CN101987947A - Adhesive composition for halogen-free coverlay film and coverlay film coated by the same - Google Patents
Adhesive composition for halogen-free coverlay film and coverlay film coated by the same Download PDFInfo
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- CN101987947A CN101987947A CN2009101778993A CN200910177899A CN101987947A CN 101987947 A CN101987947 A CN 101987947A CN 2009101778993 A CN2009101778993 A CN 2009101778993A CN 200910177899 A CN200910177899 A CN 200910177899A CN 101987947 A CN101987947 A CN 101987947A
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- halogen
- mulch film
- coverlay film
- adhesive composition
- binder composition
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
Abstract
The present invention generally relates to an adhesive composition for halogen-free coverlay film and a coverlay film coated by the same. More particularly, the invention relates to the adhesive composition for the halogen-free coverlay film and the coverlay film coated by the same. The adhesive composition has undeteriorated binding strength and heat resistance in a humidity condition in which the covering film is covered through replacing NBR (nitrile butadiene rubber) which is commonly used as the adhesive for cover binding by the acrylic acid copolymer that contains hydroxy and carboxyl. Thus the adhesive composition for the halogen-free coverlay film comprises the following components: (1) acrylic resin which contains hydroxy and carboxyl and has a weight average molar mass of 300,000-800,000 and a viscosity of 800-10,000cP in 25 DEG C; (2) phenolic resin; (3) multifunctional epoxide resin; (4) solidifying agent; (5) solidifying promoting agent; (6) flame retardant based on non-halogen; (7) inorganic particles and (8) cross linker.
Description
Technical field
Relate generally to of the present invention is used for the binder composition of halogen mulch film and scribbles the mulch film of this binder composition, more specifically, the mulch film that the present invention relates to be used for the binder composition of halogen mulch film and scribble this binder composition, this binder composition replaces using usually acting on the NBR (paracril) that covers the adherent tackiness agent by the acrylic copolymer that use contains hydroxyl and carboxyl, thereby bond strength under the humidity condition that mulch film exposed and thermotolerance can deteriorations.
Background technology
Recently, owing to require electronic product to have smaller szie, ultrathin and the trend of high integration more, the use of flexible printed circuit board (PCB) significantly increases, and the use that causes being used for the mulch film of holding circuit thus also increases.In addition, because the improvement of product function causes the structure of electronic product to become complicated more, correspondingly just strict more to the mulch film performance demands.
At present, according to WEEE (scrapping electric/electronic device), the RoHS (restriction of objectionable impurities) etc. in Europe, be starved of development environment close friend's material.Yet, the conventional tackiness agent that is used for electronic material such as mulch film, semiconductor-encapsulating material etc. used contain halogen for example the compound of bromine as fire retardant.Thereby when the burning of this tackiness agent, it produces toxic gas as based on the compound of dioxin etc.Therefore, press for the halogen tackiness agent that is used for electronic material.
Usually, mulch film is by at the binder layer of the semicure attitude of a side of heat-resistant film coating be used to protect the release paper of tackiness agent to constitute.Because this mulch film adheres to flexible printed circuit board (PCB) and goes up with the protection printed wiring, so thermotolerance, bond strength, flame retardant resistance etc. all are the required key propertys of mulch film, especially need to satisfy simultaneously these performances.
Therefore, made great efforts to have developed to use and variously replaced mulch film based on the fire retardant of halogen based on organic fire retardant; Yet this class mulch film does not satisfy all desired properties.Especially, maximum problem is and since because of environment or in the course of processing mulch film institute humidity condition of exposure repeatedly, the thermotolerance of mulch film and adhesive strength deteriorates.
Summary of the invention
Therefore, the present invention is intended to address the above problem, and the objective of the invention is, and binder composition that is used for the halogen mulch film that satisfies above-mentioned all desired properties and the mulch film that scribbles this binder composition are provided.According to the present invention, the objective of the invention is, be provided for the binder composition and the mulch film that scribbles this binder composition of halogen mulch film, this binder composition satisfies performance required in the mulch film such as flame retardant resistance, bond strength, thermotolerance etc., even and this binder composition be exposed to any deterioration that does not also show performance under the situation of high humidity.
To the detailed description of invention, these and other objects of the present invention and advantage will be apparent by subsequently.
