JP5161789B2 - Solder flux creeping-up composition, electronic member for solder coated with the composition, method for soldering the member, and electrical product - Google Patents
Solder flux creeping-up composition, electronic member for solder coated with the composition, method for soldering the member, and electrical product Download PDFInfo
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- JP5161789B2 JP5161789B2 JP2008544088A JP2008544088A JP5161789B2 JP 5161789 B2 JP5161789 B2 JP 5161789B2 JP 2008544088 A JP2008544088 A JP 2008544088A JP 2008544088 A JP2008544088 A JP 2008544088A JP 5161789 B2 JP5161789 B2 JP 5161789B2
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3452—Solder masks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
- B23K35/3613—Polymers, e.g. resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
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- Microelectronics & Electronic Packaging (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、電気接点を有する電子部品またはプリント基板等の電子部材のはんだ付けの際に、はんだ用フラックスの這い上がりを防止するための前処理剤として用いられるフラックス這い上がり防止組成物に関する。また本発明は、該組成物から形成された被膜を有するはんだ用電子部品またはプリント基板などの電子部材、該組成物を用いるはんだ付け方法、さらに、はんだ付けされた上記電子部材を含む電気製品に関する。 The present invention relates to a flux creeping-up preventing composition used as a pretreatment agent for preventing solder flux from creeping up when an electronic component having electrical contacts or an electronic member such as a printed circuit board is soldered. The present invention also relates to an electronic component such as an electronic component for soldering or a printed board having a coating formed from the composition, a soldering method using the composition, and an electric product including the soldered electronic component. .
プリント基板に各種部品をはんだ付けしたり、ＩＣソケットにＩＣをはんだ付けする際には、予め、はんだの接着性を向上させるためのフラックス処理が施される。一般のフラックスは、溶媒中に酸性成分を含む腐食剤である。このため、コネクタ、スイッチ、ボリュ−ム、半固定抵抗等の電子部品の電気接点部分、またはプリント基板のはんだ付けが不要な部分などにフラックスが浸透あるいは付着することは望ましくなく、これを防ぐ必要がある。特に、電子部品のスルーホール部分などで起きる、フラックスが毛細管現象等により這い上がる「フラックスの這い上がり」と呼ばれる現象により、はんだ付けの不要な部分にまでフラックスが付着あるいは浸透し、腐食を起こすことを防ぐ必要がある。 When various components are soldered to the printed circuit board or the IC is soldered to the IC socket, a flux treatment for improving the adhesiveness of the solder is performed in advance. A general flux is a corrosive agent containing an acidic component in a solvent. For this reason, it is not desirable for flux to permeate or adhere to electrical contact parts of electronic parts such as connectors, switches, volumes, semi-fixed resistors, or parts that do not require soldering on printed circuit boards. There is. In particular, due to the phenomenon called "flux scooping up" that occurs in the through-hole part of electronic parts, etc., due to the capillary phenomenon, the flux adheres to or penetrates to parts that are not soldered, causing corrosion. Need to prevent.
このため、はんだ付けに先立って、フラックス這い上がりを防止するための前処理が行われている。この前処理に用いられるフラックス這い上がり防止剤は、通常、フラックスの溶媒に対し撥溶媒性のあるポリマ−を含む組成物である。従来、フラックスの溶媒は典型的にＩＰＡであることから、撥ＩＰＡ性がフラックス這い上がり防止性能の目安となる指標として使用されている。そのため、フラックス這い上がり防止剤の有効成分として、撥ＩＰＡ性の高い、ポリフルオロアルキル基含有重合体が使用されてきた。 For this reason, prior to soldering, pre-treatment for preventing flux creeping is performed. The flux creep-up preventing agent used in this pretreatment is usually a composition containing a polymer having a solvent repellency with respect to the flux solvent. Conventionally, since the flux solvent is typically IPA, IPA repellency has been used as an index of the flux creep-up prevention performance. Therefore, a polyfluoroalkyl group-containing polymer having high IPA repellency has been used as an active ingredient of the flux creeping-up preventing agent.
このような従来のフラックス這い上がり防止剤の重合体としては、下記式（ａ１１）で表されるポリフルオロアルキル基含有（メタ）アクリレ−トを用いた重合体が使用されている（特許文献１参照）。
ＣＨ２＝Ｃ（Ｒ11）ＯＣＯ−Ｑ11−Ｒf1 （ａ１１）
ただし、式中の記号は以下の意味を示す。
Ｒ11：水素原子またはメチル基
Ｑ11：２価連結基
Ｒf1：炭素数４〜１４のポリフルオロアルキル基
なお本明細書中、（メタ）アクリレ−トとは、アクリル酸エステルおよびメタクリル酸エステルの両方またはどちらか一方を表す。
CH 2 = C (R 11) OCO-Q 11 -R f1 (a11)
However, the symbols in the formulas have the following meanings.
R 11 : hydrogen atom or methyl group Q 11 : divalent linking group R f1 : polyfluoroalkyl group having 4 to 14 carbon atoms In this specification, (meth) acrylate means acrylic acid ester and methacrylic acid ester Represents either or both.
米国環境保護庁（ＵＳＥＰＡ）は、野生動物や人の血液を含め、種々の環境から検出されるパ−フロオロオクタン酸（ＰＦＯＡ）の安全性に関する予備リスク調査報告書を２００３年３月に公開した。さらに、２００６年１月には、ＰＦＯＡとその類縁物質、およびこれらの前駆体物質の環境中への排出削減と製品中の含有量削減計画への参加をフッ素樹脂メ−カ−等に提唱している。 US Environmental Protection Agency (USEPA) published preliminary risk study report on safety of perfluorooctanoic acid (PFOA) detected in various environments, including wild animals and human blood, in March 2003 did. Furthermore, in January 2006, PFOA and related substances, as well as participation in fluorocarbon resin manufacturers, etc., were proposed to participate in a plan to reduce the emissions of these precursor substances into the environment and their contents in products. ing.
パ−フルオロアルキル基の炭素数が６以下になると、生体および環境へのリスクが大きく低下する。しかしながら、重合体中のパ−フルオロアルキル基に起因する、疎水性、疎油性などの性能は、パ−フルオロアルキル基の炭素数が８以上であると高いが、炭素数が６以下であると著しく低下する。これは、炭素数が８以上のパ−フルオロアルキル基が結晶性を持つためと言われている。フラックス這い上がり防止剤の性能の指標として重要な撥ＩＰＡ性も、パ−フロオロアルキル基の炭素数が６以下になると、急激に低下する。 When the carbon number of the perfluoroalkyl group is 6 or less, the risk to the living body and the environment is greatly reduced. However, the performance such as hydrophobicity and oleophobicity caused by the perfluoroalkyl group in the polymer is high when the carbon number of the perfluoroalkyl group is 8 or more, but the number of carbons is 6 or less. It drops significantly. This is said to be because a perfluoroalkyl group having 8 or more carbon atoms has crystallinity. The IPA repellency, which is important as an index of the performance of the flux creep-up preventing agent, also decreases rapidly when the carbon number of the perfluoroalkyl group is 6 or less.
本発明は、生体および環境への影響が少ない炭素数が６以下のポリフルオロアルキル基を有する不飽和化合物から導かれる重合単位を含有する重合体であるが、従来のポリフルオロアルキル基の炭素数が８以上の不飽和化合物から導かれる重合単位を含有する重合体を含むフラックス這い上がり防止剤と同等の性能を有し、フラックス這い上がり防止性能が高い、はんだ用フラックス這い上がり防止組成物の提供を目的とする。 The present invention is a polymer containing a polymer unit derived from an unsaturated compound having a polyfluoroalkyl group having 6 or less carbon atoms, which has little influence on the living body and the environment. Of a flux scooping prevention composition for a solder having a performance equivalent to that of a flux scooping prevention agent comprising a polymer containing a polymer unit derived from an unsaturated compound having a molecular weight of 8 or more and having a high flux scooping prevention performance With the goal.
