JP5519260B2 - Flexible printed circuit board reinforcing film, flexible printed circuit reinforcing plate comprising the same, and flexible printed circuit board laminate comprising the same - Google Patents
Flexible printed circuit board reinforcing film, flexible printed circuit reinforcing plate comprising the same, and flexible printed circuit board laminate comprising the same Download PDFInfo
- Publication number
- JP5519260B2 JP5519260B2 JP2009287756A JP2009287756A JP5519260B2 JP 5519260 B2 JP5519260 B2 JP 5519260B2 JP 2009287756 A JP2009287756 A JP 2009287756A JP 2009287756 A JP2009287756 A JP 2009287756A JP 5519260 B2 JP5519260 B2 JP 5519260B2
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- Prior art keywords
- printed circuit
- flexible printed
- film
- circuit board
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- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 239000012776 electronic material Substances 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- 238000007756 gravure coating Methods 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
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- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZAOCWQZQPKGTRN-UHFFFAOYSA-N nitrous acid;sodium Chemical compound [Na].ON=O ZAOCWQZQPKGTRN-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- 239000004209 oxidized polyethylene wax Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012165 plant wax Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Structure Of Printed Boards (AREA)
- Laminated Bodies (AREA)
Description
本発明は、フレキシブルプリント回路基板の補強用フィルムとして接着シートとの接着性に優れ、はんだリフロー後も接着性を保つことができ、かつ放熱性に優れたフレキシブルプリント回路基板補強用フィルム、それからなるフレキシブルプリント回路補強板およびそれらからなるフレキシブルプリント回路基板積層体に関する。 The present invention is a flexible printed circuit board reinforcing film that has excellent adhesion to an adhesive sheet as a reinforcing film for a flexible printed circuit board, can maintain the adhesiveness after solder reflow, and has excellent heat dissipation. The present invention relates to a flexible printed circuit reinforcing plate and a flexible printed circuit board laminate comprising the same.
携帯電話などの電子機器の技術進歩に伴って、フレキシブルプリント回路（以下、ＦＰＣと略記することがある）基板の需要が急激に伸びている。ＦＰＣを製造する際の加工性において、フィルムの薄膜化に伴い、基板フィルム自体の剛性が低下し、ＦＰＣを製造する際の加工性が困難になってきている。このような加工性低下を改良する方法として、基板フィルムとは別にＦＰＣ補強用フィルムを補強板として用い、加工性が求められる部位に接着シートを介して補強板をＦＰＣ基板と貼りあわせることにより保持し、全体として剛性を持たせる方法が用いられている。 With the technical progress of electronic devices such as mobile phones, the demand for flexible printed circuit (hereinafter sometimes abbreviated as FPC) substrates is growing rapidly. In the processability when manufacturing an FPC, as the film becomes thinner, the rigidity of the substrate film itself is lowered, and the processability when manufacturing an FPC is becoming difficult. As a method to improve such workability degradation, an FPC reinforcing film is used as a reinforcing plate in addition to the substrate film, and the reinforcing plate is held by attaching the reinforcing plate to the FPC substrate via an adhesive sheet at a site where workability is required. However, a method of giving rigidity as a whole is used.
従来、かかるＦＰＣ補強用フィルムにはポリイミドフィルムを２層以上貼り合わせた積層フィルムが使用されてきた。しかしながら、ポリイミドは素材の性質上、フィルム化や７５μｍ以上の膜厚フィルムの作成が困難であり、また非常に高価なものである。その他、ポリイミドは比較的吸水しやすくＦＰＣ などの電子材料として取り扱いにくい特性も有している。一方、耐熱性に優れてはいるが、本用途においては過剰品質である点も否めない。 Conventionally, a laminated film in which two or more polyimide films are bonded together has been used for the FPC reinforcing film. However, due to the nature of the material, polyimide is difficult to form into a film or to form a film with a thickness of 75 μm or more, and is very expensive. In addition, polyimide has a characteristic that it is relatively easy to absorb water and difficult to handle as an electronic material such as FPC. On the other hand, although it is excellent in heat resistance, it cannot be denied that it is excessive quality in this application.
一方、ＦＰＣ基板フィルムとしてはポリイミド以外の他素材も検討されており、例えば特許文献１では、ポリエチレンナフタレートフィルムを用いたＦＰＣ基板用フィルムが提案されており、加工時の補強用フィルムとして用いてもよいことが開示されている。しかしながら特許文献１に開示されているポリエチレンナフタレートフィルムを用いてはんだリフロー処理を行うと、接着シートとの密着性が十分でないことがあり、補強用フィルムの剥がれや、接着界面に膨れが発生したり、ＦＰＣ基板と補強用フィルムの間のピール強度が低下することがあった。
また、特許文献２においてポリエチレンナフタレートよりなるＦＰＣ基板の補強板としてポリエチレンナフタレートを用い、その片面に特定の接着剤層を形成することが開示されているが、接着性を高めるために特定の接着剤を使用する必要があった。
On the other hand, materials other than polyimide have been studied as FPC substrate films. For example, Patent Document 1 proposes an FPC substrate film using a polyethylene naphthalate film, which is used as a reinforcing film during processing. It is disclosed that However, when the solder reflow treatment is performed using the polyethylene naphthalate film disclosed in Patent Document 1, the adhesion to the adhesive sheet may not be sufficient, and the reinforcing film may be peeled off or the adhesive interface may be swollen. The peel strength between the FPC board and the reinforcing film may decrease.
Patent Document 2 discloses that polyethylene naphthalate is used as a reinforcing plate for an FPC board made of polyethylene naphthalate, and a specific adhesive layer is formed on one surface thereof. It was necessary to use an adhesive.
このように、ポリエチレンナフタレートをフレキシブル回路基板の補強用フィルムとして用いたときに、市販の接着シートを介した方法では、ポリエチレンナフタレート補強フィルムとの密着性は未だ十分ではなく、はんだリフロー工程において部分的に剥がれや膨れが生じるという課題があり、その改良が求められている。さらに、近年、電子部品の高密度化や小型化が進み、各部材からの熱の問題が生じており、回路基板が使用される用途によって回路基板には放熱対策が必要となってきている。 As described above, when polyethylene naphthalate is used as a reinforcing film for a flexible circuit board, the method using a commercially available adhesive sheet is not yet sufficient in adhesion with the polyethylene naphthalate reinforcing film, and in the solder reflow process. There is a problem that peeling or swelling partially occurs, and improvement thereof is demanded. Furthermore, in recent years, electronic components have been increased in density and miniaturized, and there has been a problem of heat from each member, and the circuit board is required to take measures against heat radiation depending on the use for which the circuit board is used.
本発明の目的は、ＦＰＣ基板の補強用フィルムとして市販の接着シートとの密着性に優れ、はんだリフロー工程において、市販の接着シートを用いてＦＰＣ基板と補強板とを貼り合せた場合であっても、接着界面に部分的な剥がれや膨れが生じず、かつ放熱性に優れたフレキシブルプリント回路基板補強用フィルム、それからなるフレキシブルプリント回路補強板およびそれらからなるフレキシブルプリント回路基板積層体を提供することにある。 The object of the present invention is excellent in adhesion to a commercially available adhesive sheet as a reinforcing film for an FPC board, and in the solder reflow process, the FPC board and the reinforcing plate are bonded together using a commercially available adhesive sheet. And providing a flexible printed circuit board reinforcing film that does not cause partial peeling or swelling at the adhesive interface and has excellent heat dissipation, a flexible printed circuit reinforcing plate comprising the same, and a flexible printed circuit board laminate comprising the same. It is in.
本発明者等は、前記課題を解決するために鋭意検討した結果、二軸配向ポリエステルフィルム基材層を有する補強用フィルムにおいて、高温での寸法安定性を有するとともに、基材層の少なくとも片面にオキサゾリン基を有するアクリル樹脂を含む高分子バインダーを含む塗布層を有することにより、市販の接着シートとの密着性が従来よりも向上し、２６０℃程度のリフロー工程における部分的な剥がれや膨れが生じなくなること、さらに二軸配向ポリエステルフィルム基材層中に放熱効果の高い無機粒子を含有させるなどの方法で補強用フィルムの熱伝導率を高めることにより、補強板と貼り合せたフレキシブルプリント回路基板の放熱効果を高めることができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have a biaxially oriented polyester film base material layer having a dimensional stability at high temperature and at least one surface of the base material layer. By having a coating layer containing a polymer binder containing an acrylic resin having an oxazoline group, the adhesion with a commercially available adhesive sheet is improved as compared with the conventional one, and partial peeling or swelling occurs at a reflow process of about 260 ° C. Furthermore, by increasing the thermal conductivity of the reinforcing film by adding inorganic particles having a high heat dissipation effect in the biaxially oriented polyester film substrate layer, the flexible printed circuit board bonded to the reinforcing plate The present inventors have found that the heat dissipation effect can be enhanced and have completed the present invention.
すなわち本発明の目的は、二軸配向ポリエステルフィルム基材層を有するフレキシブルプリント回路基板補強用フィルムであって、基材層を構成するポリエステルがポリエチレンナフタレンジカルボキシレートであり、該基材層の少なくとも片面にオキサゾリン基を有するアクリル樹脂を含む高分子バインダーを含む塗布層を有しており、かつ２３０℃で１０分間加熱処理したときの該補強用フィルムの熱収縮率がフィルム長手方向および幅方向の両方向において−３％以上３％未満であって、熱伝導率が０．２Ｗ／ｍ・Ｋ以上１０Ｗ／ｍ・Ｋ以下であるフレキシブルプリント回路基板補強用フィルムによって達成される。 That is, an object of the present invention is a flexible printed circuit board reinforcing film having a biaxially oriented polyester film base layer, wherein the polyester constituting the base layer is polyethylene naphthalene dicarboxylate, and at least of the base layer It has a coating layer containing a polymer binder containing an acrylic resin having an oxazoline group on one side, and the heat shrinkage rate of the reinforcing film when heat-treated at 230 ° C. for 10 minutes is in the film longitudinal direction and the width direction. This is achieved by a flexible printed circuit board reinforcing film having a thermal conductivity of 0.2 W / m · K or more and 10 W / m · K or less in both directions and at least −3% and less than 3%.
また本発明のフレキシブルプリント回路基板補強用フィルムは、好ましい態様として、二軸配向ポリエステルフィルム基材層に該層の重量を基準として１０重量％以上５０重量％以下の範囲で無機粒子を含有してなること、無機粒子が酸化チタン、硫酸バリウム、炭酸カルシウム、酸化アルミニウム、窒化ホウ素および二酸化ケイ素からなる群から選ばれる少なくとも１種であること、無機粒子とポリエステル相との界面におけるボイド面積が、フィルム断面において粒子面積の５％以下であること、塗布層における高分子バインダーの含有量が塗布層の重量を基準として１０重量％以上８０重量％以下であること、オキサゾリン基を有するアクリル樹脂の含有量が高分子バインダー重量を基準として３重量％以上９０重量％以下であること、の少なくとも１つを具備するものも包含する。 Moreover, the film for reinforcing a flexible printed circuit board of the present invention, as a preferred embodiment, contains inorganic particles in a biaxially oriented polyester film substrate layer in a range of 10 wt% to 50 wt% based on the weight of the layer. The inorganic particles are at least one selected from the group consisting of titanium oxide, barium sulfate, calcium carbonate, aluminum oxide, boron nitride and silicon dioxide, and the void area at the interface between the inorganic particles and the polyester phase is a film. It is 5% or less of the particle area in the cross section, the content of the polymer binder in the coating layer is 10% by weight or more and 80% by weight or less based on the weight of the coating layer, the content of the acrylic resin having an oxazoline group Is not less than 3 wt% and not more than 90 wt% based on the weight of the polymer binder It encompasses those having at least one of.
本発明はまた、本発明のフレキシブルプリント回路基板補強用フィルムを用いたフレキシブルプリント回路補強板に関するものである。
さらに本発明は、フレキシブルプリント回路基板に接着シートを介して本発明のフレキシブルプリント回路補強板が貼りあわされたフレキシブルプリント回路基板積層体に関するものであり、その好ましい態様として接着シートがエポキシ系接着シートまたはアクリル系接着シートであること、フレキシブルプリント回路基板のベースフィルムがポリイミドまたはポリエステルであること、のいずれか１つを包含するものである。
The present invention also relates to a flexible printed circuit reinforcing plate using the flexible printed circuit board reinforcing film of the present invention.
