WO2010008213A9 - Silane based compound, method for preparing the same, and surface treating agent composition for copper foil including the silane based compound - Google Patents

Silane based compound, method for preparing the same, and surface treating agent composition for copper foil including the silane based compound Download PDF

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Publication number
WO2010008213A9
WO2010008213A9 PCT/KR2009/003913 KR2009003913W WO2010008213A9 WO 2010008213 A9 WO2010008213 A9 WO 2010008213A9 KR 2009003913 W KR2009003913 W KR 2009003913W WO 2010008213 A9 WO2010008213 A9 WO 2010008213A9
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Prior art keywords
formula
copper foil
silane
based compound
treating agent
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PCT/KR2009/003913
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French (fr)
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WO2010008213A3 (en
WO2010008213A2 (en
Inventor
Jong Ho Ryu
Jong Chan Won
Yong Seok Kim
Hyun Min Jung
Jin Young Park
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Iljin Copper Foil Co., Ltd.
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Publication of WO2010008213A2 publication Critical patent/WO2010008213A2/en
Publication of WO2010008213A3 publication Critical patent/WO2010008213A3/en
Publication of WO2010008213A9 publication Critical patent/WO2010008213A9/en

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Classifications

    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils

Definitions

  • the present invention relates to a silane-based compound, a method of preparing the silane-based compound, and a surface treating agent composition for copper foil including the silane based compound, and more particularly, to a new silane-based compound, a method of preparing the silane-based compound, and a surface treating agent composition for copper foil including the silane based compound.
  • FCCL flexible copper clad laminate
  • PCB printed circuit board
  • a FCCL is a multi-layered film formed of two or three layers in which polyimide is laminated on a copper foil.
  • etching precision also increases and thus it is required to reduce the surface roughness of the copper foil.
  • peel strength between the copper foil and a substrate for example, a polyimide film
  • a means to improve the peel strength is required.
  • a copper foil for a PCB generally processed using a silane-coupling agent as a surface treating agent of the copper foil for strengthening the peel strength between the copper foil and the substrate is disclosed in Japanese Patent Application 1990-026097.
  • the present invention provides a new silane-based compound that provides excellent peel strength between a substrate and the copper foil, a method of preparing the silane-based compound, and a surface treating agent composition for copper foil including the silane-based compound.
  • R 1 , R 2 , and R 3 may be each independently a C 1 -C 3 alkyl group and R 4 and R 5 may be each independently hydrogen or a C 1 -C 5 alkyl group.
  • a surface treating agent composition for copper foil including at least one compound selected from the group consisting of silane-based compounds represented by Formulae 1 through 4, and a solvent:
  • R 1 , R 2 , and R 3 may be each independently a C 1 -C 3 alkyl group and R 4 and R 5 may be each independently hydrogen or a C 1 -C 5 alkyl group.
  • R 1 , R 2 , and R 3 may be each independently a C 1 -C 3 alkyl group and R 4 and R 5 may be each independently hydrogen or a C 1 -C 5 alkyl group.
  • a PCB prepared by using the surface treating agent composition for copper foil including the silane-based compound according to the present invention has improved peel strength compared with a PCB on which the surface treating agent composition is not used or a PCB on which a silane-based compound including a general silane-based compound is used .
  • silane-based compound a silane-based compound, a method of preparing the silane-based compound, and a surface treating agent composition for copper foil including the silane-based compound according to embodiments of the present invention will be described in more detail.
  • the silane-based compound according to the present embodiment may be represented by Formulae1 through 4 .
  • R 1 , R 2 , and R 3 are each independently a C 1 -C 3 alkyl group and R 4 and R 5 are each independently hydrogen or a C 1 -C 5 alkyl group.
  • the silane-based compounds have a siloxane group at the ends thereof for a covalent bond with the copper foil and an imidazole group and/or an imide group at the other end thereof, wherein the imidazole group and/or the imide group has a structure similar to a polyimide film and thus bonding strength with a polyimide film may be improved.
  • the bonding strength between the copper foil and a polyimide film may be improved.
  • R 1 , R 2 , and R 3 in the silane-based compounds are each independently methyl or ethyl and R 4 and R 5 may be hydrogen.
  • the surface treating agent composition for copper foil according to another embodiment of the present invention may include at least one compound selected from the group consisting of silane-based compounds represented by Formulae 1 through 4, and a solvent.
  • R 1 , R 2 , and R 3 are each independently a C 1 -C 3 alkyl group and R 4 and R 5 are each independently hydrogen or a C 1 -C 5 alkyl group.
  • silane-based compound included in the surface treating agent composition an alkoxy group is changed into a hydroxy group by performing hydrolysis with the solvent.
  • the silane-based compounds are connected to each other by a condensation reaction and the connected silane-based compounds are fixed to the copper foil by covalent bond with the hydroxy group formed on the copper foil. As a result, an organic layer of the silane-based compound is formed on the copper foil.
  • the surface treating agent composition may further include other surface treating agents or antirust agents which are well known to one of ordinary skill in the art, in addition to the silane-based compound, and the surface treating agents or the antirust agents are not particularly restricted.
  • R 1 , R 2 , and R 3 of the silane-based compounds may be each independently methyl or ethyl and R 4 and R 5 may be hydrogen.
  • the solvent included in the surface treating agent composition for copper foil may be one selected from the group consisting of water, methanol, ethanol, and mixtures thereof.
  • the solvent may be a mixture of water and alcohol (methanol or ethanol) obtained by mixing water and alcohol in a volume ratio of 1:9.
  • the amount of the silane-based compound may be in a range of 0.001 to 20 weight % of the composite, may be in a range of 0.01 to 10 weight %, 0.05 to 5 weight %, for example, 0.1 to 2 weight %.
  • the amount of the silane-based compound is 0.001 weight % or less, the organic layer obtained from the surface treating agent may not be sufficiently coated on the copper foil and thus peel strength may not be improved.
  • the amount of the silane-based compound is 20 weight % or greater, the thickness of the organic layer obtained from the surface treating agent increases and nodules on the copper foil may be covered so that peel strength may not be improved.
  • the copper foil includes a nodulation treated copper foil, a copper foil further having a heat-blocking layer and an antirust agent layer formed thereon, or a copper foil having an alloyed surface, in addition to a pure copper foil. Also, the copper foil includes any copper foil to which a general coating process used by one of ordinary skill in the art is performed.
  • the surface treating agent composition is limited to be used in the copper foil; however, may be used in other metals. Accordingly, the surface treating agent composition may be used in zinc or other alloys.
  • the surface treating agent composition may be prepared by diluting 0.001 to 20 weight % of the at least one selected from the group consisting of silane-based compounds represented by Formulae 1 through 4 in water, alcohol such as methanol or ethanol, ketone such as acetone, ester such as ethylacetate, or an aromatic group solvent such as toluene.