上記のような諸問題に鑑み、本発明は、生体および環境への影響が少ない炭素数が６以下のポリフルオロアルキル基を有する不飽和化合物から導かれる重合単位を含有する重合体であるが、該重合体中に、ウレタン結合を導入することによって、従来のポリフルオロアルキル基の炭素数が８以上の不飽和化合物から導かれる重合単位を含有する重合体を含むフラックス這い上がり防止剤と同等の性能を有するフラックス這い上がり防止剤の提供を可能とした。 In view of the above problems, the present invention is a polymer containing a polymer unit derived from an unsaturated compound having a polyfluoroalkyl group having 6 or less carbon atoms, which has little influence on the living body and the environment. By introducing a urethane bond into the polymer, the conventional polyfluoroalkyl group is equivalent to a flux creeping-up preventing agent containing a polymer containing a polymer unit derived from an unsaturated compound having 8 or more carbon atoms. It has become possible to provide a flux scooping prevention agent having performance.
本発明は、下記式（ａ）で表される不飽和化合物の少なくとも１種から導かれる重合単位を含有する重合体を含む、はんだ用フラックス這い上がり防止組成物である。本明細書においては、式（ａ）で表される化合物を化合物（ａ）と記し、他の式で表される化合物も同様に記す。
ただし、式中の記号は以下の意味を示す。
Ｒ１：水素原子またはメチル基
Ｑ１、Ｑ２：それぞれ独立して、単結合または２価の連結基
Ｒｆ：炭素−炭素原子間に挿入されたエ−テル性酸素原子を含んでいてもよい炭素数１〜６のポリフルオロアルキル基The present invention is a solder flux creeping-up composition comprising a polymer containing a polymer unit derived from at least one unsaturated compound represented by the following formula (a). In the present specification, the compound represented by the formula (a) is referred to as a compound (a), and the compounds represented by other formulas are also described in the same manner.
However, the symbols in the formulas have the following meanings.
R 1 : hydrogen atom or methyl group Q 1 , Q 2 : each independently a single bond or a divalent linking group R f : even if it contains an etheric oxygen atom inserted between carbon-carbon atoms Good C1-6 polyfluoroalkyl group
化合物（ａ）としては、Ｑ１が単結合または−Ｚ−（Ｙ）n−で表される２価の連結基（ただし、Ｚは単結合、−Ｏ−、または−ＮＨ−であり、Ｙは炭素数１〜６の直鎖アルキレン基、アミノ基、スルホニル基、またはこれらの組合せであり、ｎは０または１の整数を意味する。）であり、Ｑ２が単結合または炭素数１〜６の直鎖のアルキレン基であるものが好ましい。As the compound (a), Q 1 is a single bond or a divalent linking group represented by —Z— (Y) n — (wherein Z is a single bond, —O—, or —NH—, Is a straight-chain alkylene group having 1 to 6 carbon atoms, an amino group, a sulfonyl group, or a combination thereof, n is an integer of 0 or 1, and Q 2 is a single bond or 1 to 1 carbon atoms. Those having 6 linear alkylene groups are preferred.
化合物（ａ）としては、下記化合物（ａ１）が好ましい。
ただし、式中の記号は以下の意味を示す。
Ｒ１、Ｒｆ：前記と同じ
ｐ、ｑ：それぞれ独立して０〜６の整数As the compound (a), the following compound (a1) is preferable.
However, the symbols in the formulas have the following meanings.
R 1 , R f : same as above p, q: each independently an integer of 0-6
本発明の組成物は、重合体中の前記式（ａ）または（ａ１）で表される化合物から導かれる重合単位の割合が５０質量％以上であることが好ましい。 In the composition of the present invention, the proportion of the polymer units derived from the compound represented by the formula (a) or (a1) in the polymer is preferably 50% by mass or more.
また、本発明は、電子部材のはんだ付けする箇所の一部または全部に、上記いずれかの組成物からなる被膜を有し、はんだ用フラックス這い上がり防止性能を有する電子部材を含む。 Moreover, this invention includes the electronic member which has the film which consists of one of the said compositions in part or all of the location to which the electronic member is soldered, and has the flux climbing prevention performance for solder.
また、本発明は、電子部材のはんだ付けする箇所の一部または全部に、上記のいずれかの組成物からなる被膜を形成し、該被膜の一部または全部をはんだ用フラックスで塗布後、はんだ付けする、電子部材のはんだ付け方法を含み、該方法ではんだ付けされた電子部材を含む電気製品も含む。 The present invention also provides a method of forming a film made of any of the above-described compositions on a part or all of a part to be soldered of an electronic member, applying a part or all of the film with a soldering flux, And an electronic product including the electronic member soldered by the method.
本発明は、フラックス這い上がり防止組成物において、重合体中の炭素数が８以上のポリフルオロアルキル基の含有量を抑えて、生体および環境への安全性を確保するだけではなく、ポリフルオロアルキル基の鎖長の減少による這い上がり防止性能の低下を抑え、従来品と同程度の性能を維持することを可能にした。 The present invention provides a composition for preventing flux creep-up, not only by suppressing the content of polyfluoroalkyl groups having 8 or more carbon atoms in the polymer to ensure safety to living bodies and the environment, but also to polyfluoroalkyl. Suppression of the creeping prevention performance due to the decrease in the chain length of the group is suppressed, and it is possible to maintain the same level of performance as conventional products.
本発明のはんだ用フラックスの這い上がり防止組成物（「這い上がり防止剤」とも記す）は、被膜成分として、下記式（ａ）で表される不飽和化合物の少なくとも１種から導かれる重合単位を含有する重合体を含有する。
ただし、式中の記号は以下の意味を示す。
Ｒ１：水素原子またはメチル基
Ｑ１、Ｑ２：それぞれ独立して、単結合または２価の連結基
Ｒｆ：炭素−炭素原子間に挿入されたエ−テル性酸素原子を含んでいてもよい炭素数１〜６のポリフルオロアルキル基The composition for preventing creeping up of the solder flux of the present invention (also referred to as “scooping-up preventing agent”) has a polymer unit derived from at least one of unsaturated compounds represented by the following formula (a) as a film component. Contains the containing polymer.
However, the symbols in the formulas have the following meanings.
R 1 : hydrogen atom or methyl group Q 1 , Q 2 : each independently a single bond or a divalent linking group R f : even if it contains an etheric oxygen atom inserted between carbon-carbon atoms Good C1-6 polyfluoroalkyl group
ポリフルオロアルキル基は、アルキル基の水素原子の２個以上がフッ素原子に置換された基を意味し、このアルキル基の炭素−炭素結合間に挿入されたエ−テル性酸素原子を含むものであってもよい。
ポリフルオロアルキル基は、エーテル性酸素原子を含まない基であることが好ましい。
本明細書において、ポリフルオロアルキル基またはＲf基の表記は、炭素−炭素結合間に挿入されたエ−テル性酸素原子を含むポリフルオロアルキル基の上位概念にあたるものとして、特に断わりのない限り、該酸素原子を含まないおよび含む両方のポリフルオロアルキル基の総称を意味する。The polyfluoroalkyl group means a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms, and includes an etheric oxygen atom inserted between carbon-carbon bonds of the alkyl group. There may be.
The polyfluoroalkyl group is preferably a group not containing an etheric oxygen atom.
In the present specification, the notation of a polyfluoroalkyl group or R f group is a superordinate concept of a polyfluoroalkyl group containing an etheric oxygen atom inserted between carbon-carbon bonds, unless otherwise specified. And a generic term for both polyfluoroalkyl groups not containing and containing the oxygen atom.
上記ポリフルオロアルキル基（Ｒf基）は、炭素数１〜６のアルキル基に対応するフッ素置換数２以上の基であり、直鎖構造または分岐構造のいずれであってもよい。例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシルなどの直鎖または分岐構造のアルキル基に対応する部分フルオロ置換またはパ−フルオロ置換アルキル基などが挙げられる。分岐構造のポリフルオロアルキル基としては、イソプロピル基、３−メチルブチル基のパ−フルオロ置換アルキル基などが挙げられる。The polyfluoroalkyl group (R f group) is a group having 2 or more fluorine substituents corresponding to an alkyl group having 1 to 6 carbon atoms, and may have either a linear structure or a branched structure. Examples thereof include partially fluoro-substituted or perfluoro-substituted alkyl groups corresponding to linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and the like. Examples of the branched polyfluoroalkyl group include an isopropyl group and a perfluoro-substituted alkyl group of 3-methylbutyl group.