Furthermore, the present invention relates to a flexible printed circuit board laminate in which the flexible printed circuit reinforcing plate of the present invention is bonded to a flexible printed circuit board via an adhesive sheet, and the adhesive sheet is an epoxy-based adhesive sheet as a preferred embodiment thereof. Or it is an acrylic adhesive sheet and the base film of a flexible printed circuit board includes any one of a polyimide or polyester.
本発明のフレキシブルプリント回路基板補強用フィルムは、はんだリフロー後のフレキシブルプリント回路基板との密着性が良好で、部分的な剥がれや膨れがなく生産性に優れており、かつフレキシブルプリント回路基板の補強板としてフレキシブルプリント回路基板と貼り合せて使用することにより、電子部品実装時および回路の使用時にフレキシブルプリント回路基板に発生する熱の放熱性に優れることから、その工業的価値は極めて高い。 The flexible printed circuit board reinforcing film of the present invention has good adhesion with the flexible printed circuit board after solder reflow, is excellent in productivity without partial peeling or swelling, and is reinforced in the flexible printed circuit board. When used as a board by being bonded to a flexible printed circuit board, the industrial value is extremely high because heat dissipation generated in the flexible printed circuit board is excellent when mounting electronic components and using a circuit.
＜二軸配向ポリエステルフィルム基材層＞
本発明のフレキシブルプリント回路基板補強用フィルムは、二軸配向ポリエステルフィルム基材層を有する。該基材層を構成するポリエステルは、ポリエチレンナフタレンジカルボキシレートである。また、該基材層には、該基材層の重量を基準として１０重量％以上５０重量％以下の範囲で無機粒子を含有してなることが好ましい。
<Biaxially oriented polyester film substrate layer>
The flexible printed circuit board reinforcing film of the present invention has a biaxially oriented polyester film base layer. The polyester constituting the substrate layer is polyethylene naphthalene dicarboxylate. The base material layer preferably contains inorganic particles in a range of 10 wt% to 50 wt% based on the weight of the base material layer.
（ポリエチレンナフタレンジカルボキシレート）
本発明の二軸配向ポリエステルフィルム基材層を構成するポリエステルは、ナフタレンジカルボン酸またはその誘導体とエチレングリコールとの重縮合によって得られるポリエチレンナフタレンジカルボキシレートであり、中でもポリエチレン−２，６−ナフタレンジカルボキシレートが好ましい。ポリエステルとしてポリエチレンナフタレンジカルボキシレートが用いられることにより、フィルムの耐熱寸法安定性が高まる。
(Polyethylene naphthalene dicarboxylate)
The polyester constituting the biaxially oriented polyester film substrate layer of the present invention is a polyethylene naphthalene dicarboxylate obtained by polycondensation of naphthalene dicarboxylic acid or a derivative thereof and ethylene glycol, and particularly polyethylene-2,6-naphthalene. Carboxylates are preferred. The use of polyethylene naphthalene dicarboxylate as the polyester increases the heat-resistant dimensional stability of the film.
本発明のポリエステルは、ホモポリマーであってもよく、また共重合体、２種以上のポリエステルとの混合体のいずれであってもかまわない。共重合体または混合体における他の成分は、全酸成分を基準として１０モル％以下、さらに５モル％以下であることが好ましい。共重合成分としては、ジエチレングリコール、ネオペンチルグリコール、ポリアルキレングリコールなどのジオール成分、アジピン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸、５−ナトリウムスルホイソフタル酸などのジカルボン酸成分が挙げられる。 The polyester of the present invention may be a homopolymer, or may be a copolymer or a mixture of two or more kinds of polyesters. The other components in the copolymer or mixture are preferably 10 mol% or less, more preferably 5 mol% or less, based on the total acid components. Examples of the copolymer component include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and 5-sodium sulfoisophthalic acid.
ポリエステルは公知の方法を適用して製造することができる。例えば、ジオールとジカルボン酸および必要に応じて共重合成分をエステル化反応させ、次いで得られる反応生成物を重縮合反応させてポリエステルとする方法で製造することができる。また、これらの原料モノマーの誘導体をエステル交換反応させ、次いで得られる反応生成物を重縮合反応させてポリエステルとする方法で製造してもよい。 Polyester can be produced by applying a known method. For example, it can be produced by a method in which a diol, a dicarboxylic acid and, if necessary, a copolymerization component are esterified, and then a reaction product obtained is polycondensed to form a polyester. Alternatively, these raw material monomer derivatives may be transesterified, and then the resulting reaction product may be subjected to a polycondensation reaction to obtain a polyester.
ポリエステルの固有粘度は、ｏ−クロロフェノール中、３５℃において０．４０ｄｌ／ｇ以上であることが好ましく、０．４０ｄｌ／ｇ以上０．８０ｄｌ／ｇ以下であることがさらに好ましい。固有粘度が０．４０ｄｌ／ｇ未満ではフィルム製膜時に切断が多発したり、成形加工後の製品の強度が不足することがある。一方固有粘度が０．８０ｄｌ／ｇを超える場合は重合時の生産性が低下することがある。 The intrinsic viscosity of the polyester is preferably 0.40 dl / g or more, more preferably 0.40 dl / g or more and 0.80 dl / g or less at 35 ° C. in o-chlorophenol. When the intrinsic viscosity is less than 0.40 dl / g, cutting may occur frequently during film formation, or the strength of the product after forming may be insufficient. On the other hand, when the intrinsic viscosity exceeds 0.80 dl / g, productivity during polymerization may be lowered.
該基材層において、ポリエチレンナフタレンジカルボキシレートは該層の重量を基準として５０重量％以上９５重量％以下であることが好ましく、さらに好ましくは６０重量％以上９０重量％以下、特に好ましくは７０重量％以上８５重量％以下である。ポリエチレンナフタレンジカルボキシレートの含有量が下限値に満たない場合、補強板が脆くなり、補強効果が十分でないことがある。一方、ポリエチレンナフタレンジカルボキシレートの含有量が上限値を超える場合、放熱効果が十分に発現しないことがある。 In the base material layer, the polyethylene naphthalene dicarboxylate is preferably 50 wt% or more and 95 wt% or less, more preferably 60 wt% or more and 90 wt% or less, particularly preferably 70 wt%, based on the weight of the layer. % To 85% by weight. When the content of polyethylene naphthalene dicarboxylate is less than the lower limit, the reinforcing plate becomes brittle and the reinforcing effect may not be sufficient. On the other hand, when the content of polyethylene naphthalene dicarboxylate exceeds the upper limit, the heat dissipation effect may not be sufficiently exhibited.
（無機粒子）
本発明の二軸配向ポリエステル基材層は、該基材層の重量を基準として１０重量％以上５０重量％以下の範囲で無機粒子を含有することが好ましい。また無機粒子の含有量は、さらに好ましくは１０重量％以上４０重量％以下、特に好ましくは１５重量％以上３０重量％以下である。
無機粒子の含有量が下限値に満たない場合、十分な放熱効果が得られないことがある。一方、無機粒子の含有量が上限値を超えると補強板が脆くなり、折り曲げた際などに補強効果が十分でないことがある他、製膜時に切断が発生しやすくなる。また、かかる範囲内で粒子含有量が多いほど反りが低減する効果も奏する。
(Inorganic particles)
The biaxially oriented polyester base material layer of the present invention preferably contains inorganic particles in a range of 10% by weight to 50% by weight based on the weight of the base material layer. The content of the inorganic particles is more preferably 10% by weight or more and 40% by weight or less, and particularly preferably 15% by weight or more and 30% by weight or less.
When the content of the inorganic particles is less than the lower limit, a sufficient heat dissipation effect may not be obtained. On the other hand, when the content of the inorganic particles exceeds the upper limit value, the reinforcing plate becomes brittle, and the reinforcing effect may not be sufficient when bent, and the cutting is likely to occur during film formation. Moreover, there exists an effect which curvature reduces, so that there is much particle | grain content within this range.
無機粒子としては、酸化チタン、硫酸バリウム、炭酸カルシウム、酸化アルミニウム、窒化ホウ素および二酸化ケイ素からなる群から選ばれる少なくとも１種の無機粒子であることが好ましい。また、これらの無機粒子の中でも表面処理が施された酸化チタンは、樹脂相との界面におけるボイドが発生しにくくなり、放熱機能が発現しやすくなる。表面処理は、ポリエステルとの密着性が高まる処理方法であれば特に限定されないが、例えばエポキシシランやビニルシラン処理などが挙げられる。 The inorganic particles are preferably at least one inorganic particle selected from the group consisting of titanium oxide, barium sulfate, calcium carbonate, aluminum oxide, boron nitride, and silicon dioxide. In addition, among these inorganic particles, titanium oxide that has been subjected to a surface treatment is less likely to generate voids at the interface with the resin phase, and easily exhibits a heat dissipation function. The surface treatment is not particularly limited as long as it is a treatment method that improves the adhesion to polyester, and examples thereof include epoxy silane and vinyl silane treatment.
無機粒子の平均粒径は、好ましくは０．１〜３．０μｍ、さらに好ましくは０．２〜２．５μｍ、特に好ましくは０．３〜２．０μｍである。平均粒径が下限値に満たない場合、分散性が悪くなり粒子の凝集が生じやすいため、フィルムに粗大突起を形成し、生産工程上のトラブルになる可能性がある。一方、平均粒径が上限値を超える場合、フィルムの表面が粗くなり、粒子が脱落しやすい。 The average particle diameter of the inorganic particles is preferably 0.1 to 3.0 μm, more preferably 0.2 to 2.5 μm, and particularly preferably 0.3 to 2.0 μm. When the average particle diameter is less than the lower limit, dispersibility is deteriorated and the particles are likely to aggregate. Therefore, coarse protrusions are formed on the film, which may cause a trouble in the production process. On the other hand, when the average particle size exceeds the upper limit value, the surface of the film becomes rough, and the particles easily fall off.
かかる平均粒径は、電解溶液中に１個の小孔のある電極を設け、電解質溶液中に粉体粒子を分散させて粒子が小孔中を通過するときの電気抵抗値の変化量で粒子体積を、抵抗変化の発生数で粒子数を検出して粒径分布を求めるコールターカウンター法で測定した重量平均粒径である。 The average particle diameter is defined as the amount of change in electrical resistance value when an electrode having one small hole is provided in the electrolytic solution, and the powder particles are dispersed in the electrolytic solution and the particles pass through the small hole. The volume is a weight average particle diameter measured by a Coulter counter method in which the particle number distribution is detected by detecting the number of particles by the number of occurrences of resistance change.
ルチル型酸化チタンを用いる場合には、分散性を向上させるために、ステアリン酸などの脂肪酸およびその誘導体により処理してもよい。
ルチル型酸化チタンを用いる場合には、ポリエステルに添加する前に、精製プロセスを用いて、粒径調整、粗大粒子除去を行うことが好ましい。精製プロセスの工業的手段としては、粉砕手段で例えばジェットミル、ボールミルを適用することができ、分級手段としては、例えば乾式もしくは湿式遠心分離機を適用することができる。なお、これらの手段は２種以上を組み合わせ、段階的に精製してもよい。
When rutile titanium oxide is used, it may be treated with a fatty acid such as stearic acid or a derivative thereof in order to improve dispersibility.
When rutile titanium oxide is used, it is preferable to adjust the particle size and remove coarse particles using a purification process before adding to the polyester. As industrial means of the purification process, for example, a jet mill or a ball mill can be applied as a pulverizing means, and as a classification means, for example, a dry or wet centrifuge can be applied. In addition, you may refine | purify these means combining 2 or more types in steps.
これらの無機粒子を基材層を構成するポリエステル組成物に含有させる方法としては各種の方法を用いることができ、代表的な方法として、下記のような方法を挙げることができる。
（ア）ポリエステル合成時のエステル交換反応もしくはエステル化反応終了前に添加、もしくは重縮合反応開始前に添加する方法。
（イ）フィルム製膜時に、ポリエステルチップなどとともに押出機に投入し、溶融混練する方法。
（ウ）上記（ア）、（イ）の方法において、無機粒子を多量添加したマスターペレットを製造し、これらと添加剤を含有しないポリエステルとを混練して所定量の添加物を含有させる方法。
（エ）上記（ウ）のマスターペレットをそのまま使用する方法。
Various methods can be used as a method of incorporating these inorganic particles into the polyester composition constituting the base material layer, and typical methods include the following methods.
(A) A method of adding before transesterification or esterification reaction at the time of polyester synthesis or adding before the start of polycondensation reaction.