  • a polyamic acid or a polyimide film may be further coated on the copper foil on which the surface treating agent composition is already coated and thus a two-layered or three-layered flexible copper clad laminate (FCCL) may be prepared.
  • the polyimide film may be obtained by coating and hardening a polyamic acid varnish.
  • the polyamic acid may include at least one dianhydride monomer and at least one diamine monomer. Elements of the dianhydride monomers and the diamine monomers are not particularly restricted and any monomers used by one of ordinary skill in the art may be used.
  • the at least one dianhydride monomer may be selected from the group consisting of pyromellitic dianhydride and 3,3',4,4'-biphenonetetrahydrocarboxylic dianhydride (BTDA) and the at least one diamine monomer may be selected from the group consisting of 4,4'-oxydianiline (ODA), para-phenylenediamine (PDA), and siloxanediamine (SD).
  • BTDA 3,3',4,4'-biphenonetetrahydrocarboxylic dianhydride
  • SD siloxanediamine
  • the polyamic acid varnish may be, for example, a PMDA/ODA mixture, a BTDA/PDA mixture, a BTDA/PMDA/ODA/PDA mixture, or a PMDA/ODA-SD mixture
  • a method of preparing one compound selected from the group consisting of the silane-based compounds represented by Formulae 1 through 4 below includes reacting a silane-based compound represented by Formula 5 or 7 below with one selected from the group consisting of a compound represented by Formula 6 below, succinic anhydride, 2,3-pyridinedicarboxylic anhydride, and 1,2,4-benzenetricarboxylic anhydride at a temperature of -10 to 100 °C.
  • R 1 , R 2 , and R 3 are each independently a C 1 -C 3 alkyl group and R 4 and R 5 are each independently hydrogen or a C 1 -C 5 alkyl group.
  • the compound represented by Formula 5 is reacted with the compound represented by Formula 6 at a temperature of about 95 °C and thus, the silane-based compound represented by Formula 1 is obtained.
  • the compound represented by Formula 7 is reacted with the succinic anhydride at a temperature of -5 to 5 °C and thus, the silane-based compound represented by Formula 2 is obtained.
  • the compound represented by Formula 7 is reacted with the 2,3-pyridinedicarboxylic anhydride at a temperature of -5 to 5 °C and thus, the silane-based compound represented by Formula 3 is obtained.
  • the compound represented by Formula 7 is reacted with the 1,2,4-benzenetricarboxylic anhydride at a temperature of -5 to 5 °C and thus, the silane-based compound represented by Formula 4 is obtained.
  • a Compound 1 represented by Formula 1 was synthesized according to Reaction Scheme 1 below.
  • Compound 1 prepared in Example 1 was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that a mixed solution having 1.0 weight % of Compound 1 was prepared.
  • Example 2 The mixed solution prepared in Example 2 was left alone for 60 minutes so as to perform hydrolysis and then was sprayed on a Cr-coated rolled copper foil (manufactured by Iljin, IL-2). Then, the rolled copper foil was coated by using an applicator. The coated copper foil was dried in an oven at 120 °C for 30 minutes
  • the coated polyamic acid was hardened at 60 °C for 30 minutes, at 120 °C for 30 minutes, at 250 °C for 30 minutes, and 400 °C for 10 minutes under a nitrogen atmosphere so as to prepare a polyimide film and thus a copper foil on which the polyimide film was coated was prepared.
  • the copper foil prepared in Example 3 is hereinafter referred to as Sample 1.
  • the copper foil prepared in Example 4 is hereinafter referred to as Sample 2.
  • the copper foil prepared in Example 5 is hereinafter referred to as Sample 3.
  • the copper foil prepared in Comparative Example 1 is hereinafter referred to as Comparative Sample 1.
  • the copper foil prepared in Comparative Example 2 is hereinafter referred to as Comparative Sample 2.
  • the copper foil prepared in Comparative Example 3 is hereinafter referred to as Comparative Sample 3.
  • Peel strength was measured for Samples 1 through 3 and Comparative Samples 1 through 3 by using a method prescribed by ASTM D-638. Cross-Head speed was 25 mm/min. and the widths of the samples were 5 mm. The measurement was performed using an Instron 8516. The results of the measurement are shown in Table 1 below.
  • Samples 1 through 3 prepared by using the surface treating agent composition including the silane-based compound according to embodiments of the present invention shows significantly improved peel strength between the polyimide and the copper foil compared with Comparative Samples 1 and 3 prepared without using the surface treating agent composition.
  • Samples 1 through 3 were stored in a thermo-hygrostat HIRAYANA PC-R7 at 50 °C for 7 days with a relative humidity of 80 % and discoloration of Samples 1 through 3 was distinguished. 7 days later, the colors of Samples 1 through 3 were not changed.
  • a Compound 2A represented by Formula 2 was synthesized according to Reaction Scheme 2 below.
  • R is methyl
  • a Compound 2B represented by Formula 2 was synthesized according to Reaction Scheme 2 below.
  • R is ethyl
  • Compound 2A prepared in Example 6A was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that mixed solutions respectively having 0.5 weight %, 1 weight %, 2 weight %, 3 weight %, and 5 weight % of Compound 2A, were prepared.
  • Compound 2B prepared in Example 6B was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that mixed solutions respectively having 0.5 weight %, 1 weight %, 2 weight %, 3 weight %, and 5 weight % of Compound 2B were prepared.
  • the mixed solutions prepared in Examples 7 through 16 were left alone for 60 minutes so as to perform hydrolysis and then were respectively sprayed on Cr-coated rolled copper foils (manufactured by Iljin, IL-2). Then, the copper foils were coated by using an applicator (C.K TRADING. Co., model name: CKAF-1003). The coated copper foils were dried in an oven at 120 °C for 30 minutes.
  • the copper foils treated by using the surface treating agent composition were sprayed with a varnish manufactured by Jooyoung Industrial Co., Ltd. (product name: JY-001) and were coated by using a doctor blade.
  • the coated polyamic acid was hardened at 60 °C for 30 minutes, at 120 °C for 30 minutes, at 250 °C for 30 minutes, and 400 °C for 10 minutes under a nitrogen atmosphere so as to prepare a polyimide film and thus copper foils, on which the polyimide films were respectively coated, were prepared.
  • the copper foils prepared in Examples 17 through 26 are hereinafter referred to as Samples 4 through 13.
  • the copper foil prepared in Comparative Example 4 is hereinafter referred to as Comparative Sample 4.
  • Peel strength of Samples 4 through 13 and Comparative Sample 4 was measured by using a method prescribed by ASTM D-638. Cross-Head speed was 25 mm/min. and the widths of the samples were 5 mm. The measurement was performed using an Instron 8516. The results of the measurement are shown in Table 2 below.
