly reduces thermotolerance, thereby can not be with resulting composition as adhesive application.If the content of multifunctional non-halogen Resins, epoxy is greater than 200 weight parts, the gained tackiness agent is just too crisp and therefore can not keep the phase of gained film.
And at the binder composition that is used for halogen mulch film of the present invention, stiffening agent is not limited to particular type, as long as it is used as the stiffening agent of Resins, epoxy.The example of stiffening agent is amido stiffening agent, anhydride group stiffening agent, alkyd resin based stiffening agent etc., and they can independently use or wherein two or more type combination uses.Based on 100 weight part Resins, epoxy, above-mentioned stiffening agent amount in the present invention is 1 to 20 weight part.
And, for rubber linking agent of the present invention, can use the organic or inorganic superoxide, based on 100 weight part NBR of the present invention, its amount is 1 to 5 weight part.
And at the binder composition that is used for halogen mulch film of the present invention, curing catalyst is not limited to particular type, as long as it can promote the reaction between above-mentioned Resins, epoxy and the stiffening agent.The example of curing catalyst is for example glyoxal ethyline, a 2-ethyl-4-methylimidazole etc. of imidazole-based compounds, and phosphino-promotor is triphenylphosphine, tetraphenyl phosphine, tetraphenyl boric acid ester etc. for example.They can independently use or will wherein two or more are used in combination, and based on the above-mentioned Resins, epoxy of 100 weight parts, its amount is 0.1 to 5 weight part.
At the binder composition that is used for halogen mulch film of the present invention, the non-halogen flame retardant that does not comprise halogen atom is a phosphorio compound.Its required performance is preferably phosphorus content should be greater than 10 quality %; Its thermo-cracking temperature is equal to or higher than 300 ℃; And water insoluble or typical organic solvent is as acetone, methyl ethyl ketone, toluene etc.
The example of the non-halogen flame retardant of the present invention that meets the requirements and can buy on market is " Exolit OP935 " (made by Clariant, have the phosphorus content of 23 quality %).
At the binder composition that is used for halogen mulch film of the present invention, use inorganic particulate to provide thermotolerance and flame retardant resistance, and further increase punching press (punching) performance as tackiness agent.The available example of inorganic particulate is aluminium hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, silica etc.Based on 100 weight part NBR, the preferred amounts of inorganic particulate is 20 to 60 weight parts.Its amount can cause reducing flame retardant resistance, thermotolerance and the stampability of tackiness agent less than 20 weight parts.Its amount can cause reducing physicals, for example adhesive flow, binding property etc. greater than 60 weight parts.
And the phosphorus fire retardant of non-halogen and the ratio of inorganic particulate meet following condition: (1) Y be less than or equal to [X+30] (Y≤-X+30), in this case, X is 6 to 25 and comprises end value (6≤X≤25); (2) if X be 6 to 8 and comprise end value (6≤X≤8), then Y more than or equal to [2X+22] (Y 〉=-2X+22); If X is 8 to 12 and comprises end value (8≤X≤12), then Y more than or equal to [X+14] (Y 〉=-X+14); If perhaps X is 12 to 25 and comprises end value (12≤X≤25), then Y is more than or equal to 2 (Y 〉=2), wherein " X " is the phosphorus fire retardant weight based on the non-halogen of 100 weight part binder composition gross weights, and " Y " is the inorganic particulate weight based on 100 weight part binder composition gross weights.
To have the binder composition of said components and organic solvent such as methyl ethyl ketone, methyl alcohol, phenylcarbinol, toluene, tetrahydrofuran (THF), chlorobenzene etc., to be uniformly mixed into viscosity be 100 to 2,000CPS, and preferred 200 to 800CPS.The thickness that then the binder composition mixture is applied to dry back coating on heat-resistant film is 25 μ m.50 to 170 ℃ of dryings 1 to 10 minute, lamination barrier sheet or isolation processing film were to obtain mulch film thereon with described film.
Below, will the present invention be described in more detail by embodiment and comparative example.Should notice that the present invention is not limited.
The used material of embodiment and comparative example is following listed:
(1)NBR
A:27 weight % vinyl cyanide, 3.5 weight % carboxyls
(2) Resins, epoxy
A:YD-011, epoxy equivalent (weight): 475, available from Kukdo Chemical Co.
B:Epicoat 828, epoxy equivalent (weight): 185, and Nippon Epoxy Resin Co.
C:EOCN-103, epoxy equivalent (weight): 209, Nippon Chemical Co.
(3) stiffening agent
A:DDS (diamino diphenyl sulfone)
B:HF-3M, the OH equivalent: 107, Meihwa Co.
(4) curing catalyst
A:2MI (Methylimidazole)
(5) non-halogen flame retardant
A:OP-935, phosphorus content: 23 weight %, phosphine compound, Clariant Co., the thermo-cracking temperature is equal to or greater than 300 ℃.
B:SPB-100, phosphorus content: 13 weight %, phosphazene compound, Otsuka ChemicalCo., the thermo-cracking temperature is lower than 300 ℃.
(6) inorganic particulate
A: aluminum oxide (median size: 1 μ m)
Embodiment 1
To have component (30% solid) uniform mixing of following table 1 described weight part and be distributed in the methylethyl ketone solvent with homogenizer.
Mixture is administered on the polyimide film that thickness is 12.5 μ m then, making dried coat-thickness is 25 μ m, then respectively will be in 50 ℃ of baking ovens through the film thermofixation 10 minutes of coating, and about 3 minutes of thermofixation in 60 ℃ of baking ovens then.With the film of gained drying and barrier film lamination with the preparation mulch film.
Embodiment 2-14
Prepare mulch film according to the mode identical with embodiment 1, difference is, mixes the binder ingredients of embodiment 2 to 14 in the following table 1 respectively.
Table 1: the component of each embodiment (by weight)
Figure A200810082342D00091
Comparative example 1-13
Prepare mulch film according to the mode identical with embodiment 1, difference is, mixes the binder ingredients of comparative example 1 to 13 in the following table 2 respectively.
Table 2: the component of comparative example (by weight)
Figure A200810082342D00101
Estimate performance in the following manner, show the result in following table 3 and 4 with the mulch film of said components and aforesaid way preparation.
Estimate the performance of mulch film
1. binding property