Ｒf基は直鎖構造または分岐構造のいずれであってもよいが、Ｒｆ基のパッキングを上げる観点からＲｆ基は直鎖構造が好ましい。同様の理由から、分岐構造である場合には、分岐部分がＲf基の末端部分に存在する場合が好ましい。
また、Ｒf基は、実質的に全フッ素置換されたパ−フルオロアルキル基が好ましく、特に主鎖の鎖長（側鎖を含まない炭素数）が１〜６のＲｆ基であることが好ましい。The R f group may have either a linear structure or a branched structure, but the R f group preferably has a linear structure from the viewpoint of increasing the packing of the R f group. For the same reason, in the case of a branched structure, it is preferable that the branched portion is present at the terminal portion of the R f group.
Further, the R f group is substantially all fluorine-substituted Pas - that fluoroalkyl group is preferable, the R f group with a chain length of the main chain (carbon number does not include the side chain) is 1 to 6 preferable.
式中のＱ１およびＱ２は単結合または２価の連結基である。Ｑ１が単結合の場合、Ｑ１の両端に存在するＣ（＝Ｏ）の炭素原子とＮ−Ｈの窒素原子とが直接結合することを意味する。同様に、Ｑ２が単結合の場合は、Ｑ２の両端に存在する酸素原子とＲｆの炭素原子とが直接結合することを意味する。Ｑ１およびＱ２は単結合または２価の連結基であれば適宜選択可能であり、これらに限定されるものではない。Q 1 and Q 2 in the formula are a single bond or a divalent linking group. When Q 1 is a single bond, it means that a carbon atom of C (═O) present at both ends of Q 1 and a nitrogen atom of N—H are directly bonded. Similarly, when Q 2 is a single bond, it means that the oxygen atoms present at both ends of Q 2 and the carbon atom of R f are directly bonded. Q 1 and Q 2 can be appropriately selected as long as they are a single bond or a divalent linking group, and are not limited thereto.
２価の連結基としては、−Ｏ−、−Ｓ−、−ＮＨ−、−ＳＯ２−、−ＰＯ２−、−ＣＨ＝ＣＨ−、−ＣＨ＝Ｎ−、−Ｎ＝Ｎ−、−Ｎ（Ｏ）＝Ｎ−、−ＣＯＯ−、−ＣＯＳ−、−ＣＯＮＨ−、−ＣＯＣＨ２−、−Ｏ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−、−ＣＨ２−、−ＣＨ２ＮＨ−、−ＣＨ２−、−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＣＯ−、直鎖状もしくは分岐状のアルキレン基またはアルケニレン基、アルキレンオキシ基、２価の４、５、６または７員環置換基、またそれらから構成される縮合置換基、６員環芳香族基、４ないし６員環の飽和または不飽和の脂肪族基、５または６員環複素環基、またはそれらの縮合環、これら２価の連結基の組合せから構成される基が挙げられる。Examples of the divalent linking group, -O -, - S -, - NH -, - SO 2 -, - PO 2 -, - CH = CH -, - CH = N -, - N = N -, - N (O) = N -, - COO -, - COS -, - CONH -, - COCH 2 -, - O-CH 2 CH 2 -, - CH 2 CH 2 -, - CH 2 -, - CH 2 NH- , —CH 2 —, —CO—, —CH═CH—COO—, —CH═CH—CO—, linear or branched alkylene group or alkenylene group, alkyleneoxy group, divalent 4, 5, 6- or 7-membered ring substituents, condensed substituents composed thereof, 6-membered aromatic groups, 4- to 6-membered saturated or unsaturated aliphatic groups, 5- or 6-membered heterocyclic groups, or Examples thereof include a group composed of a condensed ring thereof and a combination of these divalent linking groups.
上記の連結基は、置換基を有していてもよく、置換基の例としては、ハロゲン原子（Ｆ、Ｃｌ、Ｂｒ、Ｉ）、シアノ基、アルコキシ基（メトキシ、エトキシ、ブトキシ、オクチルオキシ、メトキシエトキシなど）、アリ−ロキシ基（フェノキシなど）、アルキルチオ基（メチルチオ、エチルチオなど）、アシル基（アセチル、プロピオニル、ベンゾイルなど）、スルホニル基（メタンスルホニル、ベンゼンスルホニルなど）、アシルオキシ基（アセトキシ、ベンゾイルオキシなど）、スルホニルオキシ基（メタンスルホニルオキシ、トルエンスルホニルオキシなど）、ホスホニル基（ジエチルホスホニルなど）、アミド基（アセチルアミノ、ベンゾイルアミノなど）、カルバモイル基（Ｎ，Ｎ−ジメチルカルバモイル、Ｎ−フェニルカルバモイルなど）、アルキル基（メチル、エチル、プロピル、イソプロピル、シクロプロピル、ブチル、２−カルボキシエチル、ベンジルなど）、アリ−ル基（フェニル、トルイルなど）、複素環基（ピリジル、イミダゾリル、フラニルなど）、アルケニル基（ビニル、１−プロペニルなど）、アルコキシアシルオキシ基（アセチルオキシ、ベンゾイルオキシなど）、アルコキシカルボニル基（メトキシカルボニル、エトキシカルボニルなど）、および重合性基（ビニル基、アクリロイル基、メタクロイル基、シリル基、桂皮酸残基など）などが挙げられる。 The linking group may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a cyano group, an alkoxy group (methoxy, ethoxy, butoxy, octyloxy, Methoxyethoxy), aryloxy groups (phenoxy, etc.), alkylthio groups (methylthio, ethylthio, etc.), acyl groups (acetyl, propionyl, benzoyl, etc.), sulfonyl groups (methanesulfonyl, benzenesulfonyl, etc.), acyloxy groups (acetoxy, Benzoyloxy etc.), sulfonyloxy groups (methanesulfonyloxy, toluenesulfonyloxy etc.), phosphonyl groups (diethylphosphonyl etc.), amide groups (acetylamino, benzoylamino etc.), carbamoyl groups (N, N-dimethylcarbamoyl, N -Phenylcarbamo ), Alkyl groups (methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, 2-carboxyethyl, benzyl, etc.), aryl groups (phenyl, toluyl, etc.), heterocyclic groups (pyridyl, imidazolyl, furanyl, etc.) ), Alkenyl groups (vinyl, 1-propenyl, etc.), alkoxyacyloxy groups (acetyloxy, benzoyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, etc.), and polymerizable groups (vinyl group, acryloyl group, methacryloyl group) , A silyl group, a cinnamic acid residue, etc.).
Ｑ１は、−Ｚ−（Ｙ）n−（Ｚは、単結合、−Ｏ−または−ＮＨ−であり、Ｙは炭素数１〜６のアルキレン基、アミノ基、スルホニル基、またはこれらの組合せから得られる２価の連結基、ｎは０または１の整数）で表される２価の連結基であることが好ましい。Ｑ２は、単結合または炭素数１〜６の直鎖のアルキレン基であることが好ましい。Q 1 is —Z— (Y) n — (Z is a single bond, —O— or —NH—, and Y is an alkylene group having 1 to 6 carbon atoms, an amino group, a sulfonyl group, or a combination thereof. It is preferable that it is a divalent linking group represented by the following formula: n is an integer of 0 or 1. Q 2 is preferably a single bond or a linear alkylene group having 1 to 6 carbon atoms.
好適な化合物（ａ）は、下記構造式（ａ１）で表されるものである。特にＲｆが炭素数１〜６の直鎖のパ−フルオロアルキル基（ＲＦ）である構造の化合物が好適である。
ただし、式中の記号は以下の意味を示す。
ｐ、ｑ：それぞれ独立して０〜６の整数
Ｒ１、Ｒｆ：前記と同じA suitable compound (a) is represented by the following structural formula (a1). In particular, a compound having a structure in which R f is a linear perfluoroalkyl group (R F ) having 1 to 6 carbon atoms is suitable.
However, the symbols in the formulas have the following meanings.
p, q: each independently an integer of 0-6 R 1 , R f : the same as above
具体的には、
ＣＨ２＝ＣＨ−ＣＯＯ−（ＣＨ２）２−ＮＨＣＯＯ−（ＣＨ２）２−Ｃ６Ｆ１３、
ＣＨ２＝Ｃ（ＣＨ３）−ＣＯＯ−（ＣＨ２）２−ＮＨＣＯＯ−（ＣＨ２）２−Ｃ６Ｆ１３
などが例示される。In particular,
CH 2 = CH-COO- (CH 2) 2 -NHCOO- (CH 2) 2 -C 6 F 13,
CH 2 = C (CH 3) -COO- (CH 2) 2 -NHCOO- (CH 2) 2 -C 6 F 13
Etc. are exemplified.
本発明に係る共重合体は、上記化合物（ａ）、好ましくは（ａ１）から導かれる単位の１種を含有するが、２種以上含有していてもよい。
また、重合体中の上記化合物（ａ）、好ましくは（ａ１）の全量から導かれる単位の含有量は、好ましくは５０質量％以上であり、より好ましくは８０質量％以上であり、さらに好ましくは実質１００質量％である。化合物（ａ）、好ましくは（ａ１）の含有量が上記範囲内であると、共重合体のフラックスの這い上がり防止性能が良好である。
なお、本発明に係る重合体において、各重合単位の含有量は、実質的に、重合仕込み量とみなすことができる。The copolymer according to the present invention contains one type of unit derived from the compound (a), preferably (a1), but may contain two or more types.
The content of the unit derived from the total amount of the compound (a), preferably (a1) in the polymer is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably. It is substantially 100% by mass. When the content of the compound (a), preferably (a1) is within the above range, the creeping-up performance of the copolymer flux is good.
In the polymer according to the present invention, the content of each polymerization unit can be substantially regarded as a polymerization charge amount.
本発明に係る重合体は、上記のような化合物（ａ）、好ましくは（ａ１）から導かれる単位とともに、これら以外の化合物（ｂ）から導かれる重合単位を１種または２種以上含んでいても構わない。化合物（ｂ）は、上記（ａ）または（ａ１）と共重合体を形成しうる他の化合物であれば特に限定されない。 The polymer according to the present invention contains one or more polymer units derived from the compound (a), preferably the unit derived from (a1) and the other compound (b). It doesn't matter. The compound (b) is not particularly limited as long as it is another compound capable of forming a copolymer with the above (a) or (a1).
化合物（ｂ）としては、例えば、重合性の不飽和基を有する化合物が挙げられる。具体的には、アクリル酸、メタクリル酸、（メタ）アクリルレ−ト等のポリオレフィン系不飽和エステル、ビニル基を有する化合物、ビニル基を有するシラン化合物、スチレン化合物、エポキシ基を有する不飽和エステル、アミノ基と重合性不飽和基を有する化合物、アクリル酸ジエステル等の（メタ）アクリル酸のポリエステル、および置換アミノ基と重合性不飽和基を有する化合物などが挙げられる。 Examples of the compound (b) include compounds having a polymerizable unsaturated group. Specifically, polyolefin unsaturated esters such as acrylic acid, methacrylic acid, (meth) acrylate, compounds having vinyl groups, silane compounds having vinyl groups, styrene compounds, unsaturated esters having epoxy groups, amino And a compound having a group and a polymerizable unsaturated group, a polyester of (meth) acrylic acid such as acrylic acid diester, and a compound having a substituted amino group and a polymerizable unsaturated group.
化合物（ｂ）の例１：下記式で表されるシラン化合物
ただし、式中の記号は下記の意味を示す。
Ｒ２：水素原子またはメチル基
Ｑ３：単結合または２価の連結基
Ｒ３、Ｒ４およびＲ５：それぞれ独立してヒドロキシ基または加水分解可能な官能基
ｓ：１〜３の整数
ｔ、ｕ：それぞれ独立して０または１の整数、ただし、（４−ｓ−ｔ−ｕ）は１以上Example of compound (b) 1: Silane compound represented by the following formula
However, the symbol in a formula shows the following meaning.
R 2 : hydrogen atom or methyl group Q 3 : single bond or divalent linking group R 3 , R 4 and R 5 : each independently a hydroxy group or a hydrolyzable functional group s: an integer t of 1 to 3, u: each independently an integer of 0 or 1, provided that (4-s-t-u) is 1 or more
Ｑ３の２価の連結基としては、前記Ｑ１、Ｑ２と同様のものが挙げられる。Ｑ３としては、単結合または−Ｚ２−（Ｙ２）ｎ−（Ｚは、単結合、−ＣＯＯ−または−ＣＯＮＨ−であり、Ｙ２は２価の連結基、ｎは０または１の整数）で表わされる２価の連結基であることが好ましい。好ましいＹ２としては、アルキレン基、アミノ基、スルホニル基、またはこれらの組み合わせから得られる２価の連結基が挙げられ、より好ましくは、Ｙ２が炭素数１〜６の直鎖のアルキレン基である。Examples of the divalent linking group for Q 3 include the same groups as those described above for Q 1 and Q 2 . Q 3 is a single bond or —Z 2 — (Y 2 ) n— (Z is a single bond, —COO— or —CONH—, Y 2 is a divalent linking group, and n is 0 or 1. It is preferably a divalent linking group represented by an integer). Preferred Y 2 includes an alkylene group, an amino group, a sulfonyl group, or a divalent linking group obtained from a combination thereof, and more preferably Y 2 is a linear alkylene group having 1 to 6 carbon atoms. is there.
Ｒ３、Ｒ４およびＲ５の加水分解可能な官能基としては、アルコキシ基、ハロゲン原子、アミノ基などが挙げられ、特にアルコキシ基が好ましい。アルコキシ基としては炭素数１〜５が好ましく、特に炭素数１〜３が好ましい。
（４−ｓ−ｔ−ｕ）は１が好ましい。Examples of the hydrolyzable functional group for R 3 , R 4 and R 5 include an alkoxy group, a halogen atom and an amino group, and an alkoxy group is particularly preferable. As an alkoxy group, C1-C5 is preferable and C1-C3 is especially preferable.
(4-s-t-u) is preferably 1.
化合物（ｂ）の例２：下記式で表されるスチレン化合物
ただし、式中の記号は下記の意味を示す。
Ｒ６：−Ｈ、−ＯＨ、−ＣＨ３、−Ｃｌ、−ＣＨＯ、−ＣＯＯＨ、−ＣＨ２ＯＨ、−ＣＨ２Ｃｌ、−ＣＨ２ＮＨ２、−ＣＨ２Ｎ(ＣＨ３)２、−ＣＨ２Ｎ(ＣＨ３)３Ｃｌ、−ＣＨ２ＮＨ３Ｃｌ、−ＣＨ２ＣＮ、−ＣＨ２ＣＯＯＨ、−ＣＨ２Ｎ（ＣＨ２ＣＯＯＨ）２、−ＣＨ２ＳＨ、−ＣＨ２ＳＯ３Ｎａ、−ＣＨ２ＯＣＯＣＨ３ Example 2 of compound (b): Styrene compound represented by the following formula
However, the symbol in a formula shows the following meaning.
R 6: -H, -OH, -CH 3, -Cl, -CHO, -COOH, -CH 2 OH, -CH 2 Cl, -CH 2 NH 2, -CH 2 N (CH 3) 2, -CH 2 N (CH 3 ) 3 Cl, —CH 2 NH 3 Cl, —CH 2 CN, —CH 2 COOH, —CH 2 N (CH 2 COOH) 2 , —CH 2 SH, —CH 2 SO 3 Na, — CH 2 OCOCH 3
化合物（ｂ）の例３：下記式で表される（メタ）アクリレ−ト
ただし、式中の記号は下記の意味を示す。
Ｒ７：水素原子またはメチル基
Ｒ８：−Ｈ、−ＣＨ３、−ＣＨ２ＣＨ２ＯＨ、−ＣＨ２ＣＨ２Ｎ(ＣＨ３)２、−(ＣＨ２)ｍＨ (ｍ＝２〜２０)、−ＣＨ２ＣＨ(ＣＨ３)２、−ＣＨ２−Ｃ(ＣＨ３)２−ＯＣＯ−Ｐｈ、−(ＣＨ２ＣＨ２Ｏ)ｍＨ(ｍ＝２〜２０)、−ＣＨ２Ｐｈ、−ＣＨ２ＣＨ２ＯＰｈ、−ＣＨ２Ｎ（ＣＨ３）３Ｃｌ、−ＣＨ２ＣＨ２Ｏ−ＰＯ（ＯＨ)２、−[Ｓｉ(ＣＨ３)２Ｏ］ｍＨ（ｍ＝２〜２０)、−(ＣＨ２ＣＨ２Ｏ)ｍＣＨ３(ｍ＝２〜２０)、−(ＣＨ２)２−ＮＣＯ、
However, the symbol in a formula shows the following meaning.
R 7 : hydrogen atom or methyl group R 8 : —H, —CH 3 , —CH 2 CH 2 OH, —CH 2 CH 2 N (CH 3 ) 2 , — (CH 2 ) m H (m = 2 to 20) ), - CH 2 CH (CH 3) 2, -CH 2 -C (CH 3) 2 -OCO-Ph, - (CH 2 CH 2 O) m H (m = 2~20), - CH 2 Ph, -CH 2 CH 2 OPh, -CH 2 N (CH 3) 3 Cl, -CH 2 CH 2 O-PO (OH) 2, - [Si (CH 3) 2 O] m H (m = 2~20) , - (CH 2 CH 2 O ) m CH 3 (m = 2~20), - (CH 2) 2 -NCO,
化合物（ｂ）の例４：下記式で表される化合物
ただし、式中の記号は下記の意味を示す。
Ｒ９：水素原子またはメチル基
Ｒ１０：−ＮＨＣＨ２ＯＨ、−ＮＨＣＨ２ＳＯ３Ｈ、−ＮＨＣ(ＣＨ３)２ＣＨ２−ＣＯ−ＣＨ３、−ＣｍＨ２ｍ＋１(ｍ＝２〜２０）、−ＮＨ２ Example 4 of compound (b): Compound represented by the following formula
However, the symbol in a formula shows the following meaning.
R 9 : hydrogen atom or methyl group R 10 : —NHCH 2 OH, —NHCH 2 SO 3 H, —NHC (CH 3 ) 2 CH 2 —CO—CH 3 , —C m H 2m + 1 (m = 2 to 20) , -NH 2
化合物（ｂ）の例５：下記式で表される化合物
化合物（ｂ）の例６：下記式で表される化合物
ただし、式中の記号は下記の意味を示す。
Ｒ１１：水素原子またはメチル基。Example 6 of compound (b): Compound represented by the following formula
However, the symbol in a formula shows the following meaning.
R 11 is a hydrogen atom or a methyl group.
化合物（ｂ）の例７：下記式で表される化合物
ただし、式中の記号は下記の意味を示す。
Ｒ１２：水素原子またはメチル基
Ｑ４：単結合または２価の連結基
Ｒｆ：炭素数１〜６のポリフルオロアルキル基Example 7 of Compound (b): Compound represented by the following formula
However, the symbol in a formula shows the following meaning.
R 12 : hydrogen atom or methyl group Q 4 : single bond or divalent linking group R f : polyfluoroalkyl group having 1 to 6 carbon atoms
Ｑ４の２価の連結基としては、前記Ｑ１、Ｑ２と同様のものが挙げられる。Ｑ４としては、−Ｚ３−（Ｙ３）n−（Ｚ３は、単結合、−Ｏ−または−ＮＨ−であり、Ｙ３は２価の連結基、ｎは０または１の整数）で表される２価の連結基であることが好ましい。好ましいＹ３の例としては、アルキレン基、アミノ基、スルホニル基、またはこれらの組合せから得られる２価の連結基が挙げられ、より好ましくは、Ｙ３が炭素数１〜６の直鎖のアルキレン基である。Examples of the divalent linking group for Q 4 include the same groups as those described above for Q 1 and Q 2 . As Q 4 , —Z 3 — (Y 3 ) n — (Z 3 is a single bond, —O— or —NH—, Y 3 is a divalent linking group, and n is an integer of 0 or 1) It is preferable that it is a bivalent coupling group represented by these. Examples of preferable Y 3 include a divalent linking group obtained from an alkylene group, an amino group, a sulfonyl group, or a combination thereof, and more preferably, Y 3 is a linear alkylene having 1 to 6 carbon atoms. It is a group.
化合物（ｂ）の例８：下記式で表される（メタ）アクリレ−ト
ただし、式中の記号は下記の意味を示す。
Ｒ１３：水素原子またはメチル基
Ｒ１４：有機基（ただし、ポリフルオロアルキル基を除く）
ｒ：１〜４の整数Example 8 of compound (b): (Meth) acrylate represented by the following formula
However, the symbol in a formula shows the following meaning.
R 13 : hydrogen atom or methyl group R 14 : organic group (excluding polyfluoroalkyl group)
r: an integer from 1 to 4
本発明の係る共重合体は、上記のような化合物（ｂ）から導かれる単位を、その種類によっても異なるが、５０質量％以下、好ましくは２０質量％以下の量で含むことができる。 The copolymer according to the present invention can contain units derived from the compound (b) as described above in an amount of 50% by mass or less, preferably 20% by mass or less, depending on the type.
本発明において、重合体の分子量が適度に大きければ、十分に這い上がり防止性能を発揮することができるが、一方、分子量が余りにも大きすぎると溶媒への溶解性が悪くなる。そのため、重合体の分子量は、重量平均分子量（Ｍｗ）で、通常、１×１０3〜１×１０7が好ましく、特に１×１０５〜１×１０６が好ましい。In the present invention, if the molecular weight of the polymer is moderately large, it is possible to exhibit a sufficient creeping prevention performance. On the other hand, if the molecular weight is too large, the solubility in a solvent becomes poor. Therefore, the molecular weight of the polymer is usually a weight average molecular weight (Mw), preferably 1 × 10 3 to 1 × 10 7 , particularly preferably 1 × 10 5 to 1 × 10 6 .
本発明に係る重合体は、上記のような化合物（ａ）と、付加的な化合物（ｂ）から導かれる単位を含む以外は、重合形態などについては特に制限されない。重合形態は、ランダム、ブロック、グラフトなどのいずれでもよく、特に制限されないが、通常、ランダム共重合体が好ましい。 The polymer according to the present invention is not particularly limited with respect to the polymerization form and the like except that it contains a unit derived from the compound (a) and the additional compound (b) as described above. The polymerization form may be any of random, block, graft and the like, and is not particularly limited, but usually a random copolymer is preferred.
その製造方法についても特に制限されないが、本発明では、通常、各化合物中の不飽和基に基づき付加重合させることができる。重合に際しては、公知の不飽和化合物の付加重合条件を適宜に採択して行うことができる。たとえば重合開始源としては、特に限定されないが、有機過酸化物、アゾ化合物、過硫酸塩等の通常の開始剤が利用できる。 The production method is not particularly limited, but in the present invention, addition polymerization can usually be performed based on an unsaturated group in each compound. The polymerization can be carried out by appropriately adopting known addition polymerization conditions for unsaturated compounds. For example, the polymerization initiation source is not particularly limited, and usual initiators such as organic peroxides, azo compounds and persulfates can be used.
本発明に係る重合体は、重合する際に、前記化合物（ａ）および前記化合物（ｂ）以外に、本発明の効果を損ねない範囲において、その他の成分を含有していても良い。例としては、重合開始剤はもちろんであるが、重合調整剤、重合触媒、反応性の染料や帯電防止剤等が挙げられる。
このようなその他の成分の重合体中における含有率は１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、１質量％以下であることがさらに好ましい。The polymer according to the present invention may contain other components in addition to the compound (a) and the compound (b) as long as the effects of the present invention are not impaired. Examples include polymerization initiators, polymerization regulators, polymerization catalysts, reactive dyes and antistatic agents as well as polymerization initiators.
The content of such other components in the polymer is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less.
上記重合体を含む本発明の組成物（這い上がり防止剤）は、通常、液状形態である。このため、共重合体を後述する溶媒を重合媒体とする溶液重合で製造し、重合により液状組成物を直接調製することは好ましい態様である。重合原料の化合物が、塩化ビニルなどのガスである場合には、圧力容器を用いて、加圧下に連続供給してもよい。 The composition of the present invention containing the above-mentioned polymer (creaking prevention agent) is usually in a liquid form. For this reason, it is a preferred embodiment that the copolymer is produced by solution polymerization using a solvent described later as a polymerization medium, and the liquid composition is directly prepared by polymerization. When the polymerization raw material compound is a gas such as vinyl chloride, it may be continuously supplied under pressure using a pressure vessel.