  • Samples 4 through 13 prepared by using the surface treating agent composition including the silane-based compound according to embodiments of the present invention show significantly improved peel strength between the polyimide film and the copper foil compared with Comparative Sample 4 prepared without using the surface treating agent composition.
  • Samples 4 through 13 were stored in a thermo-hygrostat HIRAYANA PC-R7 at 50 °C for 7 days with relative humidity of 80 % and discoloration of Samples 4 through 13 was distinguished. 7 days later, the colors of Samples 4 through 13 were not changed.
  • a Compound 3 represented by Formula 3 was synthesized according to Reaction Scheme 3 below.
  • Compound 3 prepared in Example 27 was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that mixed solutions respectively having 0.5 weight % and 1 weight of Compound 3 of were prepared.
  • the mixed solutions prepared in Examples 28 through 29 were left alone for 60 minutes so as to perform hydrolysis and then were respectively sprayed on Cr-coated rolled copper foils (manufactured by Iljin, IL-2). Then, the copper foils were coated by using an applicator. The coated copper foils were dried in an oven at 120 °C for 30 minutes.
  • the copper foils treated by using the surface treating agent composition were sprayed with a Upilex type varnish (product name: U-varnish-S) manufactured by UBE Co., Ltd. and were coated by using a doctor blade.
  • a Upilex type varnish product name: U-varnish-S manufactured by UBE Co., Ltd.
  • the coated polyamic acid was hardened at 60 °C for 30 minutes, at 120 °C for 30 minutes, at 250 °C for 30 minutes, and 400 °C for 10 minutes under a nitrogen atmosphere so as to prepare a polyimide film and thus copper foils, on which the polyimide films were respectively coated, were prepared.
  • the copper foils prepared in Examples 30 through 31 are hereinafter referred to as Samples 14 through 15.
  • the copper foil prepared in Comparative Example 5 is hereinafter referred to as Comparative Sample 5.
  • Peel strength of Samples 14 and 15 and Comparative Sample 5 was measured by using a method prescribed by ASTM D-638. Cross-Head speed was 25 mm/min. and the widths of the samples were 5 mm. The measurement was performed using an Instron 8516. The results of the measurement are shown in Table 3 below.
  • Samples 14 through 15 prepared by using the surface treating agent composition including the silane-based compound according to embodiments of the present invention have significantly improved peel strength between the polyimide film and the copper foil compared with Comparative Sample 5 prepared without using the surface treating agent composition.
  • Samples 14 through 15 were stored in a thermo-hygrostat HIRAYANA PC-R7 at 50 °C for 7 days with a relative humidity of 80 % and discoloration of Samples 14 and 15 was distinguished. 7 days later, the colors of Samples 14 and 15 were not changed.
  • a Compound 4A represented by Formula 4 was synthesized according to Reaction Scheme 4 below.
  • R is methyl
  • a Compound 4B represented by Formula 4 was synthesized according to Reaction Scheme 4 below.
  • R is ethyl
  • Compound 4A prepared in Example 32A was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that mixed solutions respectively having 0.5 weight % and 1 weight % of Compound 4A were prepared.
  • Compound 4B prepared in Example 32B was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that mixed solutions respectively having 0.5 weight % and 1 weight % of Compound 4B were prepared.
  • the mixture solutions prepared in Examples 33 through 36 were left alone for 60 minutes so as to perform hydrolysis and then were respectively sprayed on Cr-coated rolled copper foils (manufactured by Iljin, IL-2), so that the copper foils were coated by using an applicator.
  • the coated copper foils were dried in an oven at 120 °C for 30 minutes.
  • the copper foils treated by using the surface treating agent composition were sprayed with a varnish (product name: JY-001) manufactured by Jooyoung Co., Ltd. and were coated by using an applicator.
  • the coated polyamic acid was hardened at 60 °C for 30 minutes, at 120 °C for 30 minutes, at 250 °C for 30 minutes, and 400 °C for 10 minutes under a nitrogen atmosphere so as to prepare polyimide films and thus copper foils, on which the polyimide films were respectively coated, were prepared.
  • the copper foils prepared in Examples 37 through 40 are hereinafter referred to as Samples 16 through 19.
  • the copper foil prepared in Comparative Example 6 is hereinafter referred to as Comparative Sample 6.
  • Peel strength of Samples 16 through 19 and Comparative Sample 6 was measured by using a method prescribed by ASTM D-638. Cross-Head speed was 25 mm/min. and the widths of the samples were 5 mm. The measurement was performed using an Instron 8516. The results of the measurement are shown in Table 4 below.
  • Samples 16 through 19 prepared by using the surface treating agent composition including the silane-based compound according to embodiments of the present invention have significantly improved peel strength between the polyimide film and the copper foil compared with Comparative Sample 6 prepared without using the surface treating agent composition.
  • Samples 16 through 19 were stored in a thermo-hygrostat HIRAYANA PC-R7 at 50 °C for 7 days with relative humidity of 80 % and discoloration of Samples 16 through 19 was distinguished. 7 days later, the colors of Samples 16 through 19 were not changed.
  • a PCB prepared by using the surface treating agent composition for copper foil including the silane-based compound according to the present invention has improved peel strength compared with a PCB on which the surface treating agent composition is not used or a PCB on which a silane-based compound including a general silane-based compound is used.
  • a PCB prepared by using the surface treating agent composition for copper foil including the silane-based compound according to the present invention has improved peel strength compared with a PCB on which the surface treating agent composition is not used or a PCB on which a silane-based compound including a general silane-based compound is used.

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Abstract

Provided is a silane-based compound represented by Formulae 1 through 4: wherein R1, R2, and R3 are each independently a C1-C3 alkyl group and R4 and R5 are each independently hydrogen or a C1-C5 alkyl group.

Description

SILANE BASED COMPOUND, METHOD FOR PREPARING THE SAME, AND SURFACE TREATING AGENT COMPOSITION FOR COPPER FOIL INCLUDING THE SILANE BASED COMPOUND Technical Field
The present invention relates to a silane-based compound, a method of preparing the silane-based compound, and a surface treating agent composition for copper foil including the silane based compound, and more particularly, to a new silane-based compound, a method of preparing the silane-based compound, and a surface treating agent composition for copper foil including the silane based compound.
Background Art
A flexible copper clad laminate (FCCL) is a type of printed circuit board (PCB) that is currently increasingly in demand. A FCCL is a multi-layered film formed of two or three layers in which polyimide is laminated on a copper foil. As precision of wirings printed on the FCCL increases, etching precision also increases and thus it is required to reduce the surface roughness of the copper foil. However, as the surface roughness of the copper foil is reduced, peel strength between the copper foil and a substrate (for example, a polyimide film) is deteriorated. In this regard, a means to improve the peel strength is required.
A copper foil for a PCB generally processed using a silane-coupling agent as a surface treating agent of the copper foil for strengthening the peel strength between the copper foil and the substrate is disclosed in Japanese Patent Application 1990-026097.
