CN101389443B - Anti-flux migration composition for solder - Google Patents
Anti-flux migration composition for solder Download PDFInfo
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- CN101389443B CN101389443B CN2007800065678A CN200780006567A CN101389443B CN 101389443 B CN101389443 B CN 101389443B CN 2007800065678 A CN2007800065678 A CN 2007800065678A CN 200780006567 A CN200780006567 A CN 200780006567A CN 101389443 B CN101389443 B CN 101389443B
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—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
- H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces
-
- 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
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
The object is to provide a composition which has a high anti-flux migration effect and is applicable to a solder to be mounted on a surface. Disclosed is an anti-flux migration composition for a solder, which comprises a copolymer having a unit derived from at least one unsaturated compound having a polyfluoroalkyl group and represented by the formula (a) and a unit derived from at least one silane-containing (meth)acrylate represented by the formula (b); and (b) wherein Q represents a single bond or a bivalent linking group; R<1> represents a hydrogen atom or a methyl group; R<f> represents a polyfluoroalkyl group which may have an etheric oxygen atom inserted between a carbon-carbon bonding; R<2> represents a hydroxyl group or a hydrolysable functional group; R<3> and R<4> independently represent a hydrogen atom, a saturated alkyl group having 1 to 4 carbon atoms, or a phenyl group; n represents an integer of 1 to 3; and m and l independently represent an integer of 0 or 1, provided that the number represented by the formula (4-n-m) is 1 or greater.
Description
Technical field
Be used as Ga り on the ( い that swashes that is used to prevent solder flux when the present invention relates to have the soldering of electronic components such as the electronic unit of electric terminal or printed base plate) the pretreating agent anti-flux migration composition.In addition; The scolding tin that the present invention relates to have the tunicle that forms by said composition with electronic components such as electronic unit or printed base plates, use the soldering method of said composition and comprise the electric product that soldering has above-mentioned electronic component.
Background technology
At the various parts of soldering on the printed base plate or on the IC socket during soldering IC, the flux of implementing to be used to make the tack of scolding tin to improve is in advance handled.General flux is for containing the corrosive agent of acid ingredient in solvent.Therefore, do not wish the flux infiltration or be attached to the electric terminal part of electronic units such as connector, switch, potentiometer, semi-fixed resistance or the part that does not need soldering of printed base plate etc., need prevent such situation.Especially, because in the through-hole section of the electronic unit phenomenon that is called as " swashing of flux " that the flux that takes place swashes by capillarity etc. of grading, flux adheres to or infiltrates into the part that does not need soldering, need prevent such situation.
Therefore, before soldering, be used to prevent the preliminary treatment of flux migration.Used flux migration prevents that agent from normally comprising the composition that the solvent of flux is had the polymer of resist solvent in this preliminary treatment.All the time, because the typical solvent of flux is IPA, be used as the index that flux migration prevents performance so refuse IPA.Therefore, prevent the active ingredient of agent, use the polymer of refusing the good polyfluorinated alkyl of IPA performance always as flux migration.
Prevent the polymer of agent as so present flux migration, can exemplify the copolymer (with reference to patent documentation 1) of the beta-unsaturated esters compound that for example has Polyfluoroalkyl and siliceous unsaturated compound.The object lesson of the siliceous unsaturated compound that is wherein disclosed is following vinyl silane compound.
In the formula, R
2Expression hydrogen atom or methyl, R
3～R
5The alkoxyl of representing methyl or carbon number 1～3 respectively independently.
Also have to disclose and to comprise and above-mentioned same unsaturated silane monomer and contain the copolymer of the beta-unsaturated esters monomer of fluorinated aliphatic group, also example flux migration prevent other document (with reference to patent documentation 2) of the coating composition of agent purposes.
Patent documentation 1: the Japan Patent spy opens the 2001-135926 communique
Patent documentation 2: the Japan Patent spy opens the 2002-146271 communique
The announcement of invention
In recent years, soldering technology changes huge, and the trend of the miniaturization of soldering parts is also arranged, as nearest technology, main flow be the scolding tin of printing paste on printed base plate, configuration surface installing component thereon, the solder reflow soldering that soldering is carried out in the scolding tin fusion with infrared ray or hot blast heating.In this solder reflow soldering, substrate is whole to be exposed under the condition of scolding tin melt temperature.But, there be melt temperature (183 ℃) the high tendency of melt temperature owing to the consideration of environment is become gradually the scolding tin of the unleaded material of main flow than in the past lead welding tin, for example high about 35 ℃.
According to these situations, prevent that for flux migration agent from also beginning the flux migration that requirement is adapted under the particular surroundings of scolding tin and preventing performance.For example, known flux migration in the past prevents that agent from can't give full play to its performance in using the solder reflow soldering of aforesaid paste scolding tin.
In addition, because the parts miniaturization, therefore swashing prevents that agent from coating distribution partly is very difficult, is applicable to parts integral body mostly.At this moment, prevent agent, then also have problem the bigger influence of the following process generation of the bonding grade of protection diaphragm seal if be used to improve high the swashing of water and oil repellant of the prevention effect of swashing of flux.