(A) A method of introducing into a extruder together with a polyester chip and melt-kneading at the time of film formation.
(C) A method in which, in the above methods (a) and (b), master pellets containing a large amount of inorganic particles are produced, and these and a polyester not containing an additive are kneaded to contain a predetermined amount of additive.
(D) A method of using the master pellet of (c) as it is.
なお、（ア）のポリエステル合成時に添加する方法を用いる場合には、粒子をグリコールに分散したスラリーとして、反応系に添加することが好ましい。
一般的にこれら無機粒子は、凝集して粗大凝集粒子となることが多く、粗大凝集粒子の個数を減らすために、製膜時のフィルターとして線径１５μｍ以下のステンレス鋼細線よりなる平均目開き１０〜１００μｍ、好ましくは平均目開き２０〜５０μｍの不織布型フィルターを用い、溶融ポリマーを濾過することが好ましい。
In addition, when using the method added at the time of the polyester synthesis | combination of (a), it is preferable to add to a reaction system as a slurry which disperse | distributed particle | grains to glycol.
In general, these inorganic particles are often aggregated into coarse aggregated particles. In order to reduce the number of coarse aggregated particles, an average opening 10 made of stainless steel fine wires having a wire diameter of 15 μm or less is used as a filter during film formation. It is preferable to filter the molten polymer using a non-woven fabric filter having a mean opening of 100 to 100 μm, preferably 20 to 50 μm.
（その他添加剤）
基材層を構成するポリエステル組成物には、その他の添加剤として、酸化防止剤、紫外線吸収剤、蛍光増白剤を本発明の目的を逸脱しない範囲内で、必要に応じて混合して含有させてもよい。
これらの添加剤を含む場合、その含有量は基材層の重量を基準として５重量％以下であることが好ましく、さらに３重量％以下、特に１重量％以下であることが好ましい。
(Other additives)
In the polyester composition constituting the base material layer, as other additives, an antioxidant, an ultraviolet absorber, and a fluorescent brightening agent are mixed as necessary within the range not departing from the object of the present invention. You may let them.
When these additives are included, the content thereof is preferably 5% by weight or less, more preferably 3% by weight or less, and particularly preferably 1% by weight or less, based on the weight of the base material layer.
また、本発明のポリエステルフィルム基材層は、フィルムを構成するポリエステルと実質的に非相溶な樹脂成分を実質的に含まないことが好ましい。実質的に含まないとは、該基材層の重量を基準として、その含有量が通常０〜３重量％、好ましくは０〜１％、さらに好ましくは０〜０．５％であることをいう。非相溶な樹脂を実質的に含有すると、延伸によりポリエチレンナフタレンジカルボキシレートとの界面にボイドが生じやすく、その断熱効果により十分な放熱機能が生じなくなることがある。 Moreover, it is preferable that the polyester film base material layer of this invention does not contain the resin component substantially incompatible with the polyester which comprises a film. “Substantially free” means that the content is usually 0 to 3% by weight, preferably 0 to 1%, more preferably 0 to 0.5% based on the weight of the base material layer. . When an incompatible resin is substantially contained, voids are likely to be generated at the interface with polyethylene naphthalene dicarboxylate due to stretching, and a sufficient heat dissipation function may not be generated due to the heat insulating effect.
＜塗布層＞
本発明のフレキシブルプリント回路基板補強用フィルムは、上述の二軸配向ポリエステルフィルム基材層の少なくとも片面に塗布層を有しており、該塗布層はオキサゾリン基を有するアクリル樹脂を含む高分子バインダーを含有してなるものである。
<Coating layer>
The flexible printed circuit board reinforcing film of the present invention has a coating layer on at least one side of the above-mentioned biaxially oriented polyester film substrate layer, and the coating layer comprises a polymer binder containing an acrylic resin having an oxazoline group. It contains.
（高分子バインダー）
塗布層を構成する高分子バインダーとして、オキサゾリン基を有するアクリル樹脂を含むことが必要である。かかる高分子バインダーを用いることにより、市販の接着シートを介してフレキシブルプリント回路基板とフレキシブルプリント回路基板補強用フィルムとの接着性を高めることができる。
(Polymer binder)
It is necessary to contain an acrylic resin having an oxazoline group as a polymer binder constituting the coating layer. By using such a polymer binder, the adhesiveness between the flexible printed circuit board and the flexible printed circuit board reinforcing film can be enhanced via a commercially available adhesive sheet.
オキサゾリン基を有するアクリル樹脂として、以下のオキサゾリン基を有するモノマーからなるアクリル樹脂が例示される。
オキサゾリン基を有するモノマーとしては、２−ビニル−２−オキサゾリン、２−ビニル−４−メチル−２−オキサゾリン、２−ビニル−５−メチル−２−オキサゾリン、２−イソプロペニル−２−オキサゾリン、２−イソプロペニル−４−メチル−２−オキサゾリン、２−イソプロペニル−５−メチル−２−オキサゾリンが挙げられ、これらの１種または２種以上の混合物を使用することができる。これらの中でも、２−イソプロペニル−２−オキサゾリンが工業的に入手しやすく好適である。
オキサゾリン基を有するアクリル樹脂を用いることにより、塗布層の凝集力が向上し、塗布層での凝集破壊の発生を防ぐことができる。そのため、接着シートと接着させる際に塗布層面に接着させることにより、接着シートとの密着性が強固なものとなり、同時に補強用フィルムの熱収縮率が一定の範囲にあることにより、はんだリフロー工程を経ても接着シートとの接着界面が剥がれにくく、また膨れの発生を抑制することができ、フレキシブルプリント回路基板補強板として十分に回路基板を補強することができる。
オキサゾリン基を有するモノマー成分は、アクリル樹脂の繰り返し単位を基準として、５モル％以上８０モル％以下であることが好ましく、１０モル％以上５０モル％以下であることがさらに好ましい。
Examples of the acrylic resin having an oxazoline group include acrylic resins composed of the following monomers having an oxazoline group.
Examples of the monomer having an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2 -Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline can be mentioned, and one or a mixture of two or more thereof can be used. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
By using an acrylic resin having an oxazoline group, the cohesive force of the coating layer can be improved and the occurrence of cohesive failure in the coating layer can be prevented. Therefore, by adhering to the coating layer surface when adhering to the adhesive sheet, the adhesiveness with the adhesive sheet becomes strong, and at the same time, the thermal shrinkage rate of the reinforcing film is in a certain range, so that the solder reflow process is performed. Even if it passes, the adhesion interface with an adhesive sheet cannot peel easily, generation | occurrence | production of a swelling can be suppressed, and a circuit board can fully be reinforced as a flexible printed circuit board reinforcement board.
The monomer component having an oxazoline group is preferably 5 mol% or more and 80 mol% or less, more preferably 10 mol% or more and 50 mol% or less, based on the repeating unit of the acrylic resin.
また、かかるアクリル樹脂の共重合成分として、さらにポリアルキレンオキシド鎖を有するモノマーを含有してもよい。かかるポリアルキレンオキシド鎖を有するモノマーとしては、アクリル酸、メタクリル酸のエステル部にポリアルキレンオキシドを付加させたものを挙げることができる。ポリアルキレンオキシド鎖はポリエチレンオキシド、ポリプロピレンオキシド、ポリブチレンオキシドなどを挙げることができる。ポリアルキレンオキシド鎖の繰り返し単位は３〜１００であることが好ましい。
高分子バインダーとして、さらにポリエステル樹脂を含む場合、ポリアルキレンオキシド鎖を有するアクリル樹脂を用いることで、ポリエステル樹脂とアクリル樹脂の相溶性がポリアルキレンオキシド鎖を含有しないアクリル樹脂に比べて向上する。
アクリル樹脂がポリアルキレンオキシド鎖を有するモノマーを含有する場合、ポリアルキレンオキシド鎖の繰り返し単位が３より少ないとポリエステル樹脂とアクリル樹脂との相溶性が十分に向上しないことがある。一方、ポリアルキレンオキシド鎖の繰り返し単位が１００より大きいと塗布層の耐湿熱性が下がり、高湿度、高温下で接着シートとの密着性が低下することがある。
Moreover, you may contain the monomer which has a polyalkylene oxide chain further as a copolymerization component of this acrylic resin. Examples of the monomer having a polyalkylene oxide chain include those obtained by adding polyalkylene oxide to an ester part of acrylic acid or methacrylic acid. Examples of the polyalkylene oxide chain include polyethylene oxide, polypropylene oxide, and polybutylene oxide. The repeating unit of the polyalkylene oxide chain is preferably 3 to 100.
When a polyester resin is further included as the polymer binder, the compatibility between the polyester resin and the acrylic resin is improved by using an acrylic resin having a polyalkylene oxide chain as compared with an acrylic resin not containing the polyalkylene oxide chain.
When the acrylic resin contains a monomer having a polyalkylene oxide chain, if the number of repeating units of the polyalkylene oxide chain is less than 3, the compatibility between the polyester resin and the acrylic resin may not be sufficiently improved. On the other hand, if the repeating unit of the polyalkylene oxide chain is larger than 100, the wet heat resistance of the coating layer is lowered, and the adhesion to the adhesive sheet may be lowered at high humidity and high temperature.
さらに、アクリル樹脂を構成するその他の共重合成分として、アルキル（メタ）アクリレート；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレートなどのヒドロキシル基含有モノマー；グリシジル（メタ）アクリレート、アリルグリシジルエーテルなどのエポキシ基含有モノマー；アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマール酸、クロトン酸、スチレンスルホン酸及びその塩（ナトリウム塩、カリウム塩、アンモニウム塩、第三級アミン塩など）などのカルボキシル基またはその塩を有するモノマー；（メタ）アクリルアミド、Ｎ−アルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミド、Ｎ−アルコキシ（メタ）アクリルアミド、Ｎ，Ｎ−ジアルコキシ（メタ）アクリルアミド、アクリロイルモルホリン、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−フェニル（メタ）アクリルアミドなどのアミド基を有するモノマー；無水マレイン酸、無水イタコン酸などの酸無水物のモノマー；ビニルイソシアネート、アリルイソシアネート、スチレン、α−メチルスチレン、ビニルメチルエーテル、ビニルエチルエーテル、ビニルトリアルコキシシラン、アルキルマレイン酸モノエステル、アルキルフマール酸モノエステル、アルキルイタコン酸モノエステル、アクリロニトリル、メタクリロニトリル、塩化ビニリデン、エチレン、プロピレン、塩化ビニル、酢酸ビニル、ブタジエンが挙げられる。 Furthermore, as other copolymerization components constituting the acrylic resin, alkyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxyl group-containing monomer such as 2-hydroxypropyl (meth) acrylate; glycidyl (meth) acrylate, Epoxy group-containing monomers such as allyl glycidyl ether; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) ) Monomers having a carboxyl group or a salt thereof; (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N-alkoxy (meth) acrylamide, N, N-dialkoxy Monomers having amide groups such as (meth) acrylamide, acryloylmorpholine, N-methylol (meth) acrylamide, N-phenyl (meth) acrylamide; monomers of acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl isocyanate, allyl isocyanate , Styrene, α-methylstyrene, vinyl methyl ether, vinyl ethyl ether, vinyl trialkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid monoester, alkyl itaconic acid monoester, acrylonitrile, methacrylonitrile, vinylidene chloride, ethylene, Examples include propylene, vinyl chloride, vinyl acetate, and butadiene.
かかる共重合成分中、アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、２−エチルヘキシル基、シクロヘキシル基が例示され、またアルコキシ基としては、メトキシ基、エトキシ基、ブトキシ基、イソブトキシ基が例示される。 Among such copolymer components, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, and a cyclohexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, and an isobutoxy group.