Then at 170 ℃/40kg fUnder the condition of/40min, the various mulch films that will prepare in embodiment and comparative example respectively with thermocompressor are adhered on the electrolysis copper film of 35 μ m thickness.Each film is cut into width 1cm and length 10cm.Behind fixing polyimide film, at 90 degree directions each copper film of speed tractive, to measure power at that time and therefore mean value to be expressed as binding property (JIS C6481) with 50mm/min.
2. in the thermotolerance in when welding
According to measure the identical mode of binding property, the electrolysis copper film is adhered on each mulch film, then film is cut into 5cm * 5cm.Film was soaked 10 seconds with predetermined temperature in solder tank, take out then to check appearance change such as layering or variable color, the top temperature when not changing to measure.
3. flame retardant resistance
For mulch film, according to the regulation of UL94 V-O, by at 170 ℃/40kg according to the preparation of embodiment and comparative example fUnder the condition of/40min, with thermocompressor the tackiness agent of each film is surveyed on the binder side of the mulch film that is adhered to embodiment 1 preparation, estimated flame retardant resistance thus with the preparation sample.When the result meets relevant criterion, it is provided " zero ", when the result does not meet standard, provide " X ".
4. ooze out
On each mulch film, make the circular port of five diameter 5mm with the interval of 2cm according to embodiment and comparative example preparation.Then at 170 ℃/40kg fUnder the condition of/40min, film is adhered on the electrolysis copper film of 35 μ m thickness with thermocompressor.With the tackiness agent around the microscopy taphole.When effusive tackiness agent shape evenly and provide " zero " when not having colour-change, otherwise when described shape is inhomogeneous or exist a large amount of adhesive melts also during effusive sign, provide " X " (referring to Fig. 1,2 and 3).
5. mobile
At first, the flexible copper membrane laminate is made the circuit with 1mm width pattern, as shown in Figure 4.At 170 ℃/40kg fUnder the condition of/40min, will be adhered on the circuit according to each mulch film of embodiment and comparative example preparation with thermocompressor.With the space between the microscopic examination circuit pattern, whether filled the space to check the tackiness agent in the mulch film.When tackiness agent has been filled 100% space, provide " zero ", when some has completely filled, do not provide " X ".
Table 3: the result of each embodiment
Flame retardant resistance (V-O) Binding property (N/cm) Thermotolerance in welding (℃) Ooze out Mobile
Embodiment
1 ○ 12 330 ○ ○
Embodiment 2 ○ 14 330 ○ ○
Embodiment 3 ○ 13 330 ○ ○
Embodiment 4 ○ 12 330 ○ ○
Embodiment 5 ○ 11 330 ○ ○
Embodiment 6 ○ 10 320 ○ ○
Embodiment 7 ○ 6 300 ○ ○
Embodiment 8 ○ 6 290 ○ ○
Embodiment 9 ○ 12 340 ○ ○
Embodiment 10 ○ 8 320 ○ ○
Embodiment 11 ○ 7 320 ○ ○
Embodiment 12 ○ 7 310 ○ ○
Embodiment 13 ○ 6 300 ○ ○
Embodiment 14 ○ 6 300 ○ ○
Table 4: the result of each comparative example
Flame retardant resistance (V-O) Binding property (N/cm) Thermotolerance in welding (℃) Ooze out Mobile
Comparative example 1 X 12 330 ○ ○
Comparative example 2 X 12 340 ○ ○
Comparative example 3 X 12 330 ○ ○
Comparative example 4 X 12 330 ○ ○
Comparative example 5 X 12 330 ○ ○
Comparative example 6 X 10 320 ○ ○
Comparative example 7 ○ 5 310 ○ X
Comparative example 8 ○ 4 300 ○ X
Comparative example 9 ○ 3 280 ○ X
Comparative example 10 ○ 2 280 ○ X
Comparative example 11 X 7 300 ○ X
Comparative example 12 ○ 14 330 X ○
Comparative example 13 ○ 14 330 X ○
Useful in practice mulch film performance must unconditionally meet UL 94V-0, and its binding property should be greater than 6N/cm, and this is lower than the binding property of the conventional mulch film that comprises halogen atom.Ooze out performance and must meet relevant criterion, because uneven tackiness agent appearance will cause defective film in the electroplating process of back.And mobile necessary 100% filling (conformance with standard) that shows will be because the incomplete filling between the circuit pattern of mulch film will cause that pattern line is by bubble partition, separation etc.
Yet with reference to result's (being shown in table 4) of comparative example, comparative example 1 and 11 does not satisfy flame-retardancy standards, because wherein do not comprise the phosphorus fire retardant of halogen.For comparative example 2,3,4,5 and 6, used fire retardant and inorganic particulate, but its amount is too little, thereby the gained film does not satisfy flame-retardancy standards.On the contrary, for comparative example 7,8,9 and 10, the amount of fire retardant and inorganic particulate is too big, thus flame retardant resistance conformance with standard but flowability does not meet standard.And, for comparative example 12 and 13, used the phosphorus fire retardant of non-halogen, but the gained film has lower thermo-cracking temperature (being lower than 300 ℃), thereby satisfied other physicals, but it oozes out performance and does not meet standard.
Table 3 in the reference, it shows the result of various embodiments of the present invention, and all results all meet UL 94 V-0, and the binding property of gained film is higher than 6N/cm.Exudative also conformance with standard.For flowability, obtained 100% and filled, thereby do not had the pattern interruption that when the space of not exclusively filling between the circuit pattern, causes and separate because of bubble.Can see that the gained film for preparing does not meet all above-mentioned requirements in comparative example.
Satisfy performances such as desired all flame retardant resistances of mulch film, binding property, thermotolerance, exudative, flowability according to the mulch film of the present invention preparation.
Can see from the description of front, under the situation that does not deviate from true spirit of the present invention and scope, can carry out various modifications and change.The description that should be appreciated that the front is used for illustration, is not to be used to limit the scope of the invention that is limited by appended claims.
Inventive point of the present invention is each and each combination of each and each novel features and described feature.
In claims, the existence of other key element shown in the use that verb " comprises " and part of speech is out of shape is not got rid of beyond the key element.The existence of a plurality of described key elements do not got rid of in the used article " " in key element front.
The description of drawing reference numeral
1: coverlay
2: electrolytic film
3: flow out to the adhesive on the coverlay
4: the copper pattern of width 1mm