In view of aforesaid variety of issue, the object of the present invention is to provide in the use of the soldering of installing and to bring into play the anti-flux migration composition that high flux migration prevents performance on the surface of being on the increase recently.In addition, its purpose also be to provide scolding tin such as electronic unit with the tunicle that forms by said composition or printed base plate with electronic component, use the soldering method of said composition and comprise the electric product that soldering has above-mentioned electronic component.
The swashing of the solder flux that provides among the present invention prevents that composition from comprising the copolymer that contains the unit of being derived by the unsaturated compound (following also note is made compound (a)) of at least a polyfluorinated alkyl with following formula (a) expression and at least a (methyl) acrylate that contains silane with following formula (b) expression (following also remember make compound (b)).
Formula (a) and (b) in,
Q: singly-bound or divalent linking group,
R
1: hydrogen atom or methyl,
R
f: can contain the Polyfluoroalkyl that is inserted in the etheric oxygen atom between carbon-carbon bond,
R
2: hydroxyl or hydrolyzable functional group,
R
3, R
4: independent respectively is hydrogen atom, the saturated alkyl of carbon number 1～4, phenyl,
The integer of n:1～3,
M, l: independently be respectively 0 or 1 integer,
Wherein, (4-n-m-l) more than 1.
Polyfluoroalkyl in the described formula (a) is (in the formula (a) with R
fBasis representation) better is perfluoroalkyl, is generally the perfluoroalkyl of carbon number 1～20.
In the preferred form of copolymer of the present invention, 90 quality % of all Polyfluoroalkyls in the unit of deriving by above-claimed cpd (a) above for main chain carbon number below 6, be more preferably the perfluoroalkyl below 3.
The content of the unit of being derived by compound (b) of copolymer of the present invention is generally 1～50 quality %.
Copolymer of the present invention can also contain by except that above-claimed cpd (a) with the unit of deriving of the fluorine-free unsaturated compound (c) (b).
The composition that comprises aforesaid copolymer is brought into play high flux migration for the main paste scolding tin that adopts in the solder reflow soldering and is prevented performance.Therefore, swashing of solder flux of the present invention prevents that composition can be used for the soldering that install on the surface well.In addition, scolding tin is under the situation of Pb-free solder, also can use well.
In addition, part or all that the invention provides its surface has the scolding tin electronic component that flux migration prevents performance that has of the tunicle that formed by composition of the present invention.
Also have, in this specification, electronic unit and printed base plate etc. is referred to as electronic component by the processed member of soldering.
Part or all of surface that the present invention also is provided at electronic component forms the tunicle that is formed by above-mentioned composition, with part or all of the surface of described electronic component with the solder flux processing after, carry out the soldering method of the electronic component of soldering.
The electric product of the electronic component that has comprised by this method soldering also is provided in addition.
The swashing of solder flux of the present invention prevents that composition from can bring into play swashing of high flux and preventing performance, brings into play high flux migration for the main paste scolding tin that adopts in the solder reflow soldering and prevents performance.Therefore, also can adapt to surface mounting technique.In addition, of the present invention swashing prevents composition by comprising specific copolymer, even oil repellent is low, also can keeping swashes prevents performance, can realize simultaneously swashing preventing the performance of performance and the improvement of following process.
The best mode that carries out an invention
Swashing of solder flux of the present invention prevents that composition (also note is done " swash and prevent agent ") from comprising specific copolymer conduct by film component.This copolymer contains by the unsaturated compound of at least a polyfluorinated alkyl with following formula (a) expression and the unit that at least a (methyl) acrylate (b) that contains silane described later is derived.Also have, in this specification, (methyl) acrylate is meant at least one side in acrylate and the methacrylate.
In the formula (a), R
1Be hydrogen atom or methyl.
R
fBe Polyfluoroalkyl.This Polyfluoroalkyl is meant the group that the hydrogen atom more than 2 of alkyl is replaced by fluorine atom and get, and can be inserted with etheric oxygen atom between the carbon-carbon bond of this alkyl.In this specification, Polyfluoroalkyl or R
fThe statement correspondence of base contains the upperseat concept of the Polyfluoroalkyl that is inserted in the etheric oxygen atom between carbon-carbon bond, unless otherwise specified, all is the general name that does not contain this oxygen atom and contain these two kinds of Polyfluoroalkyls of this oxygen atom.
Above-mentioned Polyfluoroalkyl (R
fBase) fluorine that is generally corresponding to the alkyl of carbon number 1～20 replaces several groups more than 2, can be in linear chain structure and the branched structure any.For example, the part fluorine that can exemplify corresponding to the alkyl of straight chain such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl or branched structure replaces or the perfluor substituted alkyl, has the group of polyfluoro oxyalkylene group repetitives such as polyfluoro oxyethylene group, polyfluoro oxypropylene group etc.As the Polyfluoroalkyl of branched structure, can exemplify the perfluor substituted alkyl of isopropyl, 3-methyl butyl, 5-methyl hexyl, 7-Methyl Octyl etc.