また、高分子バインダーとして、該アクリル樹脂に加えて、さらに他の成分を併用することができ、例えばポリエステル樹脂を用いることが好ましい。ポリエステル樹脂を併用することにより、ポリエステル基材層と塗布層との接着性を高めることができる。
ポリエステル樹脂として、多価塩基酸成分とジオール成分から得られるポリエステルを用いることが好ましい。多価塩基成分として、テレフタル酸、イソフタル酸、フタル酸、無水フタル酸、２、６−ナフタレンジカルボン酸、１、４−シクロヘキサンジカルボン酸、アジピン酸、セバシン酸、トリメリット酸、ピロメリット酸、ダイマー酸、５−ナトリウムスルホイソフタル酸を例示することができる。高分子バインダーを構成するポリエステル樹脂としては、２種以上のジカルボン酸成分を用いた共重合ポリエステルを用いることが好ましい。ポリエステル樹脂には、若干量であればマレイン酸、イタコン酸などの不飽和多塩基酸成分、あるいはｐ−ヒドロキシ安息香酸などのごときヒドロキシカルボン酸成分が含まれていてもよい。
ポリエステル樹脂のジオール成分としては、エチレングリコール、トリメチレングリコール、１、４−ブタンジオール、ジエチレングリコール、ジプロピレングリコール、１、６−ヘキサンジオール、１、４−シクロヘキサンジメタノール、キシレングリコール、ジメチロールプロパンなどや、ポリ（エチレンオキシド）グリコール、ポリ（テトラメチレンオキシド）グリコールを例示することができる。
In addition to the acrylic resin, other components can be used in combination as the polymer binder. For example, it is preferable to use a polyester resin. By using a polyester resin in combination, the adhesion between the polyester base layer and the coating layer can be enhanced.
As the polyester resin, a polyester obtained from a polybasic acid component and a diol component is preferably used. As polyvalent base components, terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer Examples of the acid include 5-sodium sulfoisophthalic acid. As the polyester resin constituting the polymer binder, it is preferable to use a copolymerized polyester using two or more kinds of dicarboxylic acid components. The polyester resin may contain an unsaturated polybasic acid component such as maleic acid or itaconic acid, or a hydroxycarboxylic acid component such as p-hydroxybenzoic acid, if it is in a slight amount.
Examples of the diol component of the polyester resin include ethylene glycol, trimethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylene glycol, and dimethylolpropane. And poly (ethylene oxide) glycol and poly (tetramethylene oxide) glycol.
高分子バインダーのポリエステル樹脂のガラス転移点は、好ましくは４０〜１００℃、更に好ましくは６０〜８０℃である。この範囲であれば、ポリエステル基材層との優れた接着性に加え、さらに優れた耐傷性を得ることができる。他方、ガラス転移温度が４０℃未満であるとフィルム同士でブロッキングが発生しやすくなり、１００℃を超えると塗膜が硬く、また脆くなることがある。 The glass transition point of the polyester resin of the polymer binder is preferably 40 to 100 ° C, more preferably 60 to 80 ° C. If it is this range, in addition to the outstanding adhesiveness with a polyester base material layer, the further outstanding scratch resistance can be obtained. On the other hand, when the glass transition temperature is less than 40 ° C., blocking tends to occur between the films, and when it exceeds 100 ° C., the coating film may be hard and brittle.
塗布層の形成成分として高分子バインダーに加えて他の成分も用いる場合、高分子バインダーの含有量は、塗布層の重量を基準として１０重量％以上８０重量％以下であることが好ましい。また、高分子バインダーの含有量の下限値は２０重量％であることがさらに好ましく、高分子バインダーの含有量の上限値は５０重量％であることがさらに好ましい。塗布層に占める高分子バインダーの含有量がかかる範囲内にあれば、接着シートとの接着性を強固なものにすることができ、かつ補強用フィルムの熱収縮率が一定の範囲にある場合にはんだリフロー後の界面の剥がれや膨れの発生を抑制することができる。 When other components are used in addition to the polymer binder as a component for forming the coating layer, the content of the polymer binder is preferably 10% by weight or more and 80% by weight or less based on the weight of the coating layer. Further, the lower limit of the content of the polymer binder is more preferably 20% by weight, and the upper limit of the content of the polymer binder is more preferably 50% by weight. If the content of the polymer binder in the coating layer is within such a range, the adhesiveness with the adhesive sheet can be strengthened, and the heat shrinkage rate of the reinforcing film is in a certain range Generation of peeling or swelling of the interface after solder reflow can be suppressed.
また、高分子バインダーとしてオキサゾリン基を有するアクリル樹脂に加え、さらに他の成分を併用する場合、オキサゾリン基を有するアクリル樹脂の含有量は高分子バインダーの重量を基準として３重量％以上９０重量％以下であることが好ましい。また該アクリル樹脂の含有量の下限値は１５重量％であることがより好ましく、２５重量％であることがさらに好ましい。また、該アクリル樹脂の含有量の好ましい上限値は８０重量％である。
高分子バインダーに占めるオキサゾリン基を有するアクリル樹脂の割合がかかる範囲にあれば、塗布層の凝集力が向上して凝集破壊が生じにくくなり、はんだリフロー後の接着界面における剥がれや膨れを抑制することができ、好ましい範囲になるほどその効果が高くなる。一方、該アクリル樹脂が下限に満たない場合、塗布層の凝集力が低下し、接着シートとの接着性が不十分となることがある。また、該アクリル樹脂が上限を超える場合、ポリエステルフィルムと塗布層との密着性が低下することがある。
In addition to the acrylic resin having an oxazoline group as a polymer binder, when other components are used in combination, the content of the acrylic resin having an oxazoline group is 3% by weight to 90% by weight based on the weight of the polymer binder. It is preferable that Further, the lower limit of the content of the acrylic resin is more preferably 15% by weight, and further preferably 25% by weight. Moreover, the preferable upper limit of content of this acrylic resin is 80 weight%.
If the ratio of the acrylic resin having an oxazoline group in the polymer binder is within such a range, the cohesive strength of the coating layer is improved and cohesive failure is less likely to occur, and the peeling and swelling at the adhesive interface after solder reflow are suppressed. The effect becomes higher as the preferable range is reached. On the other hand, when the acrylic resin is less than the lower limit, the cohesive force of the coating layer is lowered, and the adhesion with the adhesive sheet may be insufficient. Moreover, when this acrylic resin exceeds an upper limit, the adhesiveness of a polyester film and an application layer may fall.
高分子バインダーがさらにポリエステル樹脂を含む場合、ポリエステル樹脂の含有量は、高分子バインダーの重量を基準として５重量％以上９５重量％以下であることが好ましい。またポリエステル樹脂の含有量の下限値は１０重量％であることがより好ましく、２０重量％であることがさらに好ましい。またポリエステル樹脂の含有量の上限値は９０重量％であることがより好ましく、さらには８５重量％であり、７５重量％であることが特に好ましい。 When the polymer binder further contains a polyester resin, the content of the polyester resin is preferably 5% by weight or more and 95% by weight or less based on the weight of the polymer binder. Further, the lower limit of the content of the polyester resin is more preferably 10% by weight, and further preferably 20% by weight. Further, the upper limit of the content of the polyester resin is more preferably 90% by weight, further 85% by weight, and particularly preferably 75% by weight.
（粒子）
本発明の塗布層は、フィルムの滑り性を高める目的で粒子を含有することができる。粒子の種類は特に制限されないが、炭酸カルシウム、炭酸マグネシウム、酸化カルシウム、酸化亜鉛、酸化マグネシウム、酸化ケイ素、ケイ酸ソーダ、水酸化アルミニウム、酸化鉄、酸化ジルコニウム、硫酸バリウム、酸化チタン、酸化錫、三酸化アンチモン、カーボンブラック、二硫化モリブデンなどの無機粒子、アクリル系架橋重合体、スチレン系架橋重合体、シリコーン樹脂、フッ素樹脂、ベンゾグアナミン樹脂、フェノール樹脂、ナイロン樹脂などの有機粒子を挙げることができる。これらのうち、水不溶性の固体物質は、水分散液中で沈降するのを避けるため、比重が３を超えない粒子を選ぶことが好ましい。
(particle)
The coating layer of the present invention can contain particles for the purpose of improving the slipperiness of the film. The type of particles is not particularly limited, but calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, silicon oxide, sodium silicate, aluminum hydroxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, tin oxide, Inorganic particles such as antimony trioxide, carbon black, and molybdenum disulfide, and organic particles such as acrylic cross-linked polymers, styrene cross-linked polymers, silicone resins, fluororesins, benzoguanamine resins, phenol resins, and nylon resins. . Among these, for the water-insoluble solid substance, it is preferable to select particles whose specific gravity does not exceed 3 in order to avoid sedimentation in the aqueous dispersion.
粒子の平均粒子径は４０〜１２０ｎｍの範囲が好ましい。平均粒子径が１２０ｎｍより大きいと粒子の落脱が発生しやすくなり、４０ｎｍよりも小さいと十分な滑性、耐傷性が得られない場合がある。
粒子の含有量は、塗布層の重量を基準として１０重量％未満の範囲が好ましい。１０重量％を超えると塗膜の凝集力が低くなり接着性が悪化することがある。また粒子の含有量の下限は、塗布層の重量を基準として０．１重量％であることが好ましい。
The average particle diameter of the particles is preferably in the range of 40 to 120 nm. If the average particle size is larger than 120 nm, the particles are likely to fall off, and if it is smaller than 40 nm, sufficient lubricity and scratch resistance may not be obtained.
The content of the particles is preferably in the range of less than 10% by weight based on the weight of the coating layer. If it exceeds 10% by weight, the cohesive force of the coating film becomes low and the adhesiveness may deteriorate. Moreover, it is preferable that the minimum of content of particle | grains is 0.1 weight% on the basis of the weight of an application layer.
（脂肪族ワックス）
塗布層には、ブロッキングを防止する目的で脂肪族ワックスを添加してもよい。かかる目的で脂肪族ワックスを添加する場合、その含有量は塗布層の重量を基準として、好ましくは０．５〜３０重量％、さらに好ましくは１重量％〜１０重量％である。含有量が下限に満たない場合、フィルム表面の滑性が得られず、フィルム同士がブロッキングすることがある。一方、含有量が上限を超えるとポリエステルフィルム基材層および接着シートに対する接着性が不足する場合がある。
脂肪族ワックスの具体例としては、カルナバワックスなどの植物系ワックス、ミツロウ、ラノリンなどの動物系ワックス、モンタンワックス、オゾケライト、セレシンワックスなどの鉱物系ワックス、パラフィンワックスなどの石油系ワックス、ポリエチレンワックス、酸化ポリエチレンワックス、ポリプロピレンワックス、酸化ポリプロピレンワックスなどの合成炭化水素系ワックスを挙げることができる。これらの中でも、接着シートとの接着性と滑り性が良好なことから、カルナバワックス、パラフィンワックス、ポリエチレンワックスが特に好ましい。これらは環境負荷の低減が可能であることおよび取扱のし易さから水分散体として用いることが好ましい。
(Aliphatic wax)
An aliphatic wax may be added to the coating layer for the purpose of preventing blocking. When the aliphatic wax is added for this purpose, the content is preferably 0.5 to 30% by weight, more preferably 1% to 10% by weight, based on the weight of the coating layer. When content is less than a minimum, the lubricity of a film surface is not acquired and films may block. On the other hand, when content exceeds an upper limit, the adhesiveness with respect to a polyester film base material layer and an adhesive sheet may be insufficient.
Specific examples of the aliphatic wax include plant wax such as carnauba wax, animal wax such as beeswax and lanolin, mineral wax such as montan wax, ozokerite and ceresin wax, petroleum wax such as paraffin wax, polyethylene wax, Examples thereof include synthetic hydrocarbon waxes such as oxidized polyethylene wax, polypropylene wax, oxidized polypropylene wax. Among these, carnauba wax, paraffin wax, and polyethylene wax are particularly preferable because they have good adhesion to the adhesive sheet and good sliding properties. These are preferably used as water dispersions because they can reduce the environmental burden and are easy to handle.
（その他の成分）
塗布層を形成する成分として、上記成分以外に、塗布する場合の濡れ性を改良するために界面活性剤などの濡れ剤を用いてもよい。また、所望に応じてその他の成分を配合することができる。その他の配合剤としては、メラミン樹脂などの他の樹脂、帯電防止剤、着色剤、軟質重合体、フィラー、熱安定剤、耐候安定剤、老化防止剤、レベリング剤、スリップ剤、アンチブロッキング剤、防曇剤、天然油、合成油、乳剤、充填剤、硬化剤、難燃剤などが挙げられ、その配合割合は、あくまで本発明の目的を損なわない範囲で選択される。
(Other ingredients)
As a component for forming the coating layer, in addition to the above components, a wetting agent such as a surfactant may be used in order to improve wettability when coating. Moreover, other components can be mix | blended as desired. Other compounding agents include other resins such as melamine resins, antistatic agents, colorants, soft polymers, fillers, heat stabilizers, weathering stabilizers, anti-aging agents, leveling agents, slip agents, antiblocking agents, Antifogging agents, natural oils, synthetic oils, emulsions, fillers, curing agents, flame retardants and the like can be mentioned, and the blending ratio thereof is selected as long as the object of the present invention is not impaired.