However, as the requirement for a physical property of the copper foil used in the PCB becomes tight, the copper foil for the PCB on which the surface treatment film having more improved physical property is formed is still required
 Technical Solution
The present invention provides a new silane-based compound that provides excellent peel strength between a substrate and the copper foil, a method of preparing the silane-based compound, and a surface treating agent composition for copper foil including the silane-based compound.
According to an aspect of the present invention, there is provided a silane-based compound represented by Formulae 1 through 4:
<Formula 1> <Formula 2>
Figure PCTKR2009003913-appb-I000001
Figure PCTKR2009003913-appb-I000002
<Formula 3> <Formula 4>
Figure PCTKR2009003913-appb-I000003
Figure PCTKR2009003913-appb-I000004
wherein R1, R2, and R3 may be each independently a C1-C3 alkyl group and R4 and R5 may be each independently hydrogen or a C1-C5 alkyl group.
According to another aspect of the present invention, there is provided a surface treating agent composition for copper foil including at least one compound selected from the group consisting of silane-based compounds represented by Formulae 1 through 4, and a solvent:
<Formula 1> <Formula 2>
Figure PCTKR2009003913-appb-I000005
Figure PCTKR2009003913-appb-I000006
<Formula 3> <Formula 4>
Figure PCTKR2009003913-appb-I000007
Figure PCTKR2009003913-appb-I000008
wherein R1, R2, and R3 may be each independently a C1-C3 alkyl group and R4 and R5 may be each independently hydrogen or a C1-C5 alkyl group.
According to another aspect of the present invention, there is provided a method of preparing one compound selected from the group consisting of silane-based compounds represented by Formulae 1 through 4, the method including reacting a silane-based compound represented by Formula 5 or 7 below with one selected from the group consisting of a compound represented by Formula 6 below, succinic anhydride, 2,3-pyridinedicarboxylic anhydride, and 1,2,4-benzenetricarboxylic anhydride at a temperature of -10 to 100 ℃:
<Formula 1> <Formula 2>
Figure PCTKR2009003913-appb-I000009
Figure PCTKR2009003913-appb-I000010
<Formula 3> <Formula 4>
Figure PCTKR2009003913-appb-I000011
Figure PCTKR2009003913-appb-I000012
<Formula 5> <Formula 6>
Figure PCTKR2009003913-appb-I000013
Figure PCTKR2009003913-appb-I000014
<Formula 7>
Figure PCTKR2009003913-appb-I000015
wherein, R1, R2, and R3 may be each independently a C1-C3 alkyl group and R4 and R5 may be each independently hydrogen or a C1-C5 alkyl group.
 Advantageous Effects
A PCB prepared by using the surface treating agent composition for copper foil including the silane-based compound according to the present invention has improved peel strength compared with a PCB on which the surface treating agent composition is not used or a PCB on which a silane-based compound including a general silane-based compound is used .
 Best Mode
Hereinafter, a silane-based compound, a method of preparing the silane-based compound, and a surface treating agent composition for copper foil including the silane-based compound according to embodiments of the present invention will be described in more detail.
The silane-based compound according to the present embodiment may be represented by Formulae1 through 4 .
<Formula 1> <Formula 2>
Figure PCTKR2009003913-appb-I000016
Figure PCTKR2009003913-appb-I000017
<Formula 3> <Formula 4>
Figure PCTKR2009003913-appb-I000018
Figure PCTKR2009003913-appb-I000019
wherein R1, R2, and R3 are each independently a C1-C3 alkyl group and R4 and R5 are each independently hydrogen or a C1-C5 alkyl group.
The silane-based compounds have a siloxane group at the ends thereof for a covalent bond with the copper foil and an imidazole group and/or an imide group at the other end thereof, wherein the imidazole group and/or the imide group has a structure similar to a polyimide film and thus bonding strength with a polyimide film may be improved. Thus, the bonding strength between the copper foil and a polyimide film may be improved.
According to another embodiment of the present invention, R1, R2, and R3 in the silane-based compounds are each independently methyl or ethyl and R4 and R5 may be hydrogen.
The surface treating agent composition for copper foil according to another embodiment of the present invention may include at least one compound selected from the group consisting of silane-based compounds represented by Formulae 1 through 4, and a solvent.
<Formula 1> <Formula 2>
Figure PCTKR2009003913-appb-I000020
Figure PCTKR2009003913-appb-I000021
<Formula 3> <Formula 4>
Figure PCTKR2009003913-appb-I000022
Figure PCTKR2009003913-appb-I000023
In Formulae 1 through 4 above, R1, R2, and R3 are each independently a C1-C3 alkyl group and R4 and R5 are each independently hydrogen or a C1-C5 alkyl group.
In the silane-based compound included in the surface treating agent composition, an alkoxy group is changed into a hydroxy group by performing hydrolysis with the solvent. The silane-based compounds are connected to each other by a condensation reaction and the connected silane-based compounds are fixed to the copper foil by covalent bond with the hydroxy group formed on the copper foil. As a result, an organic layer of the silane-based compound is formed on the copper foil.
The surface treating agent composition may further include other surface treating agents or antirust agents which are well known to one of ordinary skill in the art, in addition to the silane-based compound, and the surface treating agents or the antirust agents are not particularly restricted.
According to another embodiment of the present invention, R1, R2, and R3 of the silane-based compounds may be each independently methyl or ethyl and R4 and R5 may be hydrogen.
According to another embodiment of the present invention, the solvent included in the surface treating agent composition for copper foil may be one selected from the group consisting of water, methanol, ethanol, and mixtures thereof. For example, the solvent may be a mixture of water and alcohol (methanol or ethanol) obtained by mixing water and alcohol in a volume ratio of 1:9.
The amount of the silane-based compound may be in a range of 0.001 to 20 weight % of the composite, may be in a range of 0.01 to 10 weight %, 0.05 to 5 weight %, for example, 0.1 to 2 weight %. When the amount of the silane-based compound is 0.001 weight % or less, the organic layer obtained from the surface treating agent may not be sufficiently coated on the copper foil and thus peel strength may not be improved. When the amount of the silane-based compound is 20 weight % or greater, the thickness of the organic layer obtained from the surface treating agent increases and nodules on the copper foil may be covered so that peel strength may not be improved.
The copper foil includes a nodulation treated copper foil, a copper foil further having a heat-blocking layer and an antirust agent layer formed thereon, or a copper foil having an alloyed surface, in addition to a pure copper foil. Also, the copper foil includes any copper foil to which a general coating process used by one of ordinary skill in the art is performed.
The surface treating agent composition is limited to be used in the copper foil; however, may be used in other metals. Accordingly, the surface treating agent composition may be used in zinc or other alloys.
The surface treating agent composition may be prepared by diluting 0.001 to 20 weight % of the at least one selected from the group consisting of silane-based compounds represented by Formulae 1 through 4 in water, alcohol such as methanol or ethanol, ketone such as acetone, ester such as ethylacetate, or an aromatic group solvent such as toluene.