Claims (4)

1. binder composition that is used for the halogen mulch film is characterized in that comprising:
(1) comprises carboxyl and have 10,000 to 200,000 molecular weight and acrylonitrile content is the paracril (NBR) of 20 to 40 weight parts;
(2) to have two or more epoxide groups and molecular weight be 200 to 1,000 non-halogen polyfunctional epoxy resin to per molecule;
(3) stiffening agent;
(4) curing catalyst;
(5) phosphorus content is equal to or greater than the phosphorus fire retardant that 10 quality % and thermo-cracking temperature are equal to or higher than 300 ℃ non-halogen; With
(6) inorganic particulate, for example aluminium hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT or silica.
2. binder composition as claimed in claim 1 is characterized in that the phosphorus fire retardant of described non-halogen and the ratio of described inorganic particulate meet following condition:
(1) Y be less than or equal to [X+30] (Y≤-X+30), in this case, X is 6 to 25 and comprises end value (6≤X≤25); With
(2) if X be 6 to 8 and comprise end value (6≤X≤8), then Y more than or equal to [2X+22] (Y 〉=-2X+22); If X is 8 to 12 and comprises end value (8≤X≤12), then Y more than or equal to [X+14] (Y 〉=-X+14); If perhaps X is 12 to 25 and comprises end value (12≤X≤25), then Y is more than or equal to 2 (Y 〉=2),
Wherein " X " is the phosphorus fire retardant weight based on the non-halogen of 100 weight part binder composition gross weights, and " Y " is the inorganic particulate weight based on 100 weight part binder composition gross weights.
3. binder composition as claimed in claim 2, the phosphorus fire retardant that it is characterized in that described non-halogen are organic secondary phosphine acid salt compound fire retardants, and described inorganic particulate is an aluminium hydroxide.
4. the mulch film with the binder composition that is used for the halogen mulch film is characterized in that each described binder composition that is used for the halogen mulch film in the claim 1 to 3 is administered to the polyimide basilar membrane as binder layer.
CN2008100823427A 2008-01-14 2008-02-29 Adhesive composition used for non-halogen coating and coating using the same Active CN101486883B (en)