Top purpose is achieved by the binder composition that is used for the halogen mulch film, and this binder composition comprises: (1) contains the acrylic resin of hydroxyl and carboxyl, and its weight-average molecular weight is 300,000～800,000,25 ℃ viscosity is 800～10,000cP; (2) resol; (3) polyfunctional epoxy resin; (4) solidifying agent; (5) curing catalyst; (6) based on the fire retardant of non-halogen; (7) inorganic particulate; (8) linking agent.
Top purpose further is achieved by the mulch film that is coated with the binder composition that is useful on the halogen mulch film, and the binder composition that wherein is used for the halogen mulch film is coated the polyimide substrate film as binder layer.
The present invention has all properties of satisfying such as flame retardant resistance, bond strength, stable on heating effect, even and under the situation that is exposed to the high humidity that mulch film needs, these performances can deterioration yet.
Description of drawings
Fig. 1 is the sectional view of mulch film of the present invention.
Major portion brief description in the＜accompanying drawing 〉
10: polyimide film
20: tackiness agent
30: release paper
Embodiment
Hereinafter, describe the preferred embodiments of the invention with reference to the accompanying drawings in detail.The detailed description that should be appreciated that the preferred embodiments of the invention only is exemplary, and therefore various changes and modifications within the spirit and scope of the present invention should be conspicuous to those skilled in the art.
Fig. 1 is the sectional view of mulch film of the present invention.The binder composition that is used for the halogen mulch film of the present invention comprises: (1) contains the acrylic resin of hydroxyl and carboxyl, and its weight-average molecular weight is that 300,000～800,000,25 ℃ viscosity is 800～10,000cP; (2) resol; (3) polyfunctional epoxy resin; (4) solidifying agent; (5) curing catalyst; (6) based on the fire retardant of non-halogen; (7) inorganic particulate; (8) linking agent.
The binder composition that is used for the halogen mulch film of the present invention contains the acrylic resin of hydroxyl and carboxyl, and it preferably has 300,000～800,000 weight-average molecular weight.This is because if weight-average molecular weight is lower than 300,000, so the thermostability deterioration.On the other hand, if weight-average molecular weight is higher than 800,000, the solubleness in solvent reduces so, and because the viscosity increase during preparation solution causes workability deteriorates, and also deterioration of bond strength.In addition, acrylic resin preferably have 25 ℃ 800～10, the viscosity of 000cP and the hydroxyl value of 5～35mgKOH/g (below, be called HV).If the ratio of institute's hydroxyl is 5～35mgKOH/g, bonding between it helps at the bottom of other resin and the adhesive lining so, thus cause that its bond strength increases.
As the resol that is used for the binder composition of halogen mulch film of the present invention, preferably be used alone or in combination resol type phenol resin or lacquer resins.
About the Resins, epoxy that is used for the binder composition of halogen mulch film of the present invention, use per molecule to contain the multifunctional non-halogen Resins, epoxy of two above epoxy group(ing), the example of this Resins, epoxy comprises bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic aldehyde linear epoxy resin and cresols type Resins, epoxy.Can be used in combination this two or more based epoxy resins.With respect to per 100 parts by weight of acrylic resins, the total amount of employed resol and Resins, epoxy is 50～150 weight parts.If total amount is less than 50 weight parts, the thermotolerance of tackiness agent is degenerated so, if be higher than 150 weight parts, tackiness agent becomes fragile and frangible and its adhesive strength deteriorates so.
Secondly, be not particularly limited, as long as it is usually with acting on curing agent for epoxy resin for the solidifying agent that is used for the binder composition of halogen mulch film of the present invention.The example of solidifying agent comprises the solidifying agent based on amine, the solidifying agent of acid anhydride-based etc., and these solidifying agent may be used singly or two or more in combination.With respect to per 100 weight part Resins, epoxy, preferably use 1～20 weight part solidifying agent.
Be not particularly limited for the curing catalyst that is used for the binder composition of halogen mulch film of the present invention, as long as it promotes the reaction between Resins, epoxy and the solidifying agent.The example of this curing catalyst comprises based on the compound of imidazoles such as glyoxal ethyline, 2-ethyl-4-methylimidazole etc., and based on the reagent of phosphine such as triphenylphosphine, tetraphenyl phosphine, tetraphenyl borate salts etc.With respect to per 100 weight part Resins, epoxy, the consumption of preferred consolidation promotor is 0.1～5 weight part.