A polyamic acid or a polyimide film may be further coated on the copper foil on which the surface treating agent composition is already coated and thus a two-layered or three-layered flexible copper clad laminate (FCCL) may be prepared. The polyimide film may be obtained by coating and hardening a polyamic acid varnish. The polyamic acid may include at least one dianhydride monomer and at least one diamine monomer. Elements of the dianhydride monomers and the diamine monomers are not particularly restricted and any monomers used by one of ordinary skill in the art may be used. The at least one dianhydride monomer may be selected from the group consisting of pyromellitic dianhydride and 3,3',4,4'-biphenonetetrahydrocarboxylic dianhydride (BTDA) and the at least one diamine monomer may be selected from the group consisting of 4,4'-oxydianiline (ODA), para-phenylenediamine (PDA), and siloxanediamine (SD).
The polyamic acid varnish may be, for example, a PMDA/ODA mixture, a BTDA/PDA mixture, a BTDA/PMDA/ODA/PDA mixture, or a PMDA/ODA-SD mixture
According to another embodiment of the present invention, a method of preparing one compound selected from the group consisting of the silane-based compounds represented by Formulae 1 through 4 below includes reacting a silane-based compound represented by Formula 5 or 7 below with one selected from the group consisting of a compound represented by Formula 6 below, succinic anhydride, 2,3-pyridinedicarboxylic anhydride, and 1,2,4-benzenetricarboxylic anhydride at a temperature of -10 to 100 ℃.
<Formula 1> <Formula 2>
Figure PCTKR2009003913-appb-I000024
Figure PCTKR2009003913-appb-I000025
<Formula 3> <Formula 4>
Figure PCTKR2009003913-appb-I000026
Figure PCTKR2009003913-appb-I000027
<Formula 5> <Formula 6>
Figure PCTKR2009003913-appb-I000028
Figure PCTKR2009003913-appb-I000029
<Formula 7>
Figure PCTKR2009003913-appb-I000030
wherein, R1, R2, and R3 are each independently a C1-C3 alkyl group and R4 and R5 are each independently hydrogen or a C1-C5 alkyl group.
The compound represented by Formula 5 is reacted with the compound represented by Formula 6 at a temperature of about 95 ℃ and thus, the silane-based compound represented by Formula 1 is obtained. The compound represented by Formula 7 is reacted with the succinic anhydride at a temperature of -5 to 5 ℃ and thus, the silane-based compound represented by Formula 2 is obtained. The compound represented by Formula 7 is reacted with the 2,3-pyridinedicarboxylic anhydride at a temperature of -5 to 5 ℃ and thus, the silane-based compound represented by Formula 3 is obtained. The compound represented by Formula 7 is reacted with the 1,2,4-benzenetricarboxylic anhydride at a temperature of -5 to 5 ℃ and thus, the silane-based compound represented by Formula 4 is obtained.
 Mode for Invention
Hereinafter, the present invention will be described in more detail with reference to the following examples; however, the present invention is not limited thereto. Structures of compounds synthesized in the following examples are identified using a Brucker DRX-300MHz 1H-NMR and a Jasco 610 FT-IR.
(Synthesis of silane-based compound (1))
Example 1: Synthesis of Compound 1
A Compound 1 represented by Formula 1 was synthesized according to Reaction Scheme 1 below.
<Reaction Scheme 1>
[Rectified under Rule 91 27.08.2009]
Figure WO-DOC-CHEMICAL-70
162.68 g of tetrahydrofurane, 6.259 g (0.05 mol) of glycidoxypropyltrimethoxysilane, and 11.817 g (0.05 mol) of 1-(3-aminopropyl)-imidazole were charged into a reactor and were reacted for 6 hours by maintaining the temperature of the reactor at 95 ℃ under a nitrogen atmosphere with rotating a mechanical stirrer at 300 rpm. After the reaction was completed, a solvent was removed from a resultant for 2 hours by using a rotary evaporator. Then the resultant was dried for 24 hours in a vacuum oven and 7 g (yield 98 %) of Compound 1 represented by Formula 1 was obtained thereby.
1 H NMR (300 MHz) : δ 0.62~0.68(m, 1H), 1.89~1.96(m ,8H), 1.64~1.67(t, 2H), ), 2.54~2.56(t, 7H), 2.58~2.61(m, 6H), 3.28~3.31(m, SiOCH3) 3.38~3.40(d, 3H), 3.42~3.44(d,4H), .3.50~3.58(m, 5H), 3.64(s, -NH-), 3.80(s, OH), 4.05~4.10(m, 9H), 6.95(s, 10H), 7.12~7.13(t, 11H), 7.65(s, 12H)
IR (neat, cm-1) : 3650~3200(νOH), 3300~3200(νNH), 1120~1050(νSi-(alkoxy))
(Manufacturing of surface treating agent composition for copper foil)
Example 2
Compound 1 prepared in Example 1 was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that a mixed solution having 1.0 weight % of Compound 1 was prepared.
(Manufacturing of 2-layer FCCL)
Example 3
The mixed solution prepared in Example 2 was left alone for 60 minutes so as to perform hydrolysis and then was sprayed on a Cr-coated rolled copper foil (manufactured by Iljin, IL-2). Then, the rolled copper foil was coated by using an applicator. The coated copper foil was dried in an oven at 120 ℃ for 30 minutes
The copper foil treated by using the surface treating agent composition was sprayed with a KRICT-PAA varnish (BPDA:PMDA:PDA:ODA=3:7:6:4) and was coated by using a doctor blade. The coated polyamic acid was hardened at 60 ℃ for 30 minutes, at 120 ℃ for 30 minutes, at 250 ℃ for 30 minutes, and 400 ℃ for 10 minutes under a nitrogen atmosphere so as to prepare a polyimide film and thus a copper foil on which the polyimide film was coated was prepared. The copper foil prepared in Example 3 is hereinafter referred to as Sample 1.
Example 4
A copper foil, on which a polyimide film was coated, was prepared in the same manner as in Example 3, except that a varnish manufactured by Jooyoung Industrial Co., Ltd. (product name: JY-001) was used instead of the KRICT-PAA varnish. The copper foil prepared in Example 4 is hereinafter referred to as Sample 2.
Example 5
A copper foil, on which a polyimide film was coated, was prepared in the same manner as in Example 3, except that a rolled copper foil manufactured by Nikko materials (product name: BHY-22B-T) was used instead of the Cr-coated rolled copper foil (manufactured by Iljin, IL-2) and a Upilex type varnish manufactured by UBE Co., Ltd. was used instead of the KRICT-PAA varnish. The copper foil prepared in Example 5 is hereinafter referred to as Sample 3.