Also have, need on the structure under the situation of higher rigidity, in order to improve R
fThe packed structures of base is as R
fBase selects not contain the Polyfluoroalkyl, particularly selection of etheric oxygen atom not to contain the perfluoroalkyl of etheric oxygen atom.
Among the present invention, R
fBase it is desirable to perfluoroalkyl that perfluor in fact replaces, and (following also note is made R
FBase), better be the R of carbon number 1～20
FBase, good especially is that the chain length (carbon number that does not comprise side chain) of main chain is 1～6 R
FBase.
R
fBase can be any in linear chain structure and the branched structure, better is linear chain structure.Being under the situation of branched structure, better is that component is present in R
fThe base end portion and be the situation of the short chain of carbon number about 1～3.
Of the present invention swashing prevents in the agent R
fThe base chain length prevents that performance from not having significant correlation with swashing.Even R
fThe chain length of the main chain of base surpasses 8, and also can not making swashes prevents that performance from descending, but the oil repellent grow, influence that may be bigger to the following process generation of processed parts.
Also has R
fThe base chain length with refuse water or can there be confidential relation in oil repellent, if R
fThe carbon number of chain length reaches more than 8, then can show very high water and oil repellant.Also have, for water and oil repellant, can be with contact angle as index.For example, big more for the contact angle of the oil of dodecane etc., then we can say to have high more oil repellent.
Yet swashing prevents performance and R
fChain length does not have significant correlation, therefore from the angle of the following process of processed parts, and in the copolymer, all R in the unit of deriving by compound (a)
f90 quality % of base above for main chain carbon number below 6, be more preferably the R below 3
FBase.
In the above-mentioned formula (a), Q is the linking group of singly-bound or divalent.The linking group of following example divalent, but Q can suitably select so long as the linking group of singly-bound or divalent gets final product, and is not limited to these groups.
As the linking group of divalent, can exemplify-O-,-S-,-NH-,-SO
2-,-PO
2-,-CH=CH-,-CH=N-,-N=N-,-N (O)=N-,-COO-,-COS-,-CONH-,-COCH
2-,-CH
2CH
2-,-CH
2-,-CH
2NH-,-CH
2-,-CO-,-CH=CH-COO-,-alkylidene of CH=CH-CO-, straight chain shape or branch-like or alkenylene, alkylidene oxygen base, 4,5,6 or 7 yuan of ring substituents of divalent or condense substituting group, 6 yuan of cyclophane bases, 4～6 yuan of ring fillings or undersaturated aliphatic group, 5 or 6 yuan of ring heterocyclic radicals or their condensed ring by what they constituted are by the group that constitutes of the linking group of these divalents.
These groups can have substituting group; as substituent example; halogen atom (F is arranged; Cl; Br; I); cyano group; alkoxyl (methoxyl group; ethyoxyl; the butoxy octyloxy; methoxy ethoxy etc.); aryloxy group (phenoxy group etc.); alkylthio group (methyl mercapto; ethylmercapto group etc.); acyl group (acetyl group; propiono; benzoyl etc.); sulfonyl (mesyl; benzenesulfonyl etc.); acyloxy (acetoxyl group; benzoyloxy etc.); sulfonyloxy (mesyloxy; tosyloxy etc.); phosphono (diethyl phosphonyl etc.); acylamino-(acetylamino; benzamido etc.); carbamoyl (N, N-formyl-dimethylamino; N-phenyl amino formoxyl etc.); alkyl (methyl; ethyl; propyl group; isopropyl; cyclopropyl; butyl; the 2-carboxy ethyl; benzyl etc.); aryl (phenyl; tolyl etc.); heterocyclic radical (pyridine radicals; imidazole radicals; furyl etc.); alkenyl (vinyl; 1-acrylic etc.); alkoxyl acyloxy (acetoxyl group; benzoyloxy etc.); alkoxy carbonyl (methoxycarbonyl; ethoxy carbonyl etc.) and polymerizable group (vinyl; acryloyl group; methacryl; pi-allyl; cinnamic acid residue etc.) etc.
In above-mentioned, Q better is with-Z-(Y)
n-(Z be singly-bound ,-O-or-NH-, Y is the linking group of alkylidene, amino, sulfonyl or the divalent that obtained by their combination, n is 0 or 1 integer) linking group of the divalent of expression.Y better is the alkylidene of the straight chain of carbon number 1～5.
Q in the formula (a) is-Z-(Y)
n-the preferred example of form specifically can represent with following formula (a1).
In the formula (a1),
R
1: hydrogen atom or methyl,
Z: singly-bound ,-O-,-NH-,
Y: the alkylidene of carbon number 1～5,
R
f: expression F (CF
2)
n-, (CF
3)
2CF (CF
2)
m-(integer of n=1～20, the integer of m=0～10).
Object lesson as the compound of representing with above-mentioned formula (a1) can exemplify the acrylate of following polyfluorinated alkyl or the methacrylate of polyfluorinated alkyl, and the compound among the present invention (a) is not limited to these examples.
Y in these compounds and R
fCombination be shown in following table 1.