（塗布層の形成方法）
塗布層の形成については、例えば延伸可能なポリエステルフィルムの少なくとも片面に塗膜を形成する成分を含む水溶液を塗布した後、乾燥、延伸し必要に応じて熱処理することにより積層することができる。塗布層の形成時期について、さらに具体的には、未延伸フィルム、縦方向または横方向の何れか一方に配向せしめた一軸配向フィルム、あるいは縦方向および横方向の二方向に低倍率延伸配向せしめたフィルム（最終的に縦方向また横方向に再延伸せしめて配向結晶化を完了せしめる前の二軸延伸フィルム）のいずれかの時期に塗布液を塗布することが好ましく、その後さらに縦延伸および／または横延伸させる方法が挙げられる。
(Formation method of coating layer)
Regarding the formation of the coating layer, for example, after applying an aqueous solution containing a component for forming a coating film on at least one surface of a stretchable polyester film, the polyester film can be laminated by drying, stretching, and heat treatment as necessary. More specifically, with respect to the formation time of the coating layer, more specifically, an unstretched film, a uniaxially oriented film oriented in either the longitudinal direction or the transverse direction, or a low-magnification oriented orientation in two directions, the longitudinal direction and the transverse direction. It is preferable to apply the coating solution at any time of the film (biaxially stretched film before final reorientation in the machine direction or the transverse direction to complete oriented crystallization), and then further longitudinally and / or A method of transverse stretching can be mentioned.
塗布液の固形分濃度は塗布液の重量を基準として１〜２０重量％であることが好ましい。かかる範囲にある場合、塗布斑の発生を抑制しやすい。
塗布方法としては、公知の任意の塗布方が適用できる。例えばロールコート法、グラビアコート法、ロールブラッシュ法、スプレーコート法、エアーナイフコート法、含浸法およびカーテンコート法などを単独または組み合わせて用いることができる。
The solid content concentration of the coating solution is preferably 1 to 20% by weight based on the weight of the coating solution. When it exists in this range, it is easy to suppress the occurrence of coating spots.
As a coating method, any known coating method can be applied. For example, a roll coating method, a gravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, and a curtain coating method can be used alone or in combination.
＜フィルム特性＞
（熱収縮率）
本発明のフレキシブルプリント回路基板補強用フィルムは、２３０℃で１０分間加熱処理したときの熱収縮率がフィルム長手方向および幅方向の両方向において−３％以上３％未満である。かかる熱収縮率の下限値は、好ましくは−２％、さらに好ましくは−１％、特に好ましくは０％である。また、かかる熱収縮率の上限値は、好ましくは２．５％、より好ましくは２％、さらに好ましくは１％、特に好ましくは０．５％である。
<Film characteristics>
(Heat shrinkage)
The film for reinforcing a flexible printed circuit board of the present invention has a heat shrinkage rate of −3% or more and less than 3% in both the film longitudinal direction and the width direction when heat-treated at 230 ° C. for 10 minutes. The lower limit of the heat shrinkage rate is preferably -2%, more preferably -1%, and particularly preferably 0%. Further, the upper limit of the heat shrinkage rate is preferably 2.5%, more preferably 2%, still more preferably 1%, and particularly preferably 0.5%.
補強用フィルムの熱収縮率が下限値に満たない場合あるいは上限値を超える場合は、上述の塗布層を有していても、ＦＰＣ基板との貼り合せに用いる市販の接着シートとの密着性が低下し、はんだリフロー後にその密着性を保つことができず、接着シートと補強板との接着界面に剥がれや膨れが生じる。かかる範囲内でも、補強用フィルムの熱収縮率が好ましい範囲になるほど、さらにＦＰＣ基板とのひずみが小さくなり、接着シートとの界面部分の剥がれ面積が小さくなることに加え、ＦＰＣ積層体としての反りが低減される。 When the thermal shrinkage rate of the reinforcing film is less than the lower limit value or exceeds the upper limit value, the adhesiveness to a commercially available adhesive sheet used for bonding to the FPC board is sufficient even if the coating layer has the above-mentioned coating layer. And the adhesion cannot be maintained after solder reflow, and peeling or swelling occurs at the adhesive interface between the adhesive sheet and the reinforcing plate. Even within this range, as the thermal shrinkage rate of the reinforcing film becomes a preferable range, the strain with the FPC substrate is further reduced, the peeling area of the interface portion with the adhesive sheet is reduced, and warpage as the FPC laminate. Is reduced.
本発明のフレキシブルプリント回路基板補強用フィルムは、フィルム長手方向および幅方向の両方向においてかかる熱収縮率特性を有することを要する。一方でも熱収縮率がはずれる場合、はんだリフロー後にその密着性を保つことができず、接着シートと補強板との接着界面に剥がれや膨れ、およびピール強度の低下を引き起こす。 The flexible printed circuit board reinforcing film of the present invention is required to have such heat shrinkage characteristics in both the film longitudinal direction and the width direction. On the other hand, if the thermal shrinkage is lost, the adhesion cannot be maintained after solder reflow, causing peeling or swelling at the adhesive interface between the adhesive sheet and the reinforcing plate, and a reduction in peel strength.
かかる熱収縮率は、ポリエステルの種類がポリエチレンナフタンジカルボキシレートであること、後述する延伸条件で二軸延伸を行った後に熱固定処理を施し、かかる熱固定処理温度が（Ｔｍ−１００℃）以上の温度、好ましくは２２０℃〜２５０℃の温度条件で施すこと、その後１５０℃〜２５０℃の温度条件で１〜３％の熱弛緩処理を行い、さらにオフライン工程にて１５０〜２５０℃で５分以上熱処理（アニール処理）し、５０〜８０℃で除冷することによって達成される。また、かかる熱処理条件の範囲内で温度を高くするか、または処理時間を長くすることにより、熱収縮率を好ましい範囲にすることができる。 The heat shrinkage rate is such that the type of polyester is polyethylene naphthane dicarboxylate, and a heat setting treatment is performed after biaxial stretching under the stretching conditions described below, and the heat setting temperature is (Tm-100 ° C.) or higher. At a temperature of 220 ° C. to 250 ° C., followed by 1 to 3% thermal relaxation treatment at a temperature of 150 ° C. to 250 ° C., and further at 150 to 250 ° C. for 5 minutes in an off-line process. This is achieved by heat treatment (annealing) as described above and cooling at 50 to 80 ° C. In addition, by increasing the temperature within the range of the heat treatment conditions or increasing the treatment time, the heat shrinkage rate can be brought into a preferable range.
（熱伝導率）
本発明のフレキシブルプリント回路基板補強用フィルムは、熱伝導率が０．２Ｗ／ｍ・Ｋ以上１０Ｗ／ｍ・Ｋ以下である。かかる熱伝導率は、好ましくは０．２Ｗ／ｍ・Ｋ以上５Ｗ／ｍ・Ｋ以下、さらに好ましくは０．２Ｗ／ｍ・Ｋ以上２Ｗ／ｍ・Ｋ以下、特に好ましくは０．２Ｗ／ｍ・Ｋ以上０．５Ｗ／ｍ・Ｋ以下である。
該補強用フィルムがかかる熱伝導率を有することにより、補強板としてフレキシブルプリント回路基板と貼り合せて使用した際、電子部品実装時および回路の使用時にフレキシブルプリント回路基板に発生する熱を放熱しやすくなる結果、フレキシブルプリント回路基板上の部品の発熱を拡散することができる。ここで、本発明における熱伝導率とは、レーザーフラッシュ法により求めた熱拡散率α、ＪＩＳ Ｋ７１２３に準じて測定した比熱容量Ｃｐ、および密度ρより、下記式から熱伝導度λ（Ｗ／ｃｍＫ）を求め、単位換算を実施した値で表わされる。
熱伝導度λ＝α・Ｃｐ・ρ
かかる熱伝導率特性は、基材層中に一定量の無機粒子を含有し、かつ無機粒子とポリエステル相との界面のボイド面積を調整することにより達成されるが、無機粒子含有量が多い範囲では無機粒子による効果の方が大きく、ボイド面積の影響は小さくなる。
(Thermal conductivity)
The flexible printed circuit board reinforcing film of the present invention has a thermal conductivity of 0.2 W / m · K to 10 W / m · K. The thermal conductivity is preferably 0.2 W / m · K to 5 W / m · K, more preferably 0.2 W / m · K to 2 W / m · K, particularly preferably 0.2 W / m · K. K or more and 0.5 W / m · K or less.
When the reinforcing film has such a thermal conductivity, it is easy to dissipate heat generated in the flexible printed circuit board when mounting electronic components and using the circuit when used as a reinforcing plate by being bonded to a flexible printed circuit board. As a result, the heat generated by the components on the flexible printed circuit board can be diffused. Here, the thermal conductivity in the present invention is the thermal conductivity λ (W / cmK) from the following formula based on the thermal diffusivity α determined by the laser flash method, the specific heat capacity Cp measured according to JIS K7123, and the density ρ. ) And is expressed as a unit converted value.
Thermal conductivity λ = α ・ Cp ・ ρ
Such thermal conductivity characteristics are achieved by containing a certain amount of inorganic particles in the base material layer and adjusting the void area at the interface between the inorganic particles and the polyester phase, but the range in which the inorganic particle content is large. Then, the effect by the inorganic particles is larger, and the influence of the void area becomes smaller.
（ボイド面積）
本発明の補強用フィルムは、基材層における無機粒子とポリエステル相との界面のボイド面積が、フィルム断面において粒子面積の５％以下であることが好ましい。ここでフィルム断面とは、フィルム連続製膜方向に沿った断面、フィルム幅方向に沿った断面のいずれでもよい。かかるボイド面積は、フィルム断面について走査型電子顕微鏡（日立製作所製Ｓ−４７００）を用い、１００００倍の倍率で粒子５０点について測定した値の平均値で求めることができる。ボイド面積は３％以下であることがより好ましく、２％以下であることがさらに好ましく、１％以下であることが特に好ましい。このような無機粒子を多量に含む延伸フィルムの場合、延伸工程により界面にボイドが生じやすく、その断熱効果によって無機粒子による放熱作用が十分に発現しないことがある。本発明においては、基材層中に一定量の無機粒子を含有し、かつボイド面積がかかる範囲内であることにより放熱機能が発現し、フレキシブルプリント回路基板の補強板としてフレキシブルプリント回路基板と貼り合せて使用することにより、電子部品実装時および回路の使用時にフレキシブルプリント回路基板に発生する熱を放熱しやすくなる。
(Void area)
In the reinforcing film of the present invention, the void area at the interface between the inorganic particles and the polyester phase in the base material layer is preferably 5% or less of the particle area in the film cross section. Here, the film cross section may be either a cross section along the film continuous film forming direction or a cross section along the film width direction. Such a void area can be determined by an average value of values measured for 50 particles at a magnification of 10,000 times using a scanning electron microscope (S-4700, manufactured by Hitachi, Ltd.) for the film cross section. The void area is more preferably 3% or less, further preferably 2% or less, and particularly preferably 1% or less. In the case of a stretched film containing a large amount of such inorganic particles, voids are likely to occur at the interface due to the stretching step, and the heat dissipation effect by the inorganic particles may not be sufficiently exhibited due to the heat insulating effect. In the present invention, the base material layer contains a certain amount of inorganic particles, and the void area is within such a range, so that a heat dissipation function is exhibited, and the flexible printed circuit board is attached to the flexible printed circuit board as a reinforcing plate. By using together, it becomes easy to radiate the heat generated in the flexible printed circuit board when mounting electronic components and using the circuit.
ボイド面積をかかる範囲にするための手段として、延伸条件をフィルム長手方向、幅方向ともに３．５倍以下、より好ましくはフィルム長手方向、幅方向ともに３．３倍以下、さらに好ましくはフィルム長手方向、幅方向ともに３．２倍以下、特に好ましくはフィルム長手方向、幅方向ともに３．１倍以下とする方法が挙げられる。また表面処理された酸化チタンを用いることにより、さらにその効果が高まる。 As a means for setting the void area in such a range, the stretching condition is 3.5 times or less in both the film longitudinal direction and the width direction, more preferably 3.3 times or less in both the film longitudinal direction and the width direction, and more preferably in the film longitudinal direction. The width direction is 3.2 times or less, particularly preferably 3.1 times or less in both the film longitudinal direction and the width direction. The effect is further enhanced by using surface-treated titanium oxide.
