JP5018017B2 - Cream solder flux and cream solder - Google Patents

Description

  The present invention relates to a flux for cream solder and cream solder.

  As the flux used for mounting electronic parts, etc., a liquid flux that is applied by spraying or the like, and a paste-like flux for use as a so-called cream solder composition in which a flux composition and solder powder are kneaded are known. Yes.

  The liquid flux is generally composed of rosins, activators, solvents and the like, and the cream solder composition is generally composed of rosins, solvents, activators, thixotropic agents, solder powders and the like.

  As described above, rosins (rosin or derivatives thereof) are generally used as the base resin used in the liquid flux or cream solder composition. The reason for this is considered to be due to excellent erosion resistance due to the rosin skeleton and excellent electrical characteristics such as electrical insulation resistance and dielectric characteristics. However, since rosins are hard and brittle, a flux residue film obtained after soldering a rosin-containing flux is used in an environment with a large temperature difference, for example, in a low temperature atmosphere of about −40 ° C. and a high temperature atmosphere of about 125 ° C. In the case of repeated exposure to each other, there is a problem that cracks are easily generated. When cracks occur in the flux residue film, moisture in the atmosphere adheres to and penetrates into the cracks, causing serious problems such as a decrease in insulation resistance and the occurrence of migration.

  In order to prevent the occurrence of the above problems, measures such as cleaning and removing the flux residue film after soldering with an organic solvent-based cleaning liquid such as chlorofluorocarbon, alternative chlorofluorocarbon, and organic solvents, and a moisture-proof coating treatment have been taken. It was. However, the use of the cleaning solution is not desirable from the viewpoint of protecting the global environment, and also from the viewpoint of reducing production costs, the role of the flux residual film that does not require a cleaning process or a moisture-proof coating process, that is, the role of the moisture-proof coating. There is also a need for a flux residue film that also combines. More specifically, a flux residue film that has excellent electrical reliability, does not crack even in an environment with a large temperature difference, and covers the solder surface and circuit surface after soldering to provide a moisture-proof effect is provided. The appearance of excellent flux compositions and cream solder compositions that can be made is desired.

  The present applicants have previously proposed a flux composition for cream soldering comprising a polyether ester amide resin, a solvent, an activator and a thixotropic agent (see Patent Document 1), but further printing stability, There has been a demand for improved storage stability.

JP 2004-230426 A

  The present invention provides a flux composition and cream solder capable of forming a flux residue film excellent in insulation without cracking in the flux residue film after soldering even in an environment with a large temperature difference. The purpose is to do.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by controlling the glass transition temperature of the flux residue film within a specific range, and have completed the present invention. Moreover, it discovered that it was excellent also in electrical insulation by using an acrylic resin and rosins, and can provide highly reliable cream solder.

That is, the present invention relates to a glass transition temperature of a flux residue film formed after soldering containing a rosin (A), an acrylic resin (B), an activator (C), a thixotropic agent (D) and a solvent (E). Is a flux for cream solder having a temperature of −100 to −30 ° C., and the rosin (A) contains a polymerized rosin and a hydrogenated rosin ; a solder paste flux ; a solder powder and the cream solder flux Relates to cream solder.

According to the present invention, a flux composition capable of forming a flux residue film excellent in insulation without cracking in the flux residue film after soldering even under an environment with a large difference in temperature and temperature. Cream solder can be provided.

  The flux for cream solder of the present invention is characterized in that the glass transition temperature of the flux residue film formed after soldering is −100 to −30 ° C., preferably −80 to −50 ° C. If the glass transition temperature is not within the range of −100 to −30 ° C., the flux residue will flow without forming a film, or the flux residue film will be insufficiently flexible and cracks will easily occur. It is not preferable. In the present invention, the glass transition temperature is a value measured according to a JIS K7121 plastic dislocation temperature measurement method.

  As such a cream solder flux, a flux base, an activator (C) (hereinafter referred to as (C) component), a thixotropic agent (D) (hereinafter referred to as “component”) so that the glass transition temperature after soldering is in the above range. It is obtained by mixing (D) component) and solvent (E) (hereinafter referred to as (E) component).