About the fire retardant that is used for the binder composition of halogen mulch film of the present invention based on non-halogen, the fire retardant that uses halogen atom-containing not as based on phosphorus, based on trimeric cyanamide or based on the compound of fluorine.The required ideal performance of these fire retardants comprises: pyrolysis temperature more than 300 ℃ and the insoluble in water or other common organic solvent such as acetone, methyl ethyl ketone, toluene etc.The example of the product that satisfies this class performance that can buy on the market comprises " ExolitOP935 (made phosphorus content: 23 quality %) by Clariant company (Clariant Corp.) ", and it is the organic secondary phosphine acid salt compound.With respect to the gross weight of binder composition, the consumption of fire retardant is 3%～15%.If the consumption of fire retardant is less than 3%, even if use a large amount of inorganic particulates also be difficult to realize flame retardant resistance (V-0) so,, if the consumption of fire retardant is more than 15%, so such as the performance degradation of bond strength, thermotolerance etc.
The inorganic particulate that is used for the binder composition of halogen mulch film of the present invention is mainly used in to tackiness agent thermotolerance and flame retardant resistance is provided, and they also improve stampability (punchability).The example of available inorganic particulate comprises aluminium hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, silicon-dioxide etc. among the present invention.With respect to per 100 parts by weight of acrylic resins, the desirable consumption of inorganic particulate is 5～30 weight parts.If the consumption of inorganic particulate is less than 5 weight parts, the flame retardant resistance of tackiness agent, thermotolerance and stampability deterioration so, if the consumption of inorganic particulate more than 30 weight parts, workability reduces and such as the performance degradation of bond strength during tackiness agent is made.
As the linking agent that is used for the binder composition of halogen mulch film of the present invention, can adopt based on
The compound of azoles quinoline and organic or inorganic superoxide with respect to per 100 parts by weight of acrylic resins, preferably add 1～5 parts by weight of cross-linking agent.
Utilize organic solvent such as methyl ethyl ketone, methyl alcohol, phenylcarbinol, toluene, tetrahydrofuran (THF), chlorobenzene etc., uniform mixing is according to the binder composition that is used for the halogen mulch film of aforesaid preparation of compositions.At this moment, the viscosity of composition is 100～2, and 000cP is preferably 200～800cP.As follows composition is applied on the heat-resistant film: make that dried thickness is 25 μ m, solidified 1～20 minute down at 50 ℃～170 ℃ then.Subsequently, carry out following process (lamination), will treat that wherein the processed release paper of the demoulding or film adhere on the heat-resistant film that is coated with composition, to obtain mulch film.
In addition, the present invention further comprises the mulch film that is coated with the binder composition that is useful on the halogen mulch film, and the binder composition that wherein is used for the halogen mulch film is coated the polyimide substrate film as binder layer.
Hereinafter, will the present invention more specifically be described by embodiment and comparative example.Yet the present invention is not limited to these embodiment.
Next, description is introduced the material that adopts in present embodiment and the comparative example.
(1) acrylic resin
A: product: WS-023, weight-average molecular weight: 500,000, HV:20mg KOH/g is made by long rapids Co., Ltd. (Nagase Chemtex Corp.).
(2) paracril (NBR)
A: product: N-34 contains the NBR of carboxyl, is made by Zeon Corp (NipponZeon Co.Ltd).
(3) resol
A: product: Hitanol H2181, resol type phenol resin, (Hitachi Chemical Co. Ltd.) makes to change into Co., Ltd. by Hitachi.
B: product: HF-4M, lacquer resins, (MeiwaChemical Co. Ltd.) makes by bright and KCC.
(4) Resins, epoxy
A: product: EOCN-104S, epoxy equivalent (weight): 218, (Nipponkayaku Co. Ltd.) makes by Nippon Kayaku K. K.
B: product: YD-011, epoxy equivalent (weight): 475, (Kuk DoChemical Industrial Co. Ltd.) makes by national capital Chemical Co., Ltd.
(5) solidifying agent
A:DICY (Dyhard RU 100)
(6) curing catalyst
A:2MI (Methylimidazole)
(7) based on the fire retardant of non-halogen
A: product: OP-935, phosphorus content: 23 quality %, phosphinate salt compound is made by Clariant company.