Table 1
| Y | R f |
| -(CH 2) 2- | -(CF 3) 8F |
| -(CH 2) 2- | -(CF 2) 6F |
| -(CH 2) 2- | -(CF 2) 4F |
| -CH 2- | -(CF 2) 2F |
| -CH 2- | -CF 3 |
| -(CH 2) 2- | -(CF 2) 6CF(CF 3) 2 |
| -(CH 2) 2- | -(CF 2) 4CF(CF 3) 2 |
| -(CH 2) 2- | -(CF 2) 2CF(CF 3) 2 |
| -CH 2- | -CF(CF 3) 2 |
Copolymer of the present invention can contain a kind of unit of being derived by above-claimed cpd (a), also can contain more than 2 kinds.
The content of the unit of being derived by all above-claimed cpds (a) in the copolymer better is 50～99 quality %, is more preferably 80～99 quality %.This be because if the content of the unit of deriving by compound (a) in above-mentioned scope, then the flux of copolymer swash prevent functional.Also have, in the copolymer of the present invention, the content of each polymerized unit can be regarded the polymerization feeding quantity as in fact.
(methyl) acrylate that contains silane that forms copolymer of the present invention is represented with following formula (b).
In the formula (b), Q is the linking group of singly-bound or divalent, but the same group of Q in example and the aforementioned formula (a).Wherein, as preferred Q, can exemplify singly-bound ,-(CH
2)
n-(n=1 wherein～10) ,-(CH
2CH
2O)
n-(n=1 wherein～10) ,-alkylidene of COO-, 6 yuan of cyclophane bases, straight chain shape or branch-like or by the group that constitutes of the linking group of these divalents, can more preferably exemplify the alkylidene of singly-bound, carbon number 1～5 etc.
R
1Be hydrogen atom or methyl.
R
2Be hydroxyl or hydrolyzable functional group, specifically can exemplify alkoxyl, halogen atom of carbon number 1～3 etc.
N is 1～3 integer, and n is 2 or 3 o'clock, R
2Can be identical or different.
M and l independently are respectively 0 or 1 integer.(4-n-m-l) more than 1.
R
3And R
4Independent respectively is hydrogen atom, the saturated alkyl of carbon number 1～4, phenyl.
From to the adaptation of processed parts, the angle of the preventing property of swashing, above-claimed cpd (b) better is the hydrolyzable functional group of containing more than at least 1, in the promptly above-mentioned formula (b), contains the R of at least 1 the hydrolyzable functional group of conduct
2, wherein be more preferably n=3 and all R
2It all is hydrolyzable functional group.In addition, as hydrolyzable functional group, the easiest processing of alkoxyl is preferred.As alkoxyl, better be carbon number 1～5, good especially is carbon number 1～3.
Below, the object lesson of the preferred compound (b) that example is such, but compound (b) is not limited to these examples.
Q in these compounds and R
2Combination be shown in following table 2.
Table 2
| Q | (R 2) 3 |
| Singly-bound | -(OMe) 3 |
| Singly-bound | -(OEt) 3 |
| Singly-bound | -(OPr) 3 |
| -CH 2- | -(OMe) 3 |
| -CH 2- | -(OEt) 3 |
| -CH 2- | -(OPr) 3 |
| (CH 2) 2 | (OMe) 3 |
| -(CH 2) 2- | -(OEt) 3 |
| -(CH 2) 2- | -(OPr) 3 |
| -(CH 2) 3- | -(OMe) 3 |
| (CH 2) 3 | (OEt) 3 |
| -(CH 2) 3- | -(OPr) 3 |
Copolymer of the present invention can contain a kind of unit of being derived by above-claimed cpd (b), also can contain more than 2 kinds.
In the copolymer of the present invention, even the unit of deriving only contains 1 quality %, swashing prevents that performance from also improving by compound (b).If contain more than the 5 quality %, then show very high performance.Yet if contain a large amount of unit of being derived by compound (b), the stability of copolymer is destroyed easily, so the content of the unit of being derived by all compounds (b) in the copolymer better is 1～50 quality %, is more preferably 5～20 quality %.
Copolymer of the present invention can contain aforesaid by the compound (a) and the unit of (b) deriving in, contain more than a kind or 2 kinds by the unit of deriving except that the compound them (c).This compound (c) so long as can be with above-mentioned (a) and other compound of (b) forming copolymer get final product, be not particularly limited.
As such compound (c), for example can exemplify and do not have R
fAnd the compound with unsaturated group of polymerism specifically can exemplified by acrylic, (methyl) acrylic acid polyester such as TPO beta-unsaturated esters, the compound with vinyl, the beta-unsaturated esters with epoxy radicals, the compound with amino and polymerism unsaturated group, diester acrylates such as methacrylic acid, acrylate and have substituted-amino and the compound of polymerism unsaturated group etc.
Below, the object lesson of the compound (c) that example is such, but be not limited to these examples.
The example 1 of compound (c): styrene compound (compound) with vinyl
Above-mentioned R
5For example be-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 or-CH
2OCOCH
3Deng.
