KR101862723B1 - Rosin based flux for solder paste - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rosin flux for solder which is substantially free from scattering during soldering and at the same time can suppress the heating slump of the solder paste.
A rosin derivative hydrate (A) containing maleopimaric acid anhydride (a-1) and having a melt viscosity of 100 to 1,000 mPa · s / 180 ° C. is used as a base material.

Description

[0001] Rosin based flux solder paste for solder [

The present invention relates to rosin-based fluxes and solder pastes for solder.

Solder paste is used when soldering an electronic component such as an IC, a capacitor, or a resistor to an electrode on a printed circuit board. The solder paste is composed of a solder powder and a flux composition. As the flux composition, a rosin or a derivative thereof is generally used as a base material. However, since these are thermoplastic raw materials, there is a case where a heating slump occurs in the solder paste at a high temperature during soldering. Particularly, when the solder powder is made of a solder alloy not containing lead, a solder is likely to be generated under a high temperature, thereby causing a heating slump. As a result, a small number of fine solder balls may be formed around the electrode, or bridges may be generated between the electrodes, resulting in a short circuit.

In addition, since the rosin contains various low-boiling components, the flux component is scattered from the solder paste when soldered, and is attached to the periphery of the terminal electrode to contaminate the surface of the implemented substrate or cause defective insulation. For this reason, a flux recovery device is provided in the reflux furnace or the implemented substrate is cleaned, but this leads to a complicated manufacturing process or a high cost.

As a method for preventing the heating slump, there is known a flux (JP-A-2009-154170) in which a hydride of an alcohol-modified dicyclopentadiene resin is used as a base resin instead of a rosin, but the effect is not sufficient. As for the scattering of the flux, a flux using a distillation rosin in which the content of the low boiling point component is adjusted to less than 7 wt% as the rosin base resin has been proposed (Japanese Patent Laid-Open Publication No. 2008-62241) , A large number of solder balls tend to be generated.

The main object of the present invention is to provide a rosin-based flux which can suppress the heating slump of the solder paste and hardly scatter in soldering.

As a result of intensive studies, the present inventors have found that a rosin derivative (a-1) containing maleopimaric acid anhydride (a-1) represented by the following structural formula (1) and having a melt viscosity of 100 to 1000 mPa · s / It has been found that the above problem can be solved by the flux containing the hydride (A).

[Chemical Formula 1]

(In the formula 1,

The dashed line means that carbon-carbon bonds may be present at that position).

According to the rosin flux for soldering (hereinafter, simply referred to as flux) of the present invention, it is possible to obtain a solder paste having little heat scattering and scattering of flux components when soldering. Further, since the solder joint portion is covered with the flux residue having excellent crack resistance, migration due to, for example, moisture hardly occurs. In addition, the coating film is excellent in color tone and excellent in finishing feeling and visibility of the implemented substrate. In addition, such an effect can be obtained in the same manner even when a solder not containing lead having a high melting point is used, and the flux of the present invention is particularly suitable for a solder containing no lead. On the other hand, the rosin flux for soldering of the present invention is also very suitable as a post flux for coating a terminal electrode or a flux used for soldering solder.

The flux of the present invention is a rosin derivative containing as a base a maleopimaric acid anhydride (a-1) (hereinafter referred to as a component (a-1)) represented by the following structural formula (1) (A) (hereinafter, referred to as component (A)).

(In the formula 1,

The dashed line indicates that carbon-carbon bonds may be present at that position.)

The formula 1 specifically means maleic anhydride maleic anhydride represented by the following structural formula (1-2) and / or maleic anhydride maleic anhydride represented by the following structural formula (1-3).

The method for producing the component (A) is not particularly limited, and examples thereof include (i) a method of hydrogenating a Diels-Alder reaction product of an α, β-unsaturated dicarboxylic acid and a rosin, (Ii) a method of using hydrides of modified acids (see US Patent No. 2,628,226) isolated from the above-mentioned Diels-Alder reaction by a known method, (iii) isolating the compound from rosins by a known method (See, for example, J. Am. Chem. Soc. 70, 334 (1948) and the like) and a hydride of a Diels-Alder reaction of?,? Unsaturated dicarboxylic acids . The method (i) is industrially simple, and the method will be described below.

Examples of the?,? unsaturated dicarboxylic acids include maleic anhydride, maleic acid, and fumaric acid. Examples of the rosins include raw rosins such as gum rosin, wood rosin, and tall oil rosin. On the other hