JP5161789B2 - Solder flux creeping-up composition, electronic member for solder coated with the composition, method for soldering the member, and electrical product - Google Patents

Description

  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. .

  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.

  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.

As a polymer of such a conventional flux creeping-up preventing agent, a polymer using a polyfluoroalkyl group-containing (meth) acrylate represented by the following formula (a11) is used (Patent Document 1). reference).
^{_{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.
JP-A-10-303536

  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.

  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.

  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.

  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.

ただし、式中の記号は以下の意味を示す。
Ｒ^１：水素原子またはメチル基
Ｑ^１、Ｑ^２：それぞれ独立して、単結合または２価の連結基
Ｒ^ｆ：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

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.

ただし、式中の記号は以下の意味を示す。
Ｒ^１、Ｒ^ｆ：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

  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.

  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.

  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.

  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.

ただし、式中の記号は以下の意味を示す。
Ｒ^１：水素原子またはメチル基
Ｑ^１、Ｑ^２：それぞれ独立して、単結合または２価の連結基
Ｒ^ｆ：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

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.

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.

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.

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.

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.

  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.).

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.

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
Ｒ^１、Ｒ^ｆ：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

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.

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.

  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).

  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.

ただし、式中の記号は下記の意味を示す。
Ｒ^２：水素原子またはメチル基
Ｑ^３：単結合または２価の連結基
Ｒ^３、Ｒ^４およびＲ^５：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

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.

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.

ただし、式中の記号は下記の意味を示す。
Ｒ^６：−Ｈ、−ＯＨ、−ＣＨ_３、−Ｃｌ、−ＣＨＯ、−ＣＯＯＨ、−ＣＨ_２ＯＨ、−ＣＨ_２Ｃｌ、−ＣＨ_２ＮＨ_２、−ＣＨ_２Ｎ(ＣＨ_３)_２、−ＣＨ_２Ｎ(ＣＨ_３)_３Ｃｌ、−ＣＨ_２ＮＨ_３Ｃｌ、−ＣＨ_２ＣＮ、−ＣＨ_２ＣＯＯＨ、−ＣＨ_２Ｎ（ＣＨ_２ＣＯＯＨ）_２、−ＣＨ_２ＳＨ、−ＣＨ_２ＳＯ_３Ｎａ、−ＣＨ_２ＯＣＯＣＨ_３ 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

ただし、式中の記号は下記の意味を示す。
Ｒ^７：水素原子またはメチル基
Ｒ^８：−Ｈ、−ＣＨ_３、−ＣＨ_２ＣＨ_２ＯＨ、−ＣＨ_２ＣＨ_２Ｎ(ＣＨ_３)_２、−(ＣＨ_２)_ｍＨ (ｍ＝２〜２０)、−ＣＨ_２ＣＨ(ＣＨ_３)_２、−ＣＨ_２−Ｃ(ＣＨ_３)_２−ＯＣＯ−Ｐｈ、−(ＣＨ_２ＣＨ_２Ｏ)_ｍＨ(ｍ＝２〜２０)、−ＣＨ_２Ｐｈ、−ＣＨ_２ＣＨ_２ＯＰｈ、−ＣＨ_２Ｎ（ＣＨ_３）_３Ｃｌ、−ＣＨ_２ＣＨ_２Ｏ−ＰＯ（ＯＨ)_２、−[Ｓｉ(ＣＨ_３)_２Ｏ］_ｍＨ（ｍ＝２〜２０)、−(ＣＨ_２ＣＨ_２Ｏ)_ｍＣＨ_３(ｍ＝２〜２０)、−(ＣＨ_２)_２−ＮＣＯ、

Example 3 of Compound (b): (Meth) acrylate represented by the following formula

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,

ただし、式中の記号は下記の意味を示す。
Ｒ^９：水素原子またはメチル基
Ｒ^１０：−ＮＨＣＨ_２ＯＨ、−ＮＨＣＨ_２ＳＯ_３Ｈ、−ＮＨＣ(ＣＨ_３)_２ＣＨ_２−ＣＯ−ＣＨ_３、−Ｃ_ｍＨ_２ｍ＋１(ｍ＝２〜２０）、−ＮＨ_２ 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

Example 5 of compound (b): Compound represented by the following formula

ただし、式中の記号は下記の意味を示す。
Ｒ^１１：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.

ただし、式中の記号は下記の意味を示す。
Ｒ^１２：水素原子またはメチル基
Ｑ^４：単結合または２価の連結基
Ｒ^ｆ：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

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.

ただし、式中の記号は下記の意味を示す。
Ｒ^１３：水素原子またはメチル基
Ｒ^１４：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

  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.

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 .

  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.

  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.

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.

  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.

  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-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.

  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.

  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.

  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.

  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.

  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.

  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.

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.

  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.

  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%”.

[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.

[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.

[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.

[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%.

(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.

[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.

[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.

[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.

  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)

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).

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 In the compound represented by the formula (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 And Y is a linear alkylene group having 1 to 6 carbon atoms, an amino group, a sulfonyl group, or a combination thereof, and n is an integer of 0 or 1, and Q ² is a single bond. Or the composition of Claim 1 which is a C1-C6 linear alkylene group. 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).

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   The composition according to any one of claims 1 to 3, wherein a proportion of polymerized units derived from the unsaturated compound represented by the formula (a) or the formula (a1) in the polymer is 50% by mass or more.   The electronic member which has the film which consists of a composition in any one of Claims 1-4 in the soldering location of an electronic member, and has the flux climbing prevention performance for solder.   The solder of the electronic member which solders after forming the film which consists of a composition in any one of Claims 1-4 in the location to solder of an electronic member, apply | coating the flux for solder on this film Attaching method.   An electrical product comprising an electronic member soldered by the method of claim 6.