Comparative Example 1
A copper foil, on which a polyimide film was coated, was prepared in the same manner as in Example 3, except that the step of treating the surface of the copper foil by using the surface treating agent composition was omitted. The copper foil prepared in Comparative Example 1 is hereinafter referred to as Comparative Sample 1.
Comparative Example 2
A copper foil, on which a polyimide film was coated, was prepared in the same manner as in Example 4, except that the step of treating the surface of the copper foil by using the surface treating agent composition was omitted. The copper foil prepared in Comparative Example 2 is hereinafter referred to as Comparative Sample 2.
Comparative Example 3
A copper foil, on which a polyimide film was coated, was prepared in the same manner as in Example 5, except that the step of treating the surface of the copper foil by using the surface treating agent composition was omitted. The copper foil prepared in Comparative Example 3 is hereinafter referred to as Comparative Sample 3.
Evaluative Example 1-1: peel strength test
Peel strength was measured for Samples 1 through 3 and Comparative Samples 1 through 3 by using a method prescribed by ASTM D-638. Cross-Head speed was 25 mm/min. and the widths of the samples were 5 mm. The measurement was performed using an Instron 8516. The results of the measurement are shown in Table 1 below.
<Table 1>
Figure PCTKR2009003913-appb-I000032
As shown in Table 1, Samples 1 through 3 prepared by using the surface treating agent composition including the silane-based compound according to embodiments of the present invention shows significantly improved peel strength between the polyimide and the copper foil compared with Comparative Samples 1 and 3 prepared without using the surface treating agent composition.
Evaluative Example 1-2 : moisture resistance test
Samples 1 through 3 were stored in a thermo-hygrostat HIRAYANA PC-R7 at 50 ℃ for 7 days with a relative humidity of 80 % and discoloration of Samples 1 through 3 was distinguished. 7 days later, the colors of Samples 1 through 3 were not changed.
(Synthesis of silane-based compound (2))
Example 6A: Synthesis of Compound 2A
A Compound 2A represented by Formula 2 was synthesized according to Reaction Scheme 2 below.
<Reaction Scheme 2>
[Rectified under Rule 91 27.08.2009]
Figure WO-DOC-CHEMICAL-102
wherein R is methyl.
125.712 g of tetrahydrofurane, 8.9645 g (0.05 mol) of 3-aminopropyltrimethoxysilane, and 5.0035 g (0.05 mol) of succinic anhydride were charged into a reactor and were reacted for 6 hours by maintaining the temperature of the reactor in a range of -5 to 5 ℃ under a nitrogen atmosphere with rotating a mechanical stirrer at 300 rpm. After the reaction was completed, a solvent was removed from a resultant for 2 hours by using a rotary evaporator. Then, the resultant was dried for 24 hours in a vacuum oven and 13.9 g (yield 99 %) of Compound 2A represented by Formula 2 was obtained thereby.
1 H NMR (300 MHz, (CD3)2SO) : δ 0.53~0.58(m, 1H), 1.42~1.45(m, 2H), 2.29~2.31(d, 4H), 2.38~2.43(m, 5H), 2.98~3.00(m, 3H), 3.40~3.46(m, SiOCH3), 8.00(s, -NH-). 12.00(s,-OH)
IR (neat, cm-1) : 3650~3200(νOH), 3300~3200(νNH), 1650(νCONH),1120~1050(νSi-(alkoxy))
Example 6B: Synthesis of compound 2B
A Compound 2B represented by Formula 2 was synthesized according to Reaction Scheme 2 below.
<Reaction Scheme 2>
[Rectified under Rule 91 27.08.2009]
Figure WO-DOC-CHEMICAL-110
wherein R is ethyl.
125.712 g of tetrahydrofurane, 11.0685 g (0.05 mol) of 3-aminopropyltriethoxysilane, and 5.0035 g (0.05 mol) of succinic anhydride were charged into a reactor and were reacted for 6 hours by maintaining the temperature of the reactor in a range of -5 to 5 ℃ under a nitrogen atmosphere with rotating a mechanical stirrer at 300 rpm. After the reaction was completed, a solvent was removed from a resultant for 2 hours by using a rotary evaporator. Then, the resultant was dried for 24 hours in a vacuum oven and 16 g (yield 99 %) of Compound 2B represented by Formula 2 was obtained thereby.
1 H NMR (300 MHz, (CD3)2SO) : δ0.58~0.60(m, 1H), 1,22~1.25(m, Si-CH2), 1.60~1.63(m, 2H), 2.45~2.49(m, 4H), 2.51~2.54(m, 5H), 3.20~3.25(m, 3H), 3.83~3.87(m, Si-CH3)
IR (neat, cm-1) : 3650~3200(νOH), 3300~3200(νNH), 1650(νCONH),1120~1050(νSi-(alkoxy))
(Manufacturing of surface treating agent composition for copper foil)
Examples 7 through 11
Compound 2A prepared in Example 6A was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that mixed solutions respectively having 0.5 weight %, 1 weight %, 2 weight %, 3 weight %, and 5 weight % of Compound 2A, were prepared.
Examples 12 through 16
Compound 2B prepared in Example 6B was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that mixed solutions respectively having 0.5 weight %, 1 weight %, 2 weight %, 3 weight %, and 5 weight % of Compound 2B were prepared.
(Manufacturing of 2-layer FCCL)
Examples 17 through 26
The mixed solutions prepared in Examples 7 through 16 were left alone for 60 minutes so as to perform hydrolysis and then were respectively sprayed on Cr-coated rolled copper foils (manufactured by Iljin, IL-2). Then, the copper foils were coated by using an applicator (C.K TRADING. Co., model name: CKAF-1003). The coated copper foils were dried in an oven at 120 ℃ for 30 minutes.
The copper foils treated by using the surface treating agent composition were sprayed with a varnish manufactured by Jooyoung Industrial Co., Ltd. (product name: JY-001) and were coated by using a doctor blade. The coated polyamic acid was hardened at 60 ℃ for 30 minutes, at 120 ℃ for 30 minutes, at 250 ℃ for 30 minutes, and 400 ℃ for 10 minutes under a nitrogen atmosphere so as to prepare a polyimide film and thus copper foils, on which the polyimide films were respectively coated, were prepared. The copper foils prepared in Examples 17 through 26 are hereinafter referred to as Samples 4 through 13.
Comparative Example 4
A copper foil, on which a polyimide film was coated, was prepared in the same manner as in Example 17, except that the step of treating the surface of the copper foil by using the surface treating agent composition was omitted. The copper foil prepared in Comparative Example 4 is hereinafter referred to as Comparative Sample 4.
Evaluative Example 2-1: peel strength test
Peel strength of Samples 4 through 13 and Comparative Sample 4 was measured by using a method prescribed by ASTM D-638. Cross-Head speed was 25 mm/min. and the widths of the samples were 5 mm. The measurement was performed using an Instron 8516. The results of the measurement are shown in Table 2 below.