The routine 2:(methyl of compound (c)) acrylate
Or
Above-mentioned R
6For example be-H ,-CH
3,-CH
3CH
2OH ,-CH
2CH
2N (CH
3)
2,-(CH
2)
nH (n=2 wherein～20) ,-CH
2CH (CH
3)
2,-CH
2-C (CH
3)
2-OCO-Ph ,-(CH
2CH
2O)
nH (n=2 wherein～20) ,-CH
2-Ph ,-CH
2CH
2OPh ,-CH
2N (CH
3)
3Cl ,-CH
2CH
2O-PO (OH)
2,-[Si (CH
3)
2O]
mH (m=2 wherein～20) ,-(CH
2CH
2O)
nCH
3(n=2 wherein～20),
Deng.
The example 3 of compound (c): with the compound shown in the following formula
Or
Above-mentioned R
7For example be-NHCH
2OH ,-NHCH
2SO
3H ,-NHC (CH
3)
2CH
2-CO-CH
3,-N=N (CH
3)
3,-CNH
2n+1(n=2 wherein～20) and-NH
2Deng.
The example 4 of compound (c): following compound
CH
2＝CHCl
CH
2＝CH-CN
In the above-mentioned example, n=1～10.
The example 5 of compound (c): following compound
(CH
2＝C(R)-COO-CH
2CH
2O)
2PO(OH)
CH
2＝C(R)-COO-(CH
2CH
2O)
n-CO-C(R)＝CH
2
CH
2＝C(R)-COO-(CH
2)
n-OCO-C(R)＝CH
2
(CH
3)
2C(CH
2O-CO-C(R)＝CH
2)
2
(CH
3)C(CH
2O-CO-C(R)＝CH
2)
3
C(CH
2O-CO-C(R)＝CH
2)
4
HOCH
2-C(CH
2O-CO-C(R)＝CH
2)
3
(CH
2=C (R)-COO-CH
2)
3C-CH
2OCH
2-C (CH
2O-CO-C (R)=CH
2)
3In the above-mentioned example, R is H or CH
3
The example 6 of compound (c):
Above-mentioned R
1Be hydrogen atom or methyl, R
8Be organic group (not comprising Polyfluoroalkyl), p is 1～4 integer.
Copolymer of the present invention can contain the unit of being derived by aforesaid compound (c) with the amount below the 50 quality %, and its content is also according to its kind and difference.
Among the present invention,, then can give full play to performance if the molecular weight of copolymer is moderately big; On the other hand, if molecular weight is excessive, then to the dissolubility variation of solvent, so the molecular weight of copolymer better is 1 * 10 in weight average molecular weight (Mw) usually
3～1 * 10
7, good especially is 1 * 10
4～2 * 10
5
Copolymer of the present invention is not particularly limited for polymerized form etc. except containing the unit of being derived by aforesaid compound (a) and (b) and additional (c).Polymerized form can be any in random, block, grafting etc., is not particularly limited, but better is random copolymer usually.
Also be not particularly limited for its manufacture method, can make its addition polymerization based on the unsaturated group in each compound usually among the present invention.During polymerization, can suitably adopt the addition polymerization condition of known unsaturated compound to carry out.For example,, be not particularly limited, can adopt common initators such as organic peroxide, azo-compound, persulfate as the polymerization initiating accident sequence.
The normally aqueous form of composition of the present invention (swash and prevent agent) that comprises above-mentioned copolymer.Therefore, preferred form is by being that copolymer is made in the polymerisation in solution of polymerisation medium with solvent described later, directly prepares liquid composition by polymerization.Compound as polymer raw is under the situation of gases such as vinyl chloride, can the working pressure container, depress continuous supply adding.
Can dissolve or dispersed copolymer as long as form the solvent of composition, be not particularly limited, can exemplify various organic solvents, water or their blending agent etc.Contained R in the copolymer particularly
fUnder the situation of the chain length of base, can be with the polar solvent except that alcohol as main solvent.Specifically, can exemplify as the acetone of ketone and methyl ethyl ketone, as the ethyl acetate of ester class, as oxolane of ethers etc., but be not limited thereto.If the fluorine kind solvent then can not considered the R in the copolymer
fThe chain length of base is selected.Also can use hydrochlorofluorocarazeotropic (HCFC) and perfluocarbon (PFC), if but consider social environmental problem, better be hydrogen fluorine carbon (HFC) or fluorohydrocarbon (HFE) etc.Below, the object lesson of the spendable fluorine kind solvent of example, but be not limited to these examples.
Hexafluoro meta-xylene (following note is made m-XHF)
Hexafluoro paraxylene (following note is made m-XHF)
CF
3CH
2CF
2CH
3
CF
3CH
2CF
2H
C
6F
13OCH
3
C
6F
13OC
2H
5
C
3F
7OCH
3
C
3F
7OC
2H
5
C
6F
13H
CF
2HCF
2CH
2OCF
2CF
2H
CF
3CFHCFHCF
2CH
3
CF
3(OCF
2CF
2)
n(OCF
2)
mOCF
2H
C
8F
17OCH
3
C
7F
15OCH
3
C
4F
9OCH
3
C
4F
9OC
2H
5
C
4F
9CH
2CH
3
CF
3CH
2OCF
2CF
2CF
2H
In the above-mentioned example, m, n represent 1～20.