組成物を形成する溶媒は、重合体を溶解または分散できるものであればよく、特に限定されず、各種有機溶媒、水、またはこれらの混合媒体などが挙げられる。特にフッ素系溶媒に溶解しやすく、ハイドロクロロフルオロカ−ボン（ＨＣＦＣ）およびパ−フルロカ−ボン（ＰＦＣ）の使用も可能である。社会的環境問題を考慮すると、ハイドロフルオロカ−ボン（ＨＦＣ）またはハイドロフルオロエ−テル（ＨＦＥ）などが好ましい。使用可能なフッ素系溶媒の具体例を以下に示すが、これらに限定されるものではない。 The solvent for forming the composition is not particularly limited as long as it can dissolve or disperse the polymer, and examples thereof include various organic solvents, water, or a mixed medium thereof. In particular, it is easily dissolved in a fluorinated solvent, and hydrochlorofluorocarbon (HCFC) and perflurocarbon (PFC) can be used. In consideration of social environmental problems, hydrofluorocarbon (HFC) or hydrofluoroether (HFE) is preferred. Specific examples of usable fluorine-based solvents are shown below, but are not limited thereto.
ｍ−キシレンヘキサフルオリド（以下、ｍ−ＸＨＦと記す。）
ｐ−キシレンヘキサフルオリド（以下、p−ＸＨＦと記す。）
ＣＦ３ＣＨ２ＣＦ２ＣＨ３
ＣＦ３ＣＨ２ＣＦ２Ｈ
Ｃ６Ｆ１３ＯＣＨ３
Ｃ６Ｆ１３ＯＣ２Ｈ５
Ｃ３Ｆ７ＯＣＨ３
Ｃ２Ｆ７ＯＣ２Ｈ５
Ｃ６Ｆ１３Ｈ
ＣＦ２ＨＣＦ２ＣＨ２ＯＣＦ２ＣＦ２Ｈ
ＣＦ３ＣＦＨＣＦＨＣＦ２ＣＨ３
ＣＦ３(ＯＣＦ２ＣＦ２)n(ＯＣＦ２)mＯＣＦ２Ｈ
Ｃ３Ｆ１７ＯＣＨ３
Ｃ７Ｆ１５ＯＣＨ３
Ｃ４Ｆ９ＯＣＨ３
Ｃ４Ｆ９ＯＣ２Ｈ５
Ｃ４Ｆ９ＣＨ２ＣＨ３
ＣＦ２ＣＨ２ＯＣＦ２ＣＦ２ＣＦ２Ｈ
上記式中、ｍ、ｎはいずれも１〜２０を表す。m-xylene hexafluoride (hereinafter referred to as m-XHF)
p-Xylene hexafluoride (hereinafter referred to as p-XHF)
CF 3 CH 2 CF 2 CH 3
CF 3 CH 2 CF 2 H
C 6 F 13 OCH 3
C 6 F 13 OC 2 H 5
C 3 F 7 OCH 3
C 2 F 7 OC 2 H 5
C 6 F 13 H
CF 2 HCF 2 CH 2 OCF 2 CF 2 H
CF 3 CFHCHFHCF 2 CH 3
CF 3 (OCF 2 CF 2 ) n (OCF 2 ) m OCF 2 H
C 3 F 17 OCH 3
C 7 F 15 OCH 3
C 4 F 9 OCH 3
C 4 F 9 OC 2 H 5
C 4 F 9 CH 2 CH 3
CF 2 CH 2 OCF 2 CF 2 CF 2 H
In the above formula, m and n both represent 1-20.
本発明の這い上がり防止剤は、通常、上記重合体を好ましくは０．０１〜２０質量％、より好ましくは０．０５〜５質量％の濃度で含む。重合体の濃度がこの範囲内であれば、這い上がり防止性能を十分に発揮でき、組成物の安定性も良好である。なお這い上がり防止剤の上記重合体濃度は、最終的濃度であればよく、例えば這い上がり防止剤を重合組成物として直接調製する場合には、重合直後の重合体組成物の重合体濃度（固形分濃度）が２０質量％を超えていてもなんら差し支えない。高濃度の重合組成物は、最終的に上記好ましい濃度となるように適宜に希釈することができる。 The anti-cracking agent of the present invention usually contains the above polymer in a concentration of preferably 0.01 to 20% by mass, more preferably 0.05 to 5% by mass. If the concentration of the polymer is within this range, the creeping prevention performance can be sufficiently exhibited, and the stability of the composition is also good. The polymer concentration of the scooping inhibitor may be a final concentration. For example, when the scooping inhibitor is directly prepared as a polymerization composition, the polymer concentration of the polymer composition immediately after polymerization (solid The partial concentration) may exceed 20% by mass. The high-concentration polymerization composition can be appropriately diluted so that the final desired concentration is obtained.
本発明の這い上がり防止剤は、組成物の安定性、フラックス這い上がり防止性能または外観等に悪影響を与えない範囲であれば、前記した以外の他の成分を含んでいてもよい。このような他の成分としては、例えば被膜表面の腐食を防止するためのｐＨ調整剤、防錆剤、組成物を希釈して使用する場合に液中の重合体の濃度管理をする目的や未処理部品との区別をするための染料、染料の安定剤、難燃剤、消泡剤、または帯電防止剤等が挙げられる。また、同様に、例えば化合物（ａ）を含有しない化合物（ｂ）の共重合体を併有しても良い。 The creep-up preventing agent of the present invention may contain other components than those described above as long as they do not adversely affect the stability of the composition, the flux creep-up preventing performance or the appearance. Such other components include, for example, pH control agents, rust preventives for preventing corrosion of the coating surface, and the purpose of controlling the concentration of the polymer in the liquid when the composition is used diluted. Examples thereof include dyes for distinguishing them from treated parts, dye stabilizers, flame retardants, antifoaming agents, and antistatic agents. Similarly, for example, a copolymer of compound (b) not containing compound (a) may be included.
本発明では、電子部材の表面のはんだ付けする箇所の一部または全部に、上記のような這い上がり防止剤の被膜を形成し、該被膜の一部または全部をはんだ用フラックスで処理した後、はんだ付けする、電子部材のはんだ付け方法が提供される。この際には、這い上がり防止剤を目的および用途に応じて、任意の濃度に希釈し、電子部材に被覆することができる。被覆方法としては、一般的な被覆加工方法が採用できる。例えば、浸漬塗布、スプレ−塗布、または本発明の組成物を充填したエアゾ−ル缶による塗布等の方法がある。 In the present invention, a coating film of the scooping-up preventing agent as described above is formed on a part or all of the soldering portion of the surface of the electronic member, and after treating a part or all of the coating film with a soldering flux, An electronic member soldering method for soldering is provided. In this case, the scooping-up preventing agent can be diluted to an arbitrary concentration according to the purpose and application and coated on the electronic member. As a coating method, a general coating method can be employed. For example, there are methods such as dip coating, spray coating, and coating with an aerosol can filled with the composition of the present invention.
電子部材としては、具体的に、コネクタ、スイッチ、ボリュ−ム、または半固定抵抗等の電気接点を有する電子部品、電気接点を有するプリント基板などが挙げられる。本発明の這い上がり防止剤で被覆される箇所としては、プリント基板にコネクタ等の電子部品をはんだ付けする際に、フラックスの這い上がりが起こりうる箇所が挙げられる。より詳しくは、プリント基板に取り付けるコネクタ等の電子部品の付け根部分、プリント基板の電子部品本体が実装される側の基板表面、または電子部品を取り付けるためのプリント基板に設けられたスル−ホ−ル等が挙げられる。また、電子部品またはプリント基板の表面全体に被覆してもよく、上記以外の被覆方法も採用できる。例えば、被覆効率のよい全浸漬または半浸漬による方法も採用できる。 Specific examples of the electronic member include a connector, a switch, a volume, an electronic component having an electrical contact such as a semi-fixed resistor, and a printed circuit board having an electrical contact. Examples of the location covered with the scooping preventive agent of the present invention include a location where a flux scooping may occur when an electronic component such as a connector is soldered to a printed circuit board. More specifically, a base portion of an electronic component such as a connector attached to the printed circuit board, a surface of the printed circuit board on which the electronic component main body is mounted, or a through hole provided on the printed circuit board for attaching the electronic component. Etc. Moreover, you may coat | cover the whole surface of an electronic component or a printed circuit board, and can also employ | adopt coating methods other than the above. For example, a method of full immersion or semi-immersion with good coating efficiency can be employed.