The flux base is not particularly limited, and a known one can be used. Specifically, rosins (A) (hereinafter referred to as component (A)), acrylic resin (B) (hereinafter referred to as component (B)), polyester resin, polyetheresteramide resin, polyamide resin, polyimide resin, Examples thereof include synthetic resins such as phenoxy resin and terpene resin. In these, it is preferable to use (A) component and (B) component together.

The component (A) is not particularly limited as long as it is a resin derived from rosin and rosin, and known ones can be used, but a hydrogenated rosin and a polymerized rosin must be used in combination . As the component (A), the other, mentioned gum rosin, tall oil rosin, c Tsu Dorojin, disproportionated rosin, modified rosin (e.g., acrylic acid-modified rosin), rosin esters, and other various rosin derivatives It is done .

As the component (B), a resin obtained by polymerizing a (meth) acrylic monomer can be used. It does not specifically limit as a (meth) acryl monomer to be used, A well-known (meth) acryl monomer can be used. Examples of (meth) acrylic monomers include (meth) acrylic acid alkyl esters (a) (hereinafter referred to as (a) component), anionic monomers (hereinafter referred to as (b) component), vinyl monomers other than these ( c) (hereinafter referred to as component (c)).

As component (a), methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, octyl (meth) acrylate Nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, Examples thereof include pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, and the like. The alkyl group may be linear or have a branched structure. Moreover, you may have alicyclic structures, such as aromatic functional groups, such as a phenyl group, and a cyclohexyl group. These can be used individually by 1 type or in mixture of 2 or more types.

The component (b) is not particularly limited as long as it has at least one anionic functional group and one vinyl group, and known components can be used. Specifically, for example, monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, muconic acid and citraconic acid; vinyl sulfonic acid, styrene sulfonic acid, 2- Examples thereof include organic sulfonic acids such as acrylamido-2-methylpropanesulfonic acid; and sodium salts and potassium salts of these various organic acids. These can be used individually by 1 type or in mixture of 2 or more types.

Examples of the component (c) include aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene, allylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meta ) Vinyl monomers having tertiary amino groups such as acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide or their inorganic or organic acids such as hydrochloric acid, sulfuric acid and acetic acid Acid salts or cations such as vinyl monomers containing a quaternary ammonium salt obtained by reaction of the tertiary amino group-containing vinyl monomer with a quaternizing agent such as methyl chloride, benzyl chloride, dimethyl sulfate, epichlorohydrin, etc. Monomer, N, N-dimethyl ( T) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- In addition to N-substituted acrylamides such as t-butyl (meth) acrylamide, (meth) acrylamides, allyl monomers containing allyl groups such as allyl alcohol, (meth) acrylonitrile and the like, bifunctional vinyl monomer systems such as methylenebis (meth) ) Bisacrylamide monomers such as acrylamide and ethylene bis (meth) acrylamide, and diacrylate monomers such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, diallylamine, divinyli Examples of polyfunctional vinyl monomers having three or more vinyl groups such as 1,3,5-triacroylhexahydro-S-triazine, triallyl isocyanurate, triallylamine, tetramethylolmethane tetraacrylate, etc. Is mentioned. In addition, (a) component-(c) component can be used individually by 1 type or in mixture of multiple types.

(B) Although the usage-amount of each component used in order to obtain a component is not specifically limited, Usually, polymerizing the monomer mixture containing about 5 to 100 weight% of (a) component is flexible of the residue at the time of low temperature From the viewpoint of obtaining heat resistance and heat resistance.

The method for polymerizing these monomers is not particularly limited, and a known method can be employed. Specifically, for example, the monomer mixture may be polymerized in the presence of a polymerization initiator, a solvent, a chain transfer agent, or the like, if necessary.

The weight average molecular weight of the component (B) thus obtained is usually about 1,000 to 1,000,000, preferably 2,000 to 200,000.