Of the present invention swashing prevents that agent from comprising above-mentioned copolymer with the concentration that better is 0.01～20 quality %, is more preferably 0.05～5 quality % usually.If the concentration of copolymer is in this scope, then can giving full play to swashes prevents performance, and the stability of composition is also good.Also have, the above-mentioned copolymer concentration that prevents agent that swashes is that ultimate density gets final product, for example directly prepare to swash and prevent under the situation of agent that the copolymer concentration (solid component concentration) of the polymeric compositions after polymerization has just finished is even surpass 20 quality %, and is also no problem as polymeric compositions.The polymeric compositions of high concentration can suitably dilute, and makes it finally reach above-mentioned preferred concentration.
So long as can not prevent that performance or outward appearance etc. from producing in the dysgenic scope to stability, the flux migration of composition, of the present invention swashing prevents that agent from can comprise other composition except that aforementioned.As other such composition, the pH that can exemplify the corrosion that for example is used for preventing the tunicle surface adjusts agent, antirust agent, be used to carry out the concentration management of polymer of liquid or the dyestuff of distinguishing with the parts that are untreated when the composition dilution is used, stabilizing agent, incombustible agent, defoamer or the antistatic agent etc. of dyestuff.
By the present invention, can provide aforesaid swashing prevented agent part or all formation tunicle on the surface of electronic component, after part or all of the surface of described electronic component handled with solder flux, carry out the soldering method of the electronic component of soldering.At this moment, can prevent that agent is diluted to concentration arbitrarily according to purpose and purposes, be coated on electronic component swashing.As coating method, can adopt general lining processing method.For example, there are dip coated, spraying or employing to be filled with the methods such as coating of the aerosol can of composition of the present invention.
As electronic component, specifically can exemplify the electronic unit that connector, switch, potentiometer, semi-fixed resistance etc. have electric terminal, printed base plate etc. with electric terminal.As preventing the position that agent is covered by of the present invention swashing, the position of swashing that in the time of can exemplifying on printed base plate electronic unit such as soldering connector flux may take place.More particularly, the substrate surface or be used to of a side of installation electronic unit main body that can exemplify pin part, the printed base plate of the electronic units such as connector that are installed on substrate is installed the through hole of being located at printed base plate of electronic unit etc.In addition, can be coated on the whole surface of electronic unit or printed base plate, also can adopt the coating method except that above-mentioned.For example, also can adopt the high method of lining efficient based on full dipping or half dipping.
Swash prevent agent coating after, better be under the temperature more than the boiling point of solvent, to carry out drying.Certainly, owing to the material of processed parts etc. is difficult under the situation of heat drying, should not adopt heating to carry out drying.Also have, heat treated condition is selected to get final product according to the composition of the composition of coating and spreading area etc.
Of the present invention swashing prevents that agent from forming tunicle on the surface of electronic unit or printed base plate, prevents swashing of solder flux.Therefore, by the present invention, electronic unit that the corrosion that can provide flux to cause is prevented or printed base plate.
Especially, of the present invention swashing prevents that agent is adapted to surface mounting technique, prevents the solder reflow soldering that agent is difficult to adapt to in the past flux migration, the performance high-performance.In addition, of the present invention swashing prevents also abundant adapted to leadless scolding tin of agent.
Then, the electronic unit or the printed base plate that have formed tunicle by aforesaid operations on the surface are handled by solder flux, carry out soldering again, form electronic unit or printed base plate through soldering.In addition, this electronic unit or printed base plate can be used for various electric products.This electric product is the good electric product of quality that is prevented by the problem that corrosion caused that flux causes.As the object lesson of this electric product, can exemplify used equipment such as computer usefulness equipment, television set, sound equipment usefulness equipment (radio cassette player, laser disc, miniature disc record), mobile phone etc.
Embodiment
Below, the present invention is specifically described, but the present invention is not subjected to the qualification of following embodiment.Also have, short of special qualification, in the record of following embodiment, the scale of representing with " % " shows " quality % ".The abbreviation souvenir of each compound is shown in table 3.
Table 3
[Production Example 1～20]
Make each compound (a) shown in the table 3 and compound (b) carry out polymerization, obtain to contain the polymeric compositions 1～20 of polymer 1～20 so that the mass ratio shown in the table 4 is following.
In the ampoule bottle of the glass system of 100ml with the monomer of total amount 100 mass parts, 1 mass parts as 2 of initator, Wako Pure Chemical Industries, Ltd.'s (with light Pure medicine)), 399 mass parts are reinforced as the ratio of the hexafluoro meta-xylene (m-XHF) of solvent 2 '-azo two (2 Methylpropionic acid methyl esters) (V-601:, make total feeding quantity reach 60g, reacted 18 hours at 70 ℃, obtain to comprise the polymeric compositions 1～20 of the copolymer 1 shown in the table 4～20.