＜フィルム厚み＞
本発明のフレキシブルプリント回路基板補強用フィルムのフィルム厚みは５０μｍ以上２５０μｍ以下であることが好ましい。
<Film thickness>
The film thickness of the flexible printed circuit board reinforcing film of the present invention is preferably 50 μm or more and 250 μm or less.
＜製膜＞
本発明のフィルムを得る方法を以下に具体的に述べるが、以下の例に特に限定されるものではない。
ポリエステルは所望に応じて乾燥後、押出機に供給してＴダイよりシート状に成形される。
Ｔダイより押し出されたシート状成形物を表面温度１０〜６０℃の冷却ドラムで冷却固化し、この未延伸フィルムを例えばロール加熱または赤外線加熱によって加熱した後、縦方向に延伸して縦延伸フィルムを得る。かかる縦延伸は２個以上のロールの周速差を利用して行うのが好ましい。縦延伸温度はポリエステルのガラス転移点（Ｔｇ）より高い温度、更にはＴｇより２０〜４０℃高い温度とするのが好ましい。縦延伸倍率は２．８５倍以上３．５０倍以下の範囲で行うことが好ましく、さらに好ましくは３．００倍以上３．３０倍以下の範囲、特に好ましくは３．００倍以上３．２０倍以下の範囲である。縦延伸倍率が下限に満たない場合、補強板としての強度が十分でないことがある他、フィルムの厚み斑が悪くなり良好なフィルムが得られないことがある。また縦延伸倍率が上限を超える場合、本発明の熱収縮率特性が得られず、また無機粒子とポリエステル相の界面のボイドが大きくなり、無機粒子添加による放熱性効果が低減する。
<Film formation>
The method for obtaining the film of the present invention is specifically described below, but is not particularly limited to the following examples.
The polyester is dried, if desired, and then supplied to an extruder to be formed into a sheet from a T-die.
The sheet-like molded product extruded from the T-die is cooled and solidified with a cooling drum having a surface temperature of 10 to 60 ° C., and this unstretched film is heated by, for example, roll heating or infrared heating, and then stretched in the longitudinal direction. Get. Such longitudinal stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls. The longitudinal stretching temperature is preferably higher than the glass transition point (Tg) of the polyester, more preferably 20 to 40 ° C. higher than Tg. The longitudinal stretching ratio is preferably 2.85 times or more and 3.50 times or less, more preferably 3.00 times or more and 3.30 times or less, and particularly preferably 3.00 times or more and 3.20 times. The range is as follows. When the longitudinal draw ratio is less than the lower limit, the strength as a reinforcing plate may not be sufficient, and the thickness unevenness of the film may deteriorate and a good film may not be obtained. On the other hand, when the longitudinal draw ratio exceeds the upper limit, the heat shrinkage characteristics of the present invention cannot be obtained, and voids at the interface between the inorganic particles and the polyester phase become large, and the heat dissipation effect due to the addition of the inorganic particles is reduced.
得られた縦延伸フィルムは、続いて横延伸（連続製膜方向に垂直な方向への延伸）を行い、その後熱固定、熱弛緩の処理を順次施して二軸配向フィルムとするが、かかる処理はフィルムを走行させながら行う。
横延伸処理はポリエステルのガラス転移点（Ｔｇ）より２０℃高い温度から始める。そしてポリエステルの融点（Ｔｍ）より（１２０〜３０）℃低い温度まで昇温しながら行う。この横延伸開始温度は、（Ｔｇ＋４０）℃以下であることが好ましい。また横延伸最高温度は、Ｔｍより（１００〜４０）℃低い温度であることが好ましい。
横延伸過程の昇温は連続的でも段階的（逐次的）でもよいが、通常は段階的に昇温する。例えば、ステンターの横延伸ゾーンをフィルム走行方向に沿って複数に分け、各ゾーンごとに所定温度の加熱媒体を流すことで昇温する。
The obtained longitudinally stretched film is subsequently subjected to transverse stretching (stretching in a direction perpendicular to the continuous film-forming direction), and then subjected to heat fixation and thermal relaxation treatment in order to obtain a biaxially oriented film. Is done while running the film.
The transverse stretching process starts at a temperature 20 ° C. higher than the glass transition point (Tg) of the polyester. And it heats up to (120-30) degree C temperature lower than melting | fusing point (Tm) of polyester. The transverse stretching start temperature is preferably (Tg + 40) ° C. or lower. The maximum transverse stretching temperature is preferably (100 to 40) ° C. lower than Tm.
Although the temperature increase in the transverse stretching process may be continuous or stepwise (sequential), the temperature is usually increased stepwise. For example, the transverse stretch zone of the stenter is divided into a plurality along the film running direction, and the temperature is raised by flowing a heating medium having a predetermined temperature for each zone.
横延伸倍率は２．８５倍以上３．５０倍以下の範囲で行うことが好ましく、さらに好ましくは３．００倍以上３．３０倍以下の範囲、特に好ましくは３．００倍以上３．２０倍以下の範囲である。横延伸倍率が下限値に満たない場合、補強板としての強度が十分でないことがある他、フィルムの厚み斑が悪くなり良好なフィルムが得られないことがある。また横延伸倍率が上限値を超える場合、本発明の熱収縮率特性が得られず、また無機粒子とポリエステル相の界面のボイドが大きくなり、無機粒子添加による放熱性効果が低減する。 The transverse draw ratio is preferably 2.85 times or more and 3.50 times or less, more preferably 3.00 times or more and 3.30 times or less, and particularly preferably 3.00 times or more and 3.20 times. The range is as follows. When the transverse draw ratio is less than the lower limit value, the strength as a reinforcing plate may not be sufficient, and the thickness unevenness of the film may deteriorate and a good film may not be obtained. On the other hand, when the transverse draw ratio exceeds the upper limit value, the heat shrinkage characteristics of the present invention cannot be obtained, and voids at the interface between the inorganic particles and the polyester phase become large, and the heat dissipation effect due to the addition of the inorganic particles is reduced.
二軸延伸されたフィルムは、その後熱固定処理が施される。熱固定処理温度は（Ｔｍ−１００℃）以上、さらに好ましくは（Ｔｍ−７０）℃〜（Ｔｍ−４０）℃の範囲で行うことができ、特に２２０℃〜２５０℃の範囲で行うことが好ましい。熱固定処理後、１５０℃〜２５０℃の温度条件で１〜３％の熱弛緩処理を行い、さらにオフライン工程にて１５０〜２５０℃で３０秒以上熱処理（アニール処理）し、５０〜８０℃で除冷する。これらの工程を経ることにより、本発明の熱収縮率特性を有するフィルムを得ることができる。また、オフライン工程で行うアニール処理は、かかる熱処理条件の範囲内で温度を高くするか、または処理時間を長くすることにより、熱収縮率を好ましい範囲にすることができる。アニール処理時間の上限は特に制限されないが、長時間すぎるとフィルム物性が低下する可能性があるため、高々１時間であることが好ましい。 The biaxially stretched film is then heat set. The heat setting treatment temperature can be (Tm-100 ° C) or higher, more preferably (Tm-70) ° C to (Tm-40) ° C, particularly preferably 220 ° C to 250 ° C. . After heat setting treatment, heat relaxation treatment of 1% to 3% is performed under a temperature condition of 150 ° C. to 250 ° C., and further heat treatment (annealing treatment) is performed at 150 to 250 ° C. for 30 seconds or more in an offline process, and 50 ° C. to 80 ° C. Remove the cooling. By passing through these steps, the film having the heat shrinkage characteristics of the present invention can be obtained. In the annealing process performed in the off-line process, the heat shrinkage rate can be set within a preferable range by increasing the temperature within the range of the heat treatment conditions or increasing the treatment time. The upper limit of the annealing treatment time is not particularly limited, but if it is too long, the film physical properties may be lowered, and therefore it is preferably at most 1 hour.
＜接着シート＞
本発明のフレキシブルプリント回路基板補強用フィルムとフレキシブルプリント回路基板とを貼りあわせるに際し、接着シートを介して貼りあわせることが好ましい。かかる接着シートとして市販の接着シートを用いることができ、例えばエポキシ系接着シートまたはアクリル系接着シートを用いることができる。これら市販の接着シートの具体例として、ＴＦＡ−８８０ＣＣ３５（京セラケミカル株式会社製）、ＳＡＦＶ（ニッカン工業株式会社製）、Ｄ３４１０（ソニーケミカル＆インフォメーションデバイス株式会社製）が挙げられる。
<Adhesive sheet>
When the flexible printed circuit board reinforcing film of the present invention and the flexible printed circuit board are bonded together, it is preferable to bond them together via an adhesive sheet. A commercially available adhesive sheet can be used as such an adhesive sheet, for example, an epoxy adhesive sheet or an acrylic adhesive sheet can be used. Specific examples of these commercially available adhesive sheets include TFA-880CC35 (manufactured by Kyocera Chemical Co., Ltd.), SAFV (manufactured by Nikkan Kogyo Co., Ltd.), and D3410 (manufactured by Sony Chemical & Information Device Co., Ltd.).
＜フレキシブルプリント回路基板積層体＞
本発明のフレキシブルプリント回路基板補強用フィルムを用いてフレキシブルプリント回路基板補強板に加工し、得られた補強板をフレキシブルプリント回路基板の補強が必要な部位に貼り合せて用いることができる。
本発明のフレキシブルプリント回路基板補強用フィルムと貼りあわせて用いられるフレキシブルプリント回路基板のベースフィルムとして、ポリイミドまたはポリエステルが例示される。ポリエステルとしてポリエチレンテレフタレート、ポリエチレンナフタレートなどが挙げられる。フレキシブルプリント回路基板の厚みは、通常７．５〜２５０μｍ程度である。
<Flexible printed circuit board laminate>
The flexible printed circuit board reinforcing film of the present invention is used to process into a flexible printed circuit board reinforcing plate, and the obtained reinforcing plate can be attached to a portion where the flexible printed circuit board needs to be reinforced.
Examples of the base film of the flexible printed circuit board used by being bonded to the flexible printed circuit board reinforcing film of the present invention include polyimide and polyester. Examples of the polyester include polyethylene terephthalate and polyethylene naphthalate. The thickness of the flexible printed circuit board is usually about 7.5 to 250 μm.
また、本発明のフレキシブルプリント回路基板積層体は、フレキシブルプリント回路基板に接着シートを介して本発明のフレキシブルプリント回路基板補強板を貼り合せた構成を有する。フレキシブルプリント回路基板積層体は、はんだリフロー工程後に接着シートを介した接着界面における剥がれや膨れの発生がなく、ピール強度が高く、補強効果が高いことから、部品搭載部など回路基板だけでは撓みが生じやすい部位や、コネクター接続部などコネクターに取り付ける際に折れ曲がったりしやすい部位といった、より補強性が必要とされる部位に好適に用いることができる。さらに、本発明のフレキシブルプリント回路基板補強用フィルムは熱伝導率が高いため、フレキシブルプリント回路基板の補強板としてフレキシブルプリント回路基板と貼り合せて使用することにより、電子部品実装時および回路の使用時にフレキシブルプリント回路基板に発生する熱の放熱性に優れる。 Moreover, the flexible printed circuit board laminated body of this invention has the structure which bonded the flexible printed circuit board reinforcement board of this invention to the flexible printed circuit board through the adhesive sheet. The flexible printed circuit board laminate does not cause peeling or swelling at the adhesive interface via the adhesive sheet after the solder reflow process, has high peel strength, and has a high reinforcing effect. It can be suitably used for a part that needs to be more reinforced, such as a part that easily occurs or a part that easily bends when attached to a connector, such as a connector connection part. Furthermore, since the film for reinforcing a flexible printed circuit board of the present invention has high thermal conductivity, it can be used as a reinforcing plate of the flexible printed circuit board by being bonded to the flexible printed circuit board, when mounting electronic components and using a circuit. Excellent heat dissipation of heat generated in flexible printed circuit boards.
なお、本発明のフレキシブルプリント回路のベースフィルム又は基板に形成される回路パターンについては特に制限はなく、従来から用いられている一般的なものが使用される。本発明のフレキシブルプリント回路基板積層体は、補強板の接着性及び接着部の耐熱性に優れ、かつフレキシブルプリント回路基板に発生する熱の放熱性にも優れることから、車載用の電子機器などの高温環境下で使用される電子機器の電気回路に有用である。 In addition, there is no restriction | limiting in particular about the circuit pattern formed in the base film or board | substrate of the flexible printed circuit of this invention, The general thing used conventionally is used. Since the flexible printed circuit board laminate of the present invention is excellent in the adhesiveness of the reinforcing plate and the heat resistance of the bonded portion, and also excellent in the heat dissipation of the heat generated in the flexible printed circuit board, It is useful for electric circuits of electronic equipment used in high temperature environments.