<Table 2>
Figure PCTKR2009003913-appb-I000035
As shown in Table 2, Samples 4 through 13 prepared by using the surface treating agent composition including the silane-based compound according to embodiments of the present invention show significantly improved peel strength between the polyimide film and the copper foil compared with Comparative Sample 4 prepared without using the surface treating agent composition.
Evaluative Example 2-2 : moisture resistance test
Samples 4 through 13 were stored in a thermo-hygrostat HIRAYANA PC-R7 at 50 ℃ for 7 days with relative humidity of 80 % and discoloration of Samples 4 through 13 was distinguished. 7 days later, the colors of Samples 4 through 13 were not changed.
(Synthesis of silane-based compound (3))
Example 27 : Synthesis of Compound 3
A Compound 3 represented by Formula 3 was synthesized according to Reaction Scheme 3 below.
<Reaction Scheme 3>
[Rectified under Rule 91 27.08.2009]
Figure WO-DOC-CHEMICAL-137
125.712 g of tetrahydrofurane, 8.9645 g (0.05 mol) of 3-aminopropyltrimethoxysilane, and 7.4550 g (0.05 mol) of 2,3-pyridinedicarboxylic anhydride were charged into a reactor and were reacted for 5 hours by maintaining the temperature of the reactor in a range of -5 to 5 ℃ under a nitrogen atmosphere with rotating a mechanical stirrer at 300 rpm. After the reaction was completed, a solvent was removed from a resultant for 2 hours by using a rotary evaporator. Then, the resultant was dried for 24 hours in a vacuum oven and 16.4 g (yield 99 %) of Compound 3 represented by Formula 3 was obtained thereby.
1 H NMR (300 MHz, (CD3)2SO) : δ0.57~0.59(t, 1H), 1.62~1.80(m, 2H), 03.62~3.67(m, Si-CH3), 3.85~3.87(t, 3H), 7.93~7.95(t, 4H), 8.56(s, NH), 8.64~8.67(d, 5H), 9.09~9.11(d, 6H), 13.80(s, OH)
IR (neat, cm-1) : 3650~3200(νOH), 3300~3200(νNH), 1650(νCONH),1120~1050(νSi-(alkoxy))
(Manufacturing of surface treating agent composition for copper foil)
Examples 28 through 29
Compound 3 prepared in Example 27 was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that mixed solutions respectively having 0.5 weight % and 1 weight of Compound 3 of were prepared.
(Manufacturing of 2-layer FCCL)
Examples 30 through 31
The mixed solutions prepared in Examples 28 through 29 were left alone for 60 minutes so as to perform hydrolysis and then were respectively sprayed on Cr-coated rolled copper foils (manufactured by Iljin, IL-2). Then, the copper foils were coated by using an applicator. The coated copper foils were dried in an oven at 120 ℃ for 30 minutes.
The copper foils treated by using the surface treating agent composition were sprayed with a Upilex type varnish (product name: U-varnish-S) manufactured by UBE Co., Ltd. and were coated by using a doctor blade.
The coated polyamic acid was hardened at 60 ℃ for 30 minutes, at 120 ℃ for 30 minutes, at 250 ℃ for 30 minutes, and 400 ℃ for 10 minutes under a nitrogen atmosphere so as to prepare a polyimide film and thus copper foils, on which the polyimide films were respectively coated, were prepared. The copper foils prepared in Examples 30 through 31 are hereinafter referred to as Samples 14 through 15.
Comparative Example 5
A copper foil, on which a polyimide film was coated, was prepared in the same manner as in Example 30, except that the step of treating the surface of the copper foil by using the surface treating agent composition was omitted. The copper foil prepared in Comparative Example 5 is hereinafter referred to as Comparative Sample 5.
Evaluative Example 3-1: peel strength test
Peel strength of Samples 14 and 15 and Comparative Sample 5 was measured by using a method prescribed by ASTM D-638. Cross-Head speed was 25 mm/min. and the widths of the samples were 5 mm. The measurement was performed using an Instron 8516. The results of the measurement are shown in Table 3 below.
<Table 3>
Figure PCTKR2009003913-appb-I000037
As shown in Table 3, Samples 14 through 15 prepared by using the surface treating agent composition including the silane-based compound according to embodiments of the present invention have significantly improved peel strength between the polyimide film and the copper foil compared with Comparative Sample 5 prepared without using the surface treating agent composition.
Evaluative Example 3-2 : moisture resistance test
Samples 14 through 15 were stored in a thermo-hygrostat HIRAYANA PC-R7 at 50 ℃ for 7 days with a relative humidity of 80 % and discoloration of Samples 14 and 15 was distinguished. 7 days later, the colors of Samples 14 and 15 were not changed.
(Synthesis of silane-based compound (4))
Example 32A : Synthesis of compound 4A
A Compound 4A represented by Formula 4 was synthesized according to Reaction Scheme 4 below.
<Reaction Scheme 4>
[Rectified under Rule 91 27.08.2009]
Figure WO-DOC-CHEMICAL-162
wherein R is methyl.
125.712 g of tetrahydrofurane, 8.9645 g (0.05 mol) of 3-aminopropyltrimethoxysilane, and 9.6065 g (0.05 mol) of 1,2,4-benzenetricarboxylic acid anhydride (2,3-pyridinedicarboxylic anhydride) were charged into a reactor and were reacted for 6 hours by maintaining the temperature of the reactor in a range of -5 to 5 ℃ under a nitrogen atmosphere with rotating a mechanical stirrer at 250 rpm. When the reaction was completed, a solvent was removed from a resultant for 1 hour by using a rotary evaporator. Then, the resultant was dried for 48 hours in a vacuum oven and 18.5 g (yield 99 %) of the compound 4A represented by Formula 4 was obtained thereby.
1 H NMR (300 MHz, (CD3)2SO) : δ0.62~0.65(t, 1H), 1.71~1.76(m, 2H), 3.41~3.47(m, Si-CH3), 3.56~3.60(m, 3H), 7.45(s, NH)
IR (neat, cm-1) : 3650~3200(νOH), 3300~3200(νNH), 1650(νCONH),1120~1050(νSi-(alkoxy))
Examples 32B : Synthesis of compound 4B
A Compound 4B represented by Formula 4 was synthesized according to Reaction Scheme 4 below.
<Reaction Scheme 4>
[Rectified under Rule 91 27.08.2009]
Figure WO-DOC-CHEMICAL-170
wherein R is ethyl.
125.712 g of tetrahydrofurane, 8.9645 g (0.05 mol) of 3-aminopropyltriethoxysilane, and 9.6065 g (0.05 mol) of 1,2,4-benzenetricarboxylic acid anhydride (2,3-pyridinedicarboxylic anhydride) were charged into a reactor and were reacted for 6 hours by maintaining the temperature of the reactor in a range of -5 to 5 ℃ under a nitrogen atmosphere with rotating a mechanical stirrer at 250 rpm. After the reaction was completed, a solvent was removed from a resultant for 1 hour by using a rotary evaporator. Then, the resultant was dried for 48 hours in a vacuum oven and 20.6 g (yield 99 %) of Compound 4B represented by Formula 4 was obtained thereby.