[relatively Production Example 1～8]
In the above-mentioned Production Example, except not using compound (b), similarly operate, make each compound (a) homopolymerization of representing with F (M) A in the table 3, obtain to comprise the polymeric compositions 21～25 of polymer 21～25.In addition,, similarly operate, obtain to comprise the polymeric compositions 26～28 of the polymer 26～28 shown in the table 4 with above-mentioned Production Example except with the compound (a) and compound (c) represented with C6FMA in the mass ratio use table 3 shown in the table 4.
[mensuration of weight average molecular weight]
Above-mentioned each polymeric compositions is diluted to 2% with m-XHF, as working sample.Use the Shodex GPC-104 of Showa Denko K. K (clear and Electricity worker Co., Ltd.) system, measure by following condition determination.The measurement result of the weight average molecular weight of polymer 1～28 is shown in following table 4.
＜GPC condition determination 〉
Splitter: LF-604 * 2
Acquiescence post: KF600RH * 2
Eluent: AK-225
Flow velocity: 0.2ml/ minute
Standard substance: polymethyl methacrylate
[solid component concentration of polymer composition]
Get above-mentioned polymer composition of 1g, after 2 hours, the weighing solid constituent is obtained solid constituent (copolymer) concentration (quality %) 110 ℃ of dryings.The results are shown in table 4.
Table 4
*: compound (c)
*Solid component concentration in the polymeric compositions
[embodiment 1～20]
For polymeric compositions 1～20, be diluted to 0.1% with m-XHF, carry out evaluation and measurement of contact angle that flux migration prevents performance.The results are shown in table 5.
[comparative example 1～8]
For polymeric compositions 21～28, be diluted to 0.1% with m-XHF, estimate flux migration and prevent performance.The results are shown in table 5.
[flux migration prevents the comparison of performance]
Will to copper coin carry out silver-plated (the thick 3 μ m of coating) handle and test film flood 60 seconds with each embodiment and comparative example after, carried out drying 5 minutes at 110 ℃.For the test film of having handled with each inorganic agent, and the paste scolding tin " ECO SOLDER Paste M705-GRN360-K2 " of mask printing Senju Metal Industry Co., Ltd (Senju Metal Industry Co., Ltd) system (circular φ=3mm, thickness=0.3mm).Test film is fixed with the inclination of about 73 degree, use the solderability tester SAT-5100 of power generation section of Co., Ltd. (the レ ス カ of Co., Ltd.) system, make its heat up (temperature with 70～80 ℃ begins → (2 ℃/second) → 220 ℃ * 120 seconds → (2 ℃/second) → 260 ℃ * 60 seconds).After the intensification, measure scolding tin and flux from the upper end to terminal distance.Deduct the directly value of (3mm) gained (flux sagging distance) of mask according to this distance, carry out the comparison that flux migration prevents performance.
[measurement of contact angle]
Glass plate for handle (after flooding 1 minute, 110 ℃ of dryings 5 minutes) through each embodiment carries out the contact angle determination for hexadecane.Measurement of contact angle is used consonance interface science (Association of Co., Ltd. and interface science society) the drop formula projection type contact angle meter of system.
Confirm that anti-flux migration composition of the present invention has very high swashing and prevents performance.
Table 5
| Embodiment | Composition | Flux sagging distance [mm] | Contact angle [degree] |
| ?1 | 1 | 1.7 | 77 |
| ?2 | 2 | 0.5 | 77 |
| ?3 | 3 | 0.7 | 75 |
| ?4 | 4 | 0.8 | 77 |
| ?5 | 5 | 0.7 | 67 |
| ?6 | 6 | 1.1 | 71 |
| ?7 | 7 | 1.0 | 70 |
| ?8 | 8 | 1.0 | 72 |
| ?9 | 9 | 1.6 | 68 |
| ?10 | 10 | 1.2 | 67 |
| ?11 | 11 | 0.9 | 68 |
| ?12 | 12 | 0.9 | 66 |
| ?13 | 13 | 1.9 | 60 |
| ?14 | 14 | 1.0 | 60 |
| ?15 | 15 | 0.8 | 60 |
| ?16 | 16 | 1.0 | 56 |
| ?17 | 17 | 1.7 | 49 |
| ?18 | 18 | 0.8 | 49 |
| ?19 | 19 | 0.8 | 52 |
| ?20 | 20 | 0.8 | 46 |
| Comparative example 1 | 21 | 2.9 | 76 |
| Comparative example 2 | 22 | 5.2 | 63 |
| Comparative example 3 | 23 | 7.2 | 66 |
| Comparative example 4 | 24 | 7.0 | 61 |
| Comparative example 5 | 25 | 6.2 | 52 |
| Comparative example 6 | 26 | 5.6 | 71 |
| Comparative example 7 | 27 | 2.9 | 73 |
| Comparative example 8 | 28 | 2.9 | 70 |
Claims (11)
1. anti-flux migration composition for solder, it is characterized in that, comprise the copolymer that contains by the unsaturated compound of at least a polyfluorinated alkyl with following formula (a) expression and at least a unit of deriving with (methyl) acrylate that contains silane of following formula (b) expression:
Formula (a) and (b) in,
Q: singly-bound or divalent linking group,
R
1: hydrogen atom or methyl,
R
f: can contain the Polyfluoroalkyl that is inserted in the etheric oxygen atom between carbon-carbon bond,
R
2: hydroxyl or hydrolyzable functional group,
R
3, R
4: independent respectively is hydrogen atom, the saturated alkyl of carbon number 1～4, phenyl,
The integer of n:1～3,
M, l: independently be respectively 0 or 1 integer,
Wherein, 4-n-m-l is more than 1.