這い上がり防止剤塗布後は、溶媒の沸点以上の温度で乾燥を行うことがより好ましい。無論、被処理部品の材質などにより、加熱乾燥が困難な場合には、加熱を回避して乾燥すべきである。なお、加熱条件は、塗布する組成物の組成や、塗布面積等に応じて選択すればよい。 It is more preferable to perform drying at a temperature equal to or higher than the boiling point of the solvent after the scooping-up preventing agent is applied. Of course, when heating and drying are difficult due to the material of the parts to be processed, etc., heating should be avoided to dry. In addition, what is necessary is just to select heating conditions according to the composition of the composition to apply | coat, an application area, etc.
本発明の這い上がり防止剤は、電子部品またはプリント基板の表面に被膜を形成させ、はんだ用フラックスの這い上がりを防止する。したがって本発明により、フラックスによる腐食が防止された電子部品またはプリント基板が提供される。 The scooping preventive agent of the present invention forms a film on the surface of an electronic component or a printed circuit board and prevents scooping of the solder flux. Therefore, the present invention provides an electronic component or a printed circuit board in which corrosion due to flux is prevented.
上記により被膜（乾燥）が表面に形成された電子部品またはプリント基板は、次にはんだ用フラックスで処理され、その後、はんだ付けが行われる。はんだ付けの方法は特に制限されることなく、従来公知の方法に従って実施される。
フラックス及びはんだの種類についても、特に制限されることはなく、電子部品のはんだ付けに常用されているものが使用可能である。The electronic component or printed circuit board on which the coating (dried) is formed as described above is then treated with a soldering flux, and then soldered. The soldering method is not particularly limited, and is performed according to a conventionally known method.
The types of flux and solder are not particularly limited, and those commonly used for soldering electronic components can be used.
そして該電子部品またはプリント基板は種々の電気製品の材料として用いられる。該電気製品は、フラックスによる腐食が原因で起こる障害が防止された、優れた品質の電気製品である。該電気製品の具体例としては、コンピュ−タ用機器、テレビ、オ−ディオ用機器（ラジオカセット、コンパクトディスク、ミニディスク）等に用いられる機器用、携帯電話などが挙げられる。 The electronic component or printed circuit board is used as a material for various electric products. The electrical product is an excellent quality electrical product in which a failure caused by corrosion due to flux is prevented. Specific examples of the electrical products include devices for computers, televisions, audio devices (radio cassettes, compact discs, minidiscs), mobile phones, and the like.
以下に本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、特に断わりのない限り、以下の実施例の記載において「％」で表示されるものは「質量％」を表すものとする。 The present invention will be specifically described below, but the present invention is not limited to the following examples. Unless otherwise specified, what is indicated by “%” in the description of the following examples represents “mass%”.
〔不飽和化合物の合成・調達〕
［ウレタン結合とポリフルオロアルキル基を有する不飽和化合物１の合成］
フラスコに、メタキシレンヘキサフロオリド（ｍ−ＸＨＦ）を４１.８ｇ、２−（パ−フルオロヘキシル）エタノ−ル（純度９８.９％）を１２.９ｇ、トリエチレンジアミンを０.０４ｇ、フェノチアジンを１ｍｇ加え、よく攪拌した。そこに、２−イソシアナトエチルアクリレ−ト（純度９９.７％）を５.０ｇ滴下した。滴下後、４０℃で一晩反応させた（転化率９７.５％）。得られた溶液を０.５μｍのフィルタ−で加圧濾過して、表１に示す構造の化合物１の３０質量％のｍ−ＸＨＦ溶液を得た。[Synthesis and procurement of unsaturated compounds]
[Synthesis of unsaturated compound 1 having urethane bond and polyfluoroalkyl group]
Into the flask, 41.8 g of metaxylene hexafluoride (m-XHF), 12.9 g of 2- (perfluorohexyl) ethanol (purity 98.9%), 0.04 g of triethylenediamine, 0.04 g of phenothiazine 1 mg was added and stirred well. Thereto was dropped 5.0 g of 2-isocyanatoethyl acrylate (purity 99.7%). After dripping, it was made to react at 40 degreeC overnight (conversion rate 97.5%). The obtained solution was pressure filtered through a 0.5 μm filter to obtain a 30% by mass m-XHF solution of the compound 1 having the structure shown in Table 1.
［ウレタン結合とポリフルオロアルキル基を有する不飽和化合物２の合成］
フラスコに、ｍ−ＸＨＦを３９.０ｇ、２−（パ−フルオロヘキシル）エタノ−ル（純度９８.９％）を１１.７ｇ、トリエチレンジアミンを０.０４０ｇ、およびフェノチアジンを１ｍｇ加え、よく攪拌した。そこに、２−イソシアナトエチルメタクリレ−ト（純度９９.４％）を５.０ｇ滴下した。４０℃で一晩反応させた（転化率９７.５％）。得られた溶液を０.５μｍのフィルタ−で加圧濾過して、表１に示す構造の化合物２の３０質量％のｍ−ＸＨＦ溶液を得た。[Synthesis of unsaturated compound 2 having urethane bond and polyfluoroalkyl group]
To the flask, 39.0 g of m-XHF, 11.7 g of 2- (perfluorohexyl) ethanol (purity 98.9%), 0.040 g of triethylenediamine, and 1 mg of phenothiazine were added and stirred well. . Thereto was dropped 5.0 g of 2-isocyanatoethyl methacrylate (purity 99.4%). The reaction was carried out overnight at 40 ° C. (conversion 97.5%). The obtained solution was pressure filtered through a 0.5 μm filter to obtain a 30% by mass m-XHF solution of the compound 2 having the structure shown in Table 1.
［ポリフルオロアルキル基を有する不飽和化合物（比較化合物１）の合成］
２−（パ−フルオロヘキシル）エタノ−ル（純度９８.９％）を２００.２ｇ、アクリル酸を４５.５、シクロヘキサン８０.１ｇ、およびパラトルエンスルホン酸・一水和物を５.２ｇ加え、８０℃で８時間反応（脱水留去）を行った。その後、中和と水洗を行った後、蒸留で表１に示す構造の比較化合物１（純度９９.４％）を得た。[Synthesis of unsaturated compound having polyfluoroalkyl group (Comparative Compound 1)]
Add 20.2 g of 2- (perfluorohexyl) ethanol (purity 98.9%), 45.5 g of acrylic acid, 80.1 g of cyclohexane, and 5.2 g of paratoluenesulfonic acid monohydrate. The reaction (dehydration distillation) was performed at 80 ° C. for 8 hours. Then, after neutralizing and washing with water, the comparative compound 1 (purity 99.4%) having the structure shown in Table 1 was obtained by distillation.
［ポリフルオロアルキル基を有する不飽和化合物（比較化合物２）の調達］
表１に示す構造の比較化合物２（比較化合物１のアクリル酸がメタクリル酸に変ったもの）を市場から入手した。純度は９９.８％であった。[Procurement of unsaturated compounds having a polyfluoroalkyl group (Comparative Compound 2)]
Comparative compound 2 having a structure shown in Table 1 (comparative compound 1 in which acrylic acid was changed to methacrylic acid) was obtained from the market. The purity was 99.8%.
〔重合体組成物の調製〕
［重合体組成物１、２の調製］
密閉容器に、化合物１または２を１００質量部、開始剤Ｖ−６０１［和光純薬工業（株）製］を１質量部、および溶剤としてｍ−ＸＨＦを３９９質量部、それぞれ仕込み、７０℃で２６時間反応を行い、重合体１または２を含む、重合体組成物１または２を得た。(Preparation of polymer composition)
[Preparation of polymer compositions 1 and 2]
In a sealed container, 100 parts by mass of Compound 1 or 2; 1 part by mass of initiator V-601 [manufactured by Wako Pure Chemical Industries, Ltd.]; and 399 parts by mass of m-XHF as a solvent were charged at 70 ° C. The reaction was performed for 26 hours to obtain a polymer composition 1 or 2 containing the polymer 1 or 2.