(8) inorganic particulate
A: aluminium hydroxide (median size: 1 μ m)
(9) linking agent
A:2,2 '-(1, the 3-phenyl)-two (2-
The azoles quinoline)
[embodiment 1]
Each component shown in the interpolation following table 1 and solid content are 30% methyl ethyl ketone, and mix equably with homogenizer.Next, mixed composition is applied on the polyimide film that thickness is 12.5 μ m as follows: make that dried thickness is 25 μ m, subsequently in 50 ℃ of dry and thermofixations 10 minutes in baking oven, in 160 ℃ of dry and thermofixations 3 minutes in baking oven.At last, the release paper lamination is prepared mulch film thereon.
[embodiment 2～4]
Prepare mulch film in the mode identical with embodiment 1, different is to add each component of tackiness agent as shown in the embodiment 2～4 of following table 1.
[table 1]
[comparative example 1～7]
Prepare mulch film in the mode identical with embodiment 1, different is to add each component of tackiness agent as shown in the comparative example 1～7 of following table 2.
[table 2]
Test the results are shown in table 3 and table 4 according to the performance of the mulch film of composition in top embodiment and the comparative example and method preparation.
[method of test products performance]
1. bond strength
Under the condition of 160 ℃/40kgf/30 minute, utilize hot pressing, will adhere on the electrolytic copper foil that thickness is 35 μ m according to each mulch film of top embodiment and comparative example preparation.Next, with the bar that the Copper Foil that has mulch film on it is cut into that 1cm is wide, 10cm is long, and fixing polyimide film.Then, in 90 ℃ of directions with 50mm/ minute speed tractive Copper Foil to measure bond strength.The mean value of this measuring result is represented bond strength (JIS C6481).
2. the bond strength under humidity condition
After preparing sample (test piece) in the mode identical, utilize controlled thermohygrostat, film is exposed 96 hours under the humidity condition of 40 ℃/90RH% with the method for last planar survey bond strength.Then, measure bond strength under the humidity condition in the mode identical with the method for last planar survey bond strength.
3. welding thermotolerance
Be in the same place electrolytic copper foil and mulch film are adhered to one another in the mode identical, be cut into the sheet of 5cm * 5cm then with the method for measuring bond strength., make this sheet in the solder bath under preset temperature (solder bath) floating 10 seconds thereafter, the external change of taking out sample for reference then as peel off, variable color etc., with measure sample the top temperature that external change is reached can not take place.Measurement is carried out in 210～340 ℃ temperature range, raises 10 ℃ at every turn.Obtain under this temperature to guarantee all OK temperature of OK of all three samples under each temperature three samples being tested.
4. the welding thermotolerance under humidity condition
To weld after the identical mode of stable on heating method prepares sample with last planar survey, utilize controlled thermohygrostat, film is exposed 96 hours under the humidity condition of 40 ℃/90RH%.Then, measure thermotolerance to weld the identical mode of stable on heating method with last planar survey.
5. flame retardant resistance
Under the condition of 160 ℃/40kgf/30 minute, utilize hot pressing, the mulch film made from each mulch film of making like this with according to embodiment 1 is adhered to one another to the binder side of two films, thereby makes sample.Then, based on the UL94V-0 standard, the flame retardant resistance of test sample is when sample passes through test tense marker " O ", when not passing through test tense marker " X ".
The test-results of the product performance of [table 3] embodiment
| Kind | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Bond strength (N/cm) | 14 | 11 | 15 | 12 |
| Bond strength under humidity condition (N/cm) | 13 | 11 | 12 | 11 |
| The welding thermotolerance (℃) | ＞340 | ＞340 | ＞340 | ＞340 |
| Welding thermotolerance under humidity condition (℃) | 270 | 280 | 260 | 270 |
| Flame retardant resistance (V-0) | O | O | O | O |
The test-results of the product performance of [table 4] comparative example
It is more than the 10N/cm that the Practical Performance that is suitable for conventional mulch film needs bond strength, and the bond strength under humidity condition is more than the 8N/cm.In addition, the welding thermotolerance initially needs more than 290 ℃, and being exposed to humidity condition needs more than 260 ℃ afterwards.For flame retardant resistance, need the V-0 level.Mulch film need satisfy the performance above all simultaneously.