(C) It does not specifically limit as a component, A well-known thing can be used. Specifically, for example, amine hydrohalides, organic acids and the like can be used. Examples of the amine hydrohalide include diethylamine hydrobromide, cyclohexylamine hydrobromide, diphenylguanidine hydrobromide, and the like. Examples of organic acids include capron. Examples include acid, undecanoic acid, lauric acid, stearic acid, succinic acid, glutaric acid, adipic acid, stearic acid, sebacic acid, bromosuccinic acid, dibromosuccinic acid, phenylsuccinic acid, diglycolic acid, benzoic acid and the like. In addition, these activators can be used individually by 1 type or in mixture of 2 or more types.

(D) It will not specifically limit if it is a thixotropic agent used for manufacture of a flux as a component, A well-known thing can be used. Specifically, for example, hardened castor oil, beeswax, carnauba wax, stearic acid amide, hydroxystearic acid ethylene bisamide, hydroxystearic acid hexamethylene bisamide, and the like can be used. These can be used individually by 1 type or in mixture of 2 or more types.

(E) As a component, if it is a solvent used for manufacture of a flux, it will not specifically limit, A well-known thing can be used. Specifically, alcohols such as ethanol, n-propanol, isopropanol and isobutanol, glycol ethers such as butyl carbitol and hexyl carbitol, esters such as isopropyl acetate, ethyl propionate, butyl benzoate and diethyl adipate And hydrocarbons such as n-hexane, dodecane and tetradecene. These can be used individually by 1 type or in mixture of 2 or more types.

The amount of each component used may be appropriately adjusted according to the application, but is usually about 30 to 75 parts by weight of the flux base, about 0.1 to 20 parts by weight of the component (C), and 1 to 10 parts by weight of the component (D). About 20 parts by weight of the component (E). In addition, in the flux for cream solder of this invention, additives, such as antioxidant, an antifungal agent, a rust preventive agent, and a matting agent, can be contained as needed. Moreover, when using together (A) component and (B) component as a flux base, it is preferable to set it as about 5-50 weight part of (A) component and about 5-40 weight part of (B) component.

  The cream solder of the present invention contains solder powder and the cream solder flux.

  The alloy composition of the solder powder of the present invention is not particularly limited, and various known ones can be used. For example, as a solder alloy, a conventionally known tin-lead alloy, a solder alloy composition such as a tin-silver alloy and a tin-zinc-based alloy that have been developed as a lead-free solder; , Indium, antimony and the like can be used.

Further, the shape of the solder powder is not particularly limited, and any shape such as a true sphere, an indefinite shape, or a mixture of both can be used.

Although the usage-amount of each component should just be determined suitably according to a use etc., a solder powder is about 80-95 weight part normally, and the flux for cream solder is about 5-20 weight part. Moreover, you may add various well-known additives as needed.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to the following Example.

Production Example 1
A glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen introduction tube was charged with 500 parts by weight of butyl glycol, and the mixture was stirred at 115 ° C. under a nitrogen stream, and then 250 parts by weight of butyl glycol, A mixed solution of 200 parts by weight of dodecyl methacrylate, 50 parts by weight of 2-ethylhexyl acrylate, and 15 parts by weight of azoisobutyronitrile (AIBN) was added dropwise. The reaction was further continued for 4 hours while maintaining the temperature at 100 ° C., and then unreacted substances were distilled off under reduced pressure to obtain an acrylic resin 1.

Production Example 2
A glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel and a nitrogen introduction tube was charged with 500 parts by weight of methyl isobutyl ketone, and the mixture was stirred at 100 ° C. in a nitrogen stream, and then 250 parts by weight of methyl isobutyl ketone. A mixed solution of 190 parts by weight of tridecyl acrylate, 50 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of butyl acrylate, and 17 parts by weight of AIBN was added dropwise. The reaction was further continued for 4 hours while maintaining the temperature at 100 ° C., and then unreacted substances were distilled off under reduced pressure to obtain acrylic resin 2.