1 H NMR (300 MHz) : δ 0.71~0.73(t,1H), 1.14~1.23(m, Si-CH3), 1.71~1.74(m, 2H),3.58~3.60(t, 3H), 3.79~3.86(m, Si-CH2), 8.55(s, NH)
IR (neat, cm-1) : 3650~3200( ν OH ), 3300~3200( ν NH ), 1650( ν CONH ),1120~1050( ν Si-(alkoxy) )
(Manufacturing of surface treating agent composition for copper foil)
Examples 33 through 34
Compound 4A prepared in Example 32A was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that mixed solutions respectively having 0.5 weight % and 1 weight % of Compound 4A were prepared.
Examples 35 through 36
Compound 4B prepared in Example 32B was mixed with a solvent mixture obtained by mixing water and methanol in a volume ratio of 1:9 so that mixed solutions respectively having 0.5 weight % and 1 weight % of Compound 4B were prepared.
(Manufacturing of 2-layer FCCL)
Examples 37 through 40
The mixture solutions prepared in Examples 33 through 36 were left alone for 60 minutes so as to perform hydrolysis and then were respectively sprayed on Cr-coated rolled copper foils (manufactured by Iljin, IL-2), so that the copper foils were coated by using an applicator. The coated copper foils were dried in an oven at 120 ℃ for 30 minutes.
The copper foils treated by using the surface treating agent composition were sprayed with a varnish (product name: JY-001) manufactured by Jooyoung Co., Ltd. and were coated by using an applicator.
The coated polyamic acid was hardened at 60 ℃ for 30 minutes, at 120 ℃ for 30 minutes, at 250 ℃ for 30 minutes, and 400 ℃ for 10 minutes under a nitrogen atmosphere so as to prepare polyimide films and thus copper foils, on which the polyimide films were respectively coated, were prepared. The copper foils prepared in Examples 37 through 40 are hereinafter referred to as Samples 16 through 19.
Comparative Example 6
A copper foil, on which a polyimide film was coated, was prepared in the same manner as in Example 37, except that the step of treating the surface of the copper foil by using the surface treating agent composition was omitted. The copper foil prepared in Comparative Example 6 is hereinafter referred to as Comparative Sample 6.
Evaluative Example 4-1: peel strength test
Peel strength of Samples 16 through 19 and Comparative Sample 6 was measured by using a method prescribed by ASTM D-638. Cross-Head speed was 25 mm/min. and the widths of the samples were 5 mm. The measurement was performed using an Instron 8516. The results of the measurement are shown in Table 4 below.
<Table 4>
Figure PCTKR2009003913-appb-I000040
As shown in Table 4, Samples 16 through 19 prepared by using the surface treating agent composition including the silane-based compound according to embodiments of the present invention have significantly improved peel strength between the polyimide film and the copper foil compared with Comparative Sample 6 prepared without using the surface treating agent composition.
Evaluative Example 4-2 : moisture resistance test
Samples 16 through 19 were stored in a thermo-hygrostat HIRAYANA PC-R7 at 50 ℃ for 7 days with relative humidity of 80 % and discoloration of Samples 16 through 19 was distinguished. 7 days later, the colors of Samples 16 through 19 were not changed.
As described above, a PCB prepared by using the surface treating agent composition for copper foil including the silane-based compound according to the present invention has improved peel strength compared with a PCB on which the surface treating agent composition is not used or a PCB on which a silane-based compound including a general silane-based compound is used.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
 Industrial Applicability
A PCB prepared by using the surface treating agent composition for copper foil including the silane-based compound according to the present invention has improved peel strength compared with a PCB on which the surface treating agent composition is not used or a PCB on which a silane-based compound including a general silane-based compound is used.

Claims (6)

  1. A silane-based compound represented by Formulae 1 through 4:
    <Formula 1> <Formula 2>
    Figure PCTKR2009003913-appb-I000041
    Figure PCTKR2009003913-appb-I000042
    <Formula 3> <Formula 4>
    Figure PCTKR2009003913-appb-I000043
    Figure PCTKR2009003913-appb-I000044
    wherein R1, R2, and R3 are each independently a C1-C3 alkyl group and R4 and R5 are each independently hydrogen or a C1-C5 alkyl group.
  2. The silane-based compound of claim 1, wherein the R1, R2, and R3 are each independently methyl or ethyl and the R4 and R5 are hydrogen.
  3. A surface treating agent composition for copper foil comprising at least one compound selected from the group consisting of silane-based compounds represented by Formulae 1 through 4, and a solvent:
    <Formula 1> <Formula 2>
    Figure PCTKR2009003913-appb-I000045
    Figure PCTKR2009003913-appb-I000046
    <Formula 3> <Formula 4>
    Figure PCTKR2009003913-appb-I000047
    Figure PCTKR2009003913-appb-I000048
    wherein R1, R2, and R3 are each independently a C1-C3 alkyl group and R4 and R5 are each independently hydrogen or a C1-C5 alkyl group.
  4. The surface treating agent composition for copper foil of claim 3, wherein the R1, R2, and R3 are each independently methyl or ethyl and the R4 and R5 are hydrogen.
  5. The surface treating agent composition for copper foil of claim 2, wherein the solvent comprises one selected from the group consisting of water, methanol, ethanol, and mixtures thereof.
  6. A method of preparing one compound selected from the group consisting of silane-based compounds represented by Formulae 1 through 4, the method comprising reacting a silane-based compound represented by Formula 5 or 7 below with one selected from the group consisting of a compound represented by Formula 6 below, succinic anhydride, 2,3-pyridinedicarboxylic anhydride, and 1,2,4-benzenetricarboxylic anhydride at a temperature of -10 to 100 ℃:
    <Formula 1> <Formula 2>
    Figure PCTKR2009003913-appb-I000049
    Figure PCTKR2009003913-appb-I000050
    <Formula 3> <Formula 4>
    Figure PCTKR2009003913-appb-I000051
    Figure PCTKR2009003913-appb-I000052
    <Formula 5> <Formula 6>
    Figure PCTKR2009003913-appb-I000053
    Figure PCTKR2009003913-appb-I000054
    <Formula 7>
    Figure PCTKR2009003913-appb-I000055
    wherein, R1, R2, and R3 are each independently a C1-C3 alkyl group and R4 and R5 are each independently hydrogen or a C1-C5 alkyl group.
PCT/KR2009/003913 2008-07-18 2009-07-16 Silane based compound, method for preparing the same, and surface treating agent composition for copper foil including the silane based compound WO2010008213A2 (en)

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