The test-results of the embodiment from table 3 and table 4 and the product performance of comparative example as can be seen, embodiment has satisfied all desired properties such as bond strength, the bond strength under humidity condition, welding thermotolerance, welding thermotolerance and flame retardant resistance under humidity condition; Yet comparative example does not satisfy all desired properties.Under the situation of the mulch film in comparative example 1-4, promptly for the mulch film that adopts the NBR preparation according to routine techniques, mulch film had excellent performance (bond strength, thermotolerance etc.) before being exposed to humidity condition; Yet, be exposed to the humidity condition rapid deterioration of its performance afterwards.This is because the part carbon-to-carbon double bond is arranged in the NBR molecular structure, and this part carbon-to-carbon double bond is so weak so that because of fracture easily such as oxidation, moisture at structural formula.Since this fracture of molecular structure, the flexibility decrease of rubber, thus cause performance degradation.On the other hand, the acrylic resin in the embodiment of the invention has saturated structure fully, and without any unsaturated structure, this causes that again performance can or only have very little deterioration because of oxidation and moisture deterioration hardly in the molecule.In addition, comparative example 5 and 6 shows, when not having fire retardant and inorganic particulate or only using a kind of in these components, is difficult to realize flame retardant resistance.In addition, comparative example 7 shows, cause because there not being linking agent lacking in the tackiness agent crosslinked, so the welding thermotolerance under humidity condition descends.
Claims (2)
1. binder composition that is used for the halogen mulch film, it comprises:
(1) contain the acrylic resin of hydroxyl and carboxyl, its weight-average molecular weight is that 300,000～800,000,25 ℃ viscosity is 800～10,00cP;
(2) resol;
(3) polyfunctional epoxy resin;
(4) solidifying agent;
(5) curing catalyst;
(6) based on the fire retardant of non-halogen;
(7) inorganic particulate; With
(8) linking agent.
2. mulch film, it is coated with the binder composition that is useful on the halogen mulch film, and wherein the binder composition that is used for the halogen mulch film of claim 1 is applied in the polyimide substrate film as binder layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2009-0069392 | 2009-07-29 | ||
| KR1020090069392A KR101100381B1 (en) | 2009-07-29 | 2009-07-29 | Adhesive Composition for Halogen-Free Coverlay Film and Coverlay Film Coated by the Same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101987947A true CN101987947A (en) | 2011-03-23 |
| CN101987947B CN101987947B (en) | 2012-10-10 |
Family
ID=43744743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101778993A Expired - Fee Related CN101987947B (en) | 2009-07-29 | 2009-09-24 | Adhesive composition for halogen-free covering film and covering film coated by the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101100381B1 (en) |
| CN (1) | CN101987947B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016064190A1 (en) * | 2014-10-24 | 2016-04-28 | 주식회사 두산 | Metal-clad laminate for coverlay, and coverlay-free multilayered flexible printed circuit board |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102179483B1 (en) | 2019-10-02 | 2020-11-16 | 한화솔루션 주식회사 | Adhesive Composition for coverlay film and coverlay film for flexible printedcircuit board comprising the same |
| KR102216722B1 (en) | 2019-10-02 | 2021-02-16 | 한화솔루션 주식회사 | Adhesive Composition for coverlay film and coverlay film for flexible printedcircuit board comprising the same |
| KR102259563B1 (en) | 2019-10-02 | 2021-06-01 | 한화솔루션 주식회사 | Adhesive Composition for coverlay film and coverlay film for flexible printedcircuit board comprising the same |
| KR102216726B1 (en) | 2019-10-02 | 2021-02-16 | 한화솔루션 주식회사 | Adhesive Composition for coverlay film and coverlay film for flexible printedcircuit board comprising the same |
| KR20210039859A (en) | 2019-10-02 | 2021-04-12 | 한화솔루션 주식회사 | Adhesive Composition for coverlay film and coverlay film for flexible printedcircuit board comprising the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4434569B2 (en) * | 2002-10-18 | 2010-03-17 | 日立化成ポリマー株式会社 | Halogen-free flame-retardant adhesive composition and coverlay film |
| KR20090078051A (en) * | 2008-01-14 | 2009-07-17 | 도레이새한 주식회사 | Adhesive composition for halogen-free coverlay film and coverlay film using the same |
-
2009
- 2009-07-29 KR KR1020090069392A patent/KR101100381B1/en not_active IP Right Cessation
- 2009-09-24 CN CN2009101778993A patent/CN101987947B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016064190A1 (en) * | 2014-10-24 | 2016-04-28 | 주식회사 두산 | Metal-clad laminate for coverlay, and coverlay-free multilayered flexible printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101987947B (en) | 2012-10-10 |
| KR20110011918A (en) | 2011-02-09 |
| KR101100381B1 (en) | 2011-12-30 |
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