［比較重合体組成物１、２の調製］
密閉容器に、比較化合物１または２を１００質量部、開始剤Ｖ−６０１［和光純薬工業（株）製］を１質量部、および溶剤としてｍ−ＸＨＦを３９９質量部）、それぞれ仕込み、７０℃で２６時間反応を行い、比較重合体１または２を含む、比較重合体組成物１または２を得た。[Preparation of Comparative Polymer Compositions 1 and 2]
In a sealed container, 100 parts by mass of Comparative Compound 1 or 2, 1 part by mass of initiator V-601 [manufactured by Wako Pure Chemical Industries, Ltd.], and 399 parts by mass of m-XHF as a solvent) were charged, respectively. The reaction was carried out at 26 ° C. for 26 hours to obtain a comparative polymer composition 1 or 2 containing the comparative polymer 1 or 2.
［実施例１〜２、比較例１〜２］
[防止組成物の調製]
重合体組成物１および２、ならびに、比較重合体組成物１および２をそれぞれ１ｇ採取し、１１０℃で２時間乾燥させた後、固形分を秤量して固形分（重合体）濃度（質量％）を求めた。その後、ｍ−ＸＨＦを用いて重合組成物１および２、ならびに、比較重合体組成物１および２の固形分濃度の各々が０.１質量％になるように希釈し、フラックス這い上がり防止組成物１および２、ならびに、比較防止組成物１および２を得た。[Examples 1-2, Comparative Examples 1-2]
[Preparation of prevention composition]
1 g of each of the polymer compositions 1 and 2 and the comparative polymer compositions 1 and 2 was collected and dried at 110 ° C. for 2 hours, and then the solid content was weighed to determine the solid content (polymer) concentration (mass%). ) Thereafter, using m-XHF, the polymer compositions 1 and 2 and the comparative polymer compositions 1 and 2 are each diluted so that the solid content concentration is 0.1% by mass, and the flux scooping-up preventing composition 1 and 2 and comparative prevention compositions 1 and 2 were obtained.
［接触角の測定］
ガラス板を防止剤組成物１および２、ならびに、比較防止剤組成物１および２の各々に、常温で１分間浸漬後、取出し、１１０℃で５分間乾燥して、這い上がり防止剤の被膜を有するガラス板を得た。
該ガラス板に、２−プロパノ−ル（ＩＰＡ）を滴下して接触角の測定を行った。結果を表３に示した。接触角の測定には、液滴式投影型接触角計［協和界面科学（株）製］を用いた。[Measurement of contact angle]
The glass plate is immersed in each of the inhibitor compositions 1 and 2 and the comparative inhibitor compositions 1 and 2 at room temperature for 1 minute, then taken out and dried at 110 ° C. for 5 minutes to form a scooping inhibitor film. A glass plate was obtained.
2-propanol (IPA) was dropped onto the glass plate, and the contact angle was measured. The results are shown in Table 3. For the measurement of the contact angle, a drop-type projection contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) was used.
上記のように、本発明の組成物は、ＩＰＡの接触角が大きく、高い撥ＩＰＡ性を有する。これから、フラックス這い上がり防止剤としての高い性能を有するものと考えられる。 As described above, the composition of the present invention has a large IPA contact angle and high IPA repellency. From this, it is thought that it has the high performance as a flux creeping-up prevention agent.
Claims (7)
Ｒ１：水素原子またはメチル基
Ｑ１、Ｑ２：それぞれ独立して、単結合または２価の連結基
Ｒｆ：炭素−炭素原子間に挿入されたエ−テル性酸素原子を含んでいてもよい炭素数１〜６のポリフルオロアルキル基A solder flux creeping-up composition comprising a polymer containing a polymer unit derived from at least one unsaturated compound represented by the following formula (a).
R 1 : hydrogen atom or methyl group Q 1 , Q 2 : each independently a single bond or a divalent linking group R f : even if it contains an etheric oxygen atom inserted between carbon-carbon atoms Good C1-6 polyfluoroalkyl group
Ｒ１、Ｒｆ：前記と同じ
ｐ、ｑ：それぞれ独立して０〜６の整数The composition according to claim 1 or 2, wherein the compound represented by the formula (a) is an unsaturated compound represented by the following formula (a1).
R 1 , R f : same as above p, q: each independently an integer of 0-6
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008544088A JP5161789B2 (en) | 2006-11-17 | 2007-09-13 | Solder flux creeping-up composition, electronic member for solder coated with the composition, method for soldering the member, and electrical product |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006311641 | 2006-11-17 | ||
| JP2006311641 | 2006-11-17 | ||
| PCT/JP2007/067823 WO2008059654A1 (en) | 2006-11-17 | 2007-09-13 | Composition for preventing solder flux scrambling, electronic member for soldering coated with the composition, method of soldering the member, and electrical product |
| JP2008544088A JP5161789B2 (en) | 2006-11-17 | 2007-09-13 | Solder flux creeping-up composition, electronic member for solder coated with the composition, method for soldering the member, and electrical product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2008059654A1 JPWO2008059654A1 (en) | 2010-02-25 |
| JP5161789B2 true JP5161789B2 (en) | 2013-03-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008544088A Expired - Fee Related JP5161789B2 (en) | 2006-11-17 | 2007-09-13 | Solder flux creeping-up composition, electronic member for solder coated with the composition, method for soldering the member, and electrical product |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5161789B2 (en) |
| CN (1) | CN101541471A (en) |
| TW (1) | TW200843892A (en) |
| WO (1) | WO2008059654A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102751093B (en) | 2008-12-26 | 2015-07-08 | 株式会社村田制作所 | Method for manufacturing ceramic electronic component and ceramic electronic component |
| US9000110B2 (en) | 2009-08-20 | 2015-04-07 | Agc Seimi Chemical Co., Ltd. | Fluoroalkyl group-containing n-substituted (meth)acrylamide compound, polymer thereof, and use thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6010694A (en) * | 1983-06-30 | 1985-01-19 | 石井 銀弥 | Method of soldering printed circuit board |
| JPS6049859A (en) * | 1983-08-30 | 1985-03-19 | Asahi Glass Co Ltd | Agent for preventing creeping up of flux for soldering |
| JPH07201501A (en) * | 1993-12-28 | 1995-08-04 | Dainippon Ink & Chem Inc | Method of preventing penetration of flux into electronic component |
| JPH1098253A (en) * | 1996-09-24 | 1998-04-14 | Nof Corp | Diffusion preventing agent for soldering flux |
| JPH11154783A (en) * | 1997-09-16 | 1999-06-08 | Seimi Chem Co Ltd | Composition for preventing creeping up of flux for soldering |
| JP2001135926A (en) * | 1999-11-02 | 2001-05-18 | Seimi Chem Co Ltd | Solder flux creep-up preventing agent composition, and application thereof |
-
2007
- 2007-09-13 WO PCT/JP2007/067823 patent/WO2008059654A1/en active Application Filing
- 2007-09-13 CN CNA2007800427414A patent/CN101541471A/en active Pending
- 2007-09-13 JP JP2008544088A patent/JP5161789B2/en not_active Expired - Fee Related
- 2007-11-13 TW TW96142876A patent/TW200843892A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6010694A (en) * | 1983-06-30 | 1985-01-19 | 石井 銀弥 | Method of soldering printed circuit board |
| JPS6049859A (en) * | 1983-08-30 | 1985-03-19 | Asahi Glass Co Ltd | Agent for preventing creeping up of flux for soldering |
| JPH07201501A (en) * | 1993-12-28 | 1995-08-04 | Dainippon Ink & Chem Inc | Method of preventing penetration of flux into electronic component |
| JPH1098253A (en) * | 1996-09-24 | 1998-04-14 | Nof Corp | Diffusion preventing agent for soldering flux |
| JPH11154783A (en) * | 1997-09-16 | 1999-06-08 | Seimi Chem Co Ltd | Composition for preventing creeping up of flux for soldering |
| JP2001135926A (en) * | 1999-11-02 | 2001-05-18 | Seimi Chem Co Ltd | Solder flux creep-up preventing agent composition, and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101541471A (en) | 2009-09-23 |
| TW200843892A (en) | 2008-11-16 |
| WO2008059654A1 (en) | 2008-05-22 |
| JPWO2008059654A1 (en) | 2010-02-25 |
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