Production Example 3
A glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen introduction tube was charged with 500 parts by weight of hexyl carbitol, and the mixture was heated to 110 ° C. with stirring in a nitrogen stream, and then hexyl carbitol 250 wt. A mixed solution of 100 parts by weight of dodecyl methacrylate, 100 parts by weight of 2-ethylhexyl acrylate, 45 parts by weight of butyl acrylate, 5 parts by weight of methacrylic acid, and 20 parts by weight of AIBN was added dropwise. The reaction was further continued for 4 hours while maintaining the temperature at 100 ° C., and then unreacted substances were distilled off under reduced pressure to obtain an acrylic resin 3.

Examples 1-3 and Comparative Examples 1-2
(Preparation of flux composition)
Each component of the flux shown in Table 1 (the amount used of each component is parts by weight) was charged in a container, heated and dissolved at about 200 ° C., and then cooled to obtain a cream solder flux.

(Preparation of cream solder composition)
89 parts by weight of solder powder (Sn—Ag—Cu alloy having a particle size of 20 to 40 μm, Sn / Ag / Cu content is 96.5 wt% / 3 wt% / 0.5 wt%) 11 parts by weight of each flux composition prepared by the method was placed in a container and stirred to prepare a cream solder composition.

(Evaluation)
(Cooling cycle test)
After the cream solder composition obtained by the above method is printed on the QFP pattern provided on the glass epoxy substrate and reflowed, the cycle is -40 ° C, 30 minutes, 125 ° C, 30 minutes, 1000-2500. The presence or absence of cracks in the flux residue film after the cooling / heating cycle was observed. Judgment criteria are as follows. The results are shown in Table 1.
○: Good (no crack), △: Usable (crack is observed, but does not penetrate to the substrate surface or solder surface), ×: Bad (crack penetrates to the substrate surface or solder surface)

(Insulation resistance test)
After printing the cream solder composition on a comb-shaped electrode substrate JISII type (no resist) and reflowing it, putting it in a constant temperature and humidity chamber at a temperature of 85 ° C and a relative humidity of 85%, the insulation resistance value after 1000 hours Measured using a meter.
○: 1 × 10 ⁹ Ω or more ×: 1 × 10 ⁸ Ω or less

(Solderability)
Conforms to “JIS Z 3284 Annex 10 Wetting Efficacy and Dewetting Test”. Judgment criteria followed the extent of spread. The results are shown in Table 1.
○: Spread degree category 2 or more ×: Spread degree category 3 or less

(Glass-transition temperature)
Conforms to “JIS K7121 Plastic Dislocation Temperature Measurement Method”. After printing and reflowing the cream solder composition, 10 mg of the flux residue film was used as a sample, and measured using a differential scanning calorimeter (DSC220C manufactured by Seiko Denshi Kogyo Co., Ltd.) at a temperature rising rate of 10 ° C./second. The intersection point was determined by the tangent method to determine the glass transition temperature.

In the table, hydrogenated rosin is manufactured by Arakawa Chemical Industries, Ltd., trade name “KR-614”, and polymerized rosin is manufactured by Arakawa Chemical Industries, Ltd., trade name “China Polymerized Rosin 140”, polyether ester amide resin. Is a reaction product of linear diamine, polymerized fatty acid and polyethylene glycol, having a glass transition temperature of −60 ° C. and a number average molecular weight of 30000 (polystyrene conversion value by gel permeation chromatography), hydrogenated dimer acid is Unikema The product name “Pripol 1010” manufactured by the company, and the castor wax made by Toyokuni Oil Co., Ltd. were used as the hardened castor oil.

Claims (2)

The glass transition temperature of the flux residue film formed after soldering containing rosin (A), acrylic resin (B), activator (C), thixotropic agent (D) and solvent (E) is -100 to -30. A flux for cream solder at a temperature of 0 ° C., wherein the rosin (A) contains a polymerized rosin and a hydrogenated rosin . A cream solder comprising the solder powder and the cream solder flux according to claim 1.