2. composition as claimed in claim 1 is characterized in that, the Polyfluoroalkyl in the described formula (a) is a perfluoroalkyl.
3. composition as claimed in claim 1 is characterized in that, above by 90 quality % of all Polyfluoroalkyls in the unit of described compound deriving with formula (a) expression is the perfluoroalkyl of main chain carbon number below 6.
4. composition as claimed in claim 3 is characterized in that, above by 90 quality % of all Polyfluoroalkyls in the unit of described compound deriving with formula (a) expression is the perfluoroalkyl of main chain carbon number below 3.
5. composition as claimed in claim 1 is characterized in that, the content by with the unit of the compound deriving of formula (b) expression of described copolymer is 1～50 quality %.
6. composition as claimed in claim 1, it is characterized in that, described copolymer also contain by except that described with the compound of formula (a) expression and the unit of deriving with the fluorine-free unsaturated compound (c) (methyl) acrylate that contains silane of formula (b) expression.
7. composition as claimed in claim 1 is characterized in that, is used for the soldering that install on the surface.
8. composition as claimed in claim 7 is characterized in that, described scolding tin is Pb-free solder.
9. have flux migration and prevent the scolding tin electronic component of performance, it is at least a electronic component that is selected from electronic unit and printed base plate, it is characterized in that, and part or all of its surface has the tunicle that is formed by each the described composition in the claim 1～8.
10. the soldering method of electronic component, it is characterized in that, form the tunicle that forms by each the described composition in the claim 1～8 in part or all of the surface of at least a electronic component that is selected from electronic unit and printed base plate, after part or all of the surface of described electronic component handled with solder flux, carry out soldering.
11. electric product is characterized in that, the electronic component that has comprised by the described method soldering of claim 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006054976 | 2006-03-01 | ||
| JP054976/2006 | 2006-03-01 | ||
| PCT/JP2007/052492 WO2007099760A1 (en) | 2006-03-01 | 2007-02-13 | Anti-flux migration composition for solder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101389443A CN101389443A (en) | 2009-03-18 |
| CN101389443B true CN101389443B (en) | 2011-05-25 |
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|---|---|---|---|
| CN2007800065678A Expired - Fee Related CN101389443B (en) | 2006-03-01 | 2007-02-13 | Anti-flux migration composition for solder |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5124441B2 (en) |
| CN (1) | CN101389443B (en) |
| WO (1) | WO2007099760A1 (en) |
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|---|---|---|---|---|
| CN101952082B (en) * | 2008-01-18 | 2013-03-13 | Agc清美化学股份有限公司 | Flux creeping-up preventive composition for solder, electronic member for solder coated with the composition, method for soldering the member, and electrical appliance |
| CN102782105A (en) * | 2010-02-26 | 2012-11-14 | 阿尔卑斯电气株式会社 | Surface treating agent for electrical contacts |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6049859A (en) * | 1983-08-30 | 1985-03-19 | Asahi Glass Co Ltd | Agent for preventing creeping up of flux for soldering |
| JP3516148B2 (en) * | 1993-12-28 | 2004-04-05 | 大日本インキ化学工業株式会社 | How to prevent flux from entering electronic components |
| JPH1098253A (en) * | 1996-09-24 | 1998-04-14 | Nof Corp | Diffusion preventing agent for soldering flux |
| JPH10303536A (en) * | 1997-04-24 | 1998-11-13 | Seimi Chem Co Ltd | Composition for flux creeping-up inhibitor for solder |
| JP3710290B2 (en) * | 1997-09-16 | 2005-10-26 | セイミケミカル株式会社 | Composition to prevent solder flux from creeping up |
| JP4343354B2 (en) * | 1999-11-02 | 2009-10-14 | Ａｇｃセイミケミカル株式会社 | Solder flux creeping-up inhibitor composition and its use |
-
2007
- 2007-02-13 WO PCT/JP2007/052492 patent/WO2007099760A1/en active Application Filing
- 2007-02-13 JP JP2008502689A patent/JP5124441B2/en active Active
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Non-Patent Citations (3)
| Title |
|---|
| JP特开2001-135926A 2001.05.18 |
| JP特开平10-98253A 1998.04.14 |
| JP特开平11-154783A 1999.06.08 |
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|---|---|
| CN101389443A (en) | 2009-03-18 |
| JPWO2007099760A1 (en) | 2009-07-16 |
| WO2007099760A1 (en) | 2007-09-07 |
| JP5124441B2 (en) | 2013-01-23 |
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