以下、実施例および比較例をあげて本発明をさらに具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited thereto.
１．熱収縮率
フィルムサンプルに１０ｃｍ間隔で標点をつけ、荷重をかけずに２３０℃のオーブンで１０分間熱処理を実施し、熱処理後の標点間隔を測定して、フィルム連続製膜方向（ＭＤ方向）と、製膜方向に垂直な方向（ＴＤ方向）において、下記式にて熱収縮率を算出した。
熱収縮率（％）
＝{（熱処理前標点間距離−熱処理後標点間距離）／熱処理前標点間距離}×１００
1. Heat shrinkage rate Marks are applied to film samples at intervals of 10 cm, heat treatment is carried out in an oven at 230 ° C. for 10 minutes without applying a load, the distance between the marks after heat treatment is measured, and the film is continuously formed (MD direction) ) And the direction perpendicular to the film forming direction (TD direction), the thermal contraction rate was calculated by the following formula.
Thermal shrinkage (%)
= {(Distance between heat-marks before heat treatment-Distance between heat-marks after heat treatment) / Distance between heat-marks before heat treatment} × 100
２．熱伝導率
レーザーフラッシュ法により熱拡散率α（ｃｍ２／ｓｅｃ）を測定し、別に測定した比熱容量Ｃｐ（Ｊ／ｇＫ）と密度ρ（ｇ／ｃｃ）から、熱伝導度λ（Ｗ／ｃｍＫ）をλ＝α・Ｃｐ・ρで求め、単位換算を実施した値を用いて評価を行った。
なお、熱拡散率αの測定方法であるレーザーフラッシュ法とは、試料の両面にＡｕ蒸着し、両面を黒化処理して２５℃でルビーレーザーパルス光を均一に照射する方法である。
また、密度ρは、硝酸カルシウム水溶液を用いて密度勾配管法にて測定して得ることができる。
また、比熱容量Ｃｐは、ＪＩＳ Ｋ７１２３に準じて測定された値である。
2. Thermal conductivity The thermal diffusivity α (cm 2 / sec) is measured by a laser flash method, and the thermal conductivity λ (W / cmK) is calculated from the specific heat capacity Cp (J / gK) and density ρ (g / cc) separately measured. ) Was calculated by λ = α · Cp · ρ, and evaluation was performed using values obtained by unit conversion.
The laser flash method, which is a method for measuring the thermal diffusivity α, is a method in which Au is vapor-deposited on both surfaces of the sample, both surfaces are blackened, and the ruby laser pulse light is uniformly irradiated at 25 ° C.
Further, the density ρ can be obtained by measuring with a density gradient tube method using a calcium nitrate aqueous solution.
The specific heat capacity Cp is a value measured according to JIS K7123.
３．ボイド面積
フィルム長手方向に沿った断面について、走査型電子顕微鏡（日立製作所製S-4700）を用い、１００００倍の倍率で粒子５０点について測定し、それぞれの粒子面積に対するボイド面積の割合を求め、それらの平均値より算出した。
3. Void area About the cross section along the film longitudinal direction, using a scanning electron microscope (S-4700, manufactured by Hitachi, Ltd.), measure 50 particles at a magnification of 10,000 times, and determine the ratio of the void area to each particle area, It calculated from those average values.
４．はんだリフローテスト
はんだリフローは、ピーク温度２６０℃で１０秒間のリフロー処理を行い、処理後の外観評価を行った。なお評価にあたり、以下の方法で作成された二軸配向ポリエステルフィルム／市販の補強用フィルム接着用接着シート／ポリイミドフィルムを基材とした片面銅張積層板からなるフレキシブルプリント回路基板積層体を用いた。
4). Solder reflow test For solder reflow, a reflow treatment was performed at a peak temperature of 260 ° C. for 10 seconds, and the appearance after the treatment was evaluated. In the evaluation, a flexible printed circuit board laminate composed of a single-sided copper-clad laminate based on a biaxially oriented polyester film / commercially available adhesive film for reinforcing film adhesive / polyimide film prepared by the following method was used. .
＜フレキシブルプリント回路基板積層体の作成方法＞
作成した二軸配向ポリエステルフィルムの上に、市販の補強用フィルム接着用接着シート（ＳＡＦＶ（商品名）：ニッカン工業株式会社製）、さらに接着シートの上にポリイミドフィルムを基材とした片面銅張積層板（Ｆ―３０ＶＣ１（商品名）：ニッカン工業株式会社製）をポリイミドフィルム側を接着シートに面するようにしてのせた。この積層体に温度１００℃、圧力３ＭＰａで５分間プレスした後、さらに温度を上げ１６０℃、圧力３ＭＰａで５分間プレスし、そのまま６０分間の熱処理を施した。その後室温まで冷却し取り出した。
<Method for creating flexible printed circuit board laminate>
On the prepared biaxially oriented polyester film, a commercially available adhesive sheet for reinforcing film bonding (SAFV (trade name): manufactured by Nikkan Kogyo Co., Ltd.), and further, a single-sided copper-clad with a polyimide film as a base material on the adhesive sheet A laminate (F-30VC1 (trade name): manufactured by Nikkan Kogyo Co., Ltd.) was placed on the side of the polyimide film facing the adhesive sheet. The laminated body was pressed at a temperature of 100 ° C. and a pressure of 3 MPa for 5 minutes, then further raised in temperature, pressed at 160 ° C. and a pressure of 3 MPa for 5 minutes, and directly subjected to a heat treatment for 60 minutes. Thereafter, it was cooled to room temperature and taken out.
［外観評価］
（気泡、膨れ）
リフロー処理後のフレキシブルプリント回路基板積層体について、接着シートと補強板との界面に気泡や膨れの発生があるか補強板側から観察し、測定範囲５ｃｍ×５ｃｍ四方における気泡、膨れの発生面積を求めて下記の基準で評価した。
Ａ： 気泡、膨れの発生した面積が１０％未満
Ｂ： 気泡、膨れの発生した面積が１０％以上１５％未満
Ｃ： 気泡、膨れの発生した面積が１５％以上３０％未満
Ｄ： 気泡、膨れの発生した面積が３０％以上
[Appearance evaluation]
(Bubbles, blisters)
For the flexible printed circuit board laminate after reflow treatment, observe the bubble or bulge at the interface between the adhesive sheet and the reinforcing plate from the reinforcing plate side. Obtained and evaluated according to the following criteria.
A: The area where bubbles and blisters are generated is less than 10% B: The area where bubbles and blisters are generated is 10% or more and less than 15% C: The area where bubbles and blisters are generated is 15% or more and less than 30% D: Bubbles and blisters More than 30%
（基材の反り）
試料寸法を２５ｃｍ×２５ｃｍとし、リフロー処理後のフレキシブルプリント回路基板積層体サンプルを相対湿度５５％、２３℃の雰囲気下で２４時間定盤上に置いた状態で４隅のカール状態を観測し、４隅の反り量（ｍｍ）の平均を測定した。
(Substrate warpage)
The sample dimensions were 25 cm × 25 cm, and the curled state of the four corners was observed in a state where the flexible printed circuit board laminate sample after the reflow treatment was placed on a surface plate for 24 hours in an atmosphere of relative humidity 55% and 23 ° C. The average of the amount of warping (mm) at the four corners was measured.
＜塗布層中の樹脂組成と各成分の配合比＞
実施例と比較例で用いた塗布層の組成と配合は、表１の通りである。ここで塗布層を構成する各成分は以下のものを用いた。
<Resin composition in coating layer and blending ratio of each component>
Table 1 shows the composition and composition of the coating layers used in Examples and Comparative Examples. Here, the following components were used for each component constituting the coating layer.
（アクリル）： メチルメタクリレート３０モル％／２−イソプロペニル−２−オキサゾリン３０モル％／ポリエチレンオキシド（ｎ＝１０）メタクリレート１０モル％／アクリルアミド３０モル％で構成されているアクリル樹脂（Ｔｇ＝５０℃）を用いた。なお、アクリル樹脂は次の方法で製造されたものであり、特開昭６３−３７１６７号公報の製造例１〜３に記載の方法に準じている。すなわち、四つ口フラスコに、イオン交換水３０２部を仕込んで窒素気流中で６０℃まで昇温させ、次いで重合開始剤として過硫酸アンモニウム０．５部、亜硝酸水素ナトリウム０．２部を添加し、更にモノマー類である、メタクリル酸メチル２３．３部、２−イソプロペニル−２−オキサゾリン２２．６部、ポリエチレンオキシド（ｎ＝１０）メタクリル酸４０．７部、アクリルアミド１３．３部の混合物を３時間にわたり、液温が６０〜７０℃になるよう調整しながら滴下した。滴下終了後も同温度範囲に２時間保持しつつ、撹拌下に反応を継続させ、次いで冷却して固形分が２５％のアクリルの水分散体を得た。 (Acrylic): Acrylic resin (Tg = 50 ° C.) composed of 30% by mole of methyl methacrylate / 30% by mole of 2-isopropenyl-2-oxazoline / 10% by mole of polyethylene oxide (n = 10) / 30% by mole of acrylamide ) Was used. The acrylic resin was produced by the following method, and conformed to the method described in Production Examples 1 to 3 of JP-A No. 63-37167. That is, 302 parts of ion-exchanged water was charged into a four-necked flask and heated to 60 ° C. in a nitrogen stream, and then 0.5 parts of ammonium persulfate and 0.2 part of sodium hydrogen nitrite were added as a polymerization initiator. Furthermore, a mixture of monomers, 23.3 parts of methyl methacrylate, 22.6 parts of 2-isopropenyl-2-oxazoline, 40.7 parts of polyethylene oxide (n = 10) methacrylic acid, and 13.3 parts of acrylamide. The solution was added dropwise over 3 hours while adjusting the liquid temperature to 60 to 70 ° C. After completion of dropping, the reaction was continued with stirring while maintaining the same temperature range for 2 hours, and then cooled to obtain an acrylic aqueous dispersion having a solid content of 25%.
（ポリエステル）： 酸成分が２，６−ナフタレンジカルボン酸６３モル％／イソフタル酸３２モル％／５−ナトリウムスルホイソフタル酸５モル％ 、グリコール成分がエチレングリコール９０モル％／ジエチレングリコール１０モル％で構成されているポリエステル（Ｔｇ＝７６℃、平均分子量１２０００）を用いた。なお、ポリエステルは次の方法で製造したものであり、特開平０６−１１６４８７ 号公報の実施例１に記載の方法に準じている。すなわち、２，６−ナフタレンジカルボン酸ジメチル４２部、イソフタル酸ジメチル１７部、５−ナトリウムスルホイソフタル酸ジメチル４部、エチレングリコール３３部、ジエチレングリコール２部を反応器に仕込み、これにテトラブトキシチタン０．０５部を添加して窒素雰囲気下で温度を２３０℃ にコントロールして加熱し、生成するメタノールを留去させてエステル交換反応を行った。次いで反応系の温度を徐々に２５５℃まで上昇させ系内を１ｍｍＨｇの減圧にして重縮合反応を行い、ポリエステルを得た。 (Polyester): The acid component is composed of 63 mol% of 2,6-naphthalenedicarboxylic acid / 32 mol% of isophthalic acid / 5 mol% of 5-sodium sulfoisophthalic acid, and the glycol component is composed of 90 mol% of ethylene glycol / 10 mol% of diethylene glycol. Polyester (Tg = 76 ° C., average molecular weight 12000) was used. Polyester was produced by the following method, and conformed to the method described in Example 1 of JP-A-06-116487. That is, 42 parts of dimethyl 2,6-naphthalenedicarboxylate, 17 parts of dimethyl isophthalate, 4 parts of dimethyl 5-sodium sulfoisophthalate, 33 parts of ethylene glycol and 2 parts of diethylene glycol were charged into a reactor. 05 parts were added and heated under a nitrogen atmosphere while controlling the temperature at 230 ° C., and the produced methanol was distilled off to conduct a transesterification reaction. Subsequently, the temperature of the reaction system was gradually raised to 255 ° C., and the pressure inside the system was reduced to 1 mmHg to carry out a polycondensation reaction to obtain a polyester.