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CN102516914A (en) * 2011-11-21 2012-06-27 烟台德邦电子材料有限公司 Halogen-free flame-retardant epoxy resin electronic pouring sealant
CN101987947B (en) * 2009-07-29 2012-10-10 东丽先端素材株式会社 Adhesive composition for halogen-free covering film and covering film coated by the same
CN108586847A (en) * 2018-05-21 2018-09-28 南昌正业科技有限公司 A kind of low halogen cover film
CN109246920A (en) * 2017-06-08 2019-01-18 臻鼎科技股份有限公司 Cover film and preparation method thereof
TWI660859B (en) * 2017-06-07 2019-06-01 臻鼎科技股份有限公司 Cover layer and method for making the same

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JP2005120228A (en) * 2003-10-16 2005-05-12 Nitto Denko Corp Epoxy resin composition for optical semiconductor element sealing and optical semiconductor device using the composition
CN100453593C (en) * 2005-11-02 2009-01-21 长春人造树脂厂股份有限公司 Difficult combustible epoxy resin composition not containing halogen

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CN101987947B (en) * 2009-07-29 2012-10-10 东丽先端素材株式会社 Adhesive composition for halogen-free covering film and covering film coated by the same
CN102516914A (en) * 2011-11-21 2012-06-27 烟台德邦电子材料有限公司 Halogen-free flame-retardant epoxy resin electronic pouring sealant
TWI660859B (en) * 2017-06-07 2019-06-01 臻鼎科技股份有限公司 Cover layer and method for making the same
CN109246920A (en) * 2017-06-08 2019-01-18 臻鼎科技股份有限公司 Cover film and preparation method thereof
CN109246920B (en) * 2017-06-08 2020-10-02 臻鼎科技股份有限公司 Covering film and manufacturing method thereof
CN108586847A (en) * 2018-05-21 2018-09-28 南昌正业科技有限公司 A kind of low halogen cover film

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KR20090078051A (en) 2009-07-17
TWI434907B (en) 2014-04-21
CN101486883B (en) 2012-06-13

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