（粒子）： シリカの無機粒子（平均粒径：１００ｎｍ）を用いた。 (Particles): Silica inorganic particles (average particle size: 100 nm) were used.
（濡れ剤）： ポリオキシエチレン（ｎ＝７）ラウリルエーテル（三洋化成株式会社製、商品名「ナロアクティーＮ−７０」）を用いた。 (Wetting agent): Polyoxyethylene (n = 7) lauryl ether (manufactured by Sanyo Chemical Co., Ltd., trade name “Naroacty N-70”) was used.
（添加剤）： カルナバワックス（中京油脂株式会社製、商品名「セロゾール５２４」）を用いた。 (Additive): Carnauba wax (manufactured by Chukyo Yushi Co., Ltd., trade name “Cerosol 524”) was used.
＜実施例１＞
平均粒径１．５μｍの酸化チタンを基材層の重量を基準として３０重量％含有するポリエチレンナフタレンジカルボキシレート樹脂（固有粘度０．６ｄｌ／ｇ（ｏ−クロロフェノール中、３５℃））を２９０℃に加熱された押出機に供給し、２９０℃のダイスよりシート状に成形した。さらにこのシートを表面温度６０℃の冷却ドラムで冷却固化した未延伸フィルムを１４０℃に加熱したロール群に導き、長手方向（縦方向）に３．０倍で延伸し、６０℃のロール群で冷却した後、その片面に表１に記載の塗布層用組成物からなる固形分濃度３％の水性塗液をロールコーターで均一に塗布した。続いて、縦延伸したフィルムの両端をクリップで保持しながらテンターに導き１５０℃に加熱された雰囲気中で長手に垂直な方向（横方向）に３．０倍で延伸した。その後テンタ−内で２５０℃の熱固定を行い、２４０℃で２％の弛緩後、均一に除冷して、室温まで冷やして１７５μｍ厚みの二軸延伸フィルムを得た。さらにそのロールをＩＲヒーターを用いて２２０度で１分間熱アニール処理を行った後、５０度の温度雰囲気下で除冷した。得られたフィルムの特性を表２に示す。
得られたフィルムを用いて評価方法に準じてフレキシブルプリント回路基板積層体を作成し、はんだリフローテストを行ったところ、補強板と接着シートとの界面に発生した気泡または膨れの面積は１０％未満であり、密着性良好であった。また補強板の熱伝導率が高く、フレキシブルプリント回路基板に発生した熱の放熱効果が高かった。
<Example 1>
290 of polyethylene naphthalene dicarboxylate resin (intrinsic viscosity 0.6 dl / g (in o-chlorophenol, 35 ° C.)) containing 30% by weight of titanium oxide having an average particle size of 1.5 μm based on the weight of the base material layer It was supplied to an extruder heated to 0 ° C. and formed into a sheet form from a 290 ° C. die. Furthermore, the unstretched film obtained by cooling and solidifying the sheet with a cooling drum having a surface temperature of 60 ° C. is led to a roll group heated to 140 ° C., and stretched 3.0 times in the longitudinal direction (longitudinal direction). After cooling, an aqueous coating solution having a solid content concentration of 3% composed of the composition for coating layer shown in Table 1 was uniformly coated on one side with a roll coater. Subsequently, the film was stretched by 3.0 times in a direction perpendicular to the longitudinal direction (lateral direction) in an atmosphere heated to 150 ° C. while being guided to a tenter while holding both ends of the longitudinally stretched film with clips. Thereafter, heat setting was performed at 250 ° C. in a tenter, and after 2% relaxation at 240 ° C., the film was uniformly removed and cooled to room temperature to obtain a biaxially stretched film having a thickness of 175 μm. Further, the roll was subjected to a thermal annealing treatment at 220 ° C. for 1 minute using an IR heater, and then cooled in a temperature atmosphere of 50 ° C. The properties of the obtained film are shown in Table 2.
Using the obtained film, a flexible printed circuit board laminate was prepared according to the evaluation method, and a solder reflow test was performed. The area of bubbles or blisters generated at the interface between the reinforcing plate and the adhesive sheet was less than 10%. The adhesion was good. Moreover, the thermal conductivity of the reinforcing plate was high, and the heat dissipation effect of the heat generated in the flexible printed circuit board was high.
＜実施例２＞
平均粒径が１．５μｍである酸化チタン粒子を２５重量％としたこと以外は実施例１と同様の方法によって二軸配向ポリエステルフィルムを得た。
<Example 2>
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the titanium oxide particles having an average particle size of 1.5 μm were 25% by weight.
＜実施例３＞
平均粒径が１．５μｍである酸化チタン粒子を１５重量％としたこと以外は実施例１と同様の方法によって二軸配向ポリエステルフィルムを得た。
<Example 3>
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the titanium oxide particles having an average particle diameter of 1.5 μm were changed to 15% by weight.
＜実施例４〜６＞
塗布層用組成物の種類を変更した以外は実施例１と同様の方法によって二軸配向ポリエステルフィルムを得た。
<Examples 4 to 6>
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the type of the coating layer composition was changed.
＜実施例７＞
長手方向（縦方向）に３．０倍で延伸し、長手に垂直な方向（横方向）に３．２倍で延伸したこと以外は実施例１と同様の方法によって二軸配向ポリエステルフィルムを得た。
<Example 7>
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the film was stretched 3.0 times in the longitudinal direction (longitudinal direction) and stretched 3.2 times in the direction perpendicular to the longitudinal direction (lateral direction). It was.
＜実施例８＞
長手方向（縦方向）に３．１倍で延伸し、長手に垂直な方向（横方向）に３．２倍で延伸したこと以外は実施例１と同様の方法によって二軸配向ポリエステルフィルムを得た。
<Example 8>
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the film was stretched by 3.1 times in the longitudinal direction (longitudinal direction) and stretched by 3.2 times in the direction perpendicular to the longitudinal direction (lateral direction). It was.
＜比較例１＞
平均粒径が１．５μｍである酸化チタン粒子を０重量％としたこと以外は実施例１と同様の方法によって二軸配向ポリエステルフィルムを得た。
<Comparative Example 1>
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the titanium oxide particles having an average particle diameter of 1.5 μm were changed to 0% by weight.
＜比較例２＞
平均粒径が１．５μｍである酸化チタン粒子を５重量％としたこと以外は実施例１と同様の方法によって二軸配向ポリエステルフィルムを得た。
<Comparative example 2>
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the titanium oxide particles having an average particle diameter of 1.5 μm were changed to 5% by weight.
＜比較例３＞
長手方向（縦方向）に３．２倍で延伸し、長手に垂直な方向（横方向）に３．２５倍で延伸したこと以外は実施例１と同様の方法によって二軸配向ポリエステルフィルムを得た。
<Comparative Example 3>
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the film was stretched by 3.2 times in the longitudinal direction (longitudinal direction) and stretched by 3.25 times in the direction perpendicular to the longitudinal direction (lateral direction). It was.
＜比較例４＞
平均粒径１．５μｍの酸化チタンを１５重量％含有するポリエチレンテレフタレート樹脂を２８０℃に加熱された押出機に供給し、２８０℃のダイスよりシート状に成形した。さらにこのシートを表面温度２０℃の冷却ドラムで冷却固化した未延伸フィルムを８０℃に加熱したロール群に導き、長手方向（縦方向）に３．０倍で延伸し、２０℃のロール群で冷却した。続いて、縦延伸したフィルムの両端をクリップで保持しながらテンターに導き１２０℃に加熱された雰囲気中で長手に垂直な方向（横方向）に３．１倍で延伸した。その後テンタ−内で２２０℃の熱固定を行い、２００℃で２％の弛緩後、均一に除冷して、室温まで冷やして１８０μｍ二軸延伸フィルムを得た。
<Comparative Example 4>
A polyethylene terephthalate resin containing 15% by weight of titanium oxide having an average particle diameter of 1.5 μm was supplied to an extruder heated to 280 ° C. and molded into a sheet form from a die at 280 ° C. Furthermore, the unstretched film obtained by cooling and solidifying this sheet with a cooling drum having a surface temperature of 20 ° C. is led to a roll group heated to 80 ° C., and stretched 3.0 times in the longitudinal direction (longitudinal direction). Cooled down. Subsequently, the film was stretched by a factor of 3.1 in the direction perpendicular to the longitudinal direction (lateral direction) in an atmosphere heated to 120 ° C. while being held at both ends of the longitudinally stretched film with clips. Thereafter, the film was heat-set at 220 ° C. in a tenter, relaxed by 2% at 200 ° C., uniformly cooled, and cooled to room temperature to obtain a 180 μm biaxially stretched film.
＜比較例５＞
縦方向への延伸後に塗布層を設けなかった以外は実施例１と同様の方法にて作成した。
<Comparative Example 5>
It was prepared in the same manner as in Example 1 except that the coating layer was not provided after stretching in the longitudinal direction.
＜比較例６＞
塗液の種類を変更した以外は実施例１と同様の方法にて作成した。
<Comparative Example 6>
It was prepared in the same manner as in Example 1 except that the type of coating liquid was changed.
本発明のフレキシブルプリント回路基板補強用フィルムは、はんだリフロー後のフレキシブルプリント回路基板との密着性が良好で、部分的な剥がれや膨れがなく生産性に優れており、かつフレキシブルプリント回路基板の補強板としてフレキシブルプリント回路基板と貼り合せて使用することにより、電子部品実装時および回路の使用時にフレキシブルプリント回路基板に発生する熱の放熱性に優れることから、その工業的価値は極めて高い。 The flexible printed circuit board reinforcing film of the present invention has good adhesion with the flexible printed circuit board after solder reflow, is excellent in productivity without partial peeling or swelling, and is reinforced in the flexible printed circuit board. When used as a board by being bonded to a flexible printed circuit board, the industrial value is extremely high because heat dissipation generated in the flexible printed circuit board is excellent when mounting electronic components and using a circuit.
Claims (10)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009287756A JP5519260B2 (en) | 2009-12-18 | 2009-12-18 | Flexible printed circuit board reinforcing film, flexible printed circuit reinforcing plate comprising the same, and flexible printed circuit board laminate comprising the same |
| KR1020100129079A KR101761916B1 (en) | 2009-12-18 | 2010-12-16 | Film for fpc board stiffener, fpc board stiffener therefrom and fpc board laminated body therefrom |
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| JP2009287756A JP5519260B2 (en) | 2009-12-18 | 2009-12-18 | Flexible printed circuit board reinforcing film, flexible printed circuit reinforcing plate comprising the same, and flexible printed circuit board laminate comprising the same |
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| EP3091047A1 (en) | 2015-05-07 | 2016-11-09 | Dupont Teijin Films U.S Limited Partnership | Polyester film with electrical insulation and heat conduction properties |
| US9834713B2 (en) * | 2016-02-23 | 2017-12-05 | 3M Innovative Properties Company | Oriented thermally conductive dielectric film |
| KR102399857B1 (en) | 2017-09-28 | 2022-05-20 | 닛토덴코 가부시키가이샤 | Reinforcing film |
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| JPH0952456A (en) * | 1995-08-15 | 1997-02-25 | Toppan Printing Co Ltd | Base material for recording by being heat-sensitively recorded and medium used thereof |
| JPH11168267A (en) * | 1997-12-03 | 1999-06-22 | Teijin Ltd | Flexible circuit board film |
| JP3909268B2 (en) * | 2002-03-01 | 2007-04-25 | 帝人デュポンフィルム株式会社 | Highly transparent and easily adhesive polyester film |
| JP3869752B2 (en) * | 2002-05-07 | 2007-01-17 | 帝人株式会社 | Method for producing polyethylene-2,6-naphthalate resin composition and polyethylene-2,6-naphthalate film |
| JP4141264B2 (en) * | 2003-01-20 | 2008-08-27 | 帝人株式会社 | Method for producing polyethylene-2,6-naphthalate film |
| JP2005126559A (en) * | 2003-10-23 | 2005-05-19 | Teijin Dupont Films Japan Ltd | Film for laser via processing |
| JP4916175B2 (en) * | 2004-02-18 | 2012-04-11 | 三菱樹脂株式会社 | Adhesive and coating film for electrical material using the same |
| JP4407471B2 (en) * | 2004-10-29 | 2010-02-03 | パナソニック株式会社 | Flexible wiring board, electronic device using the same, and manufacturing method thereof |
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| JP2011129759A (en) | 2011-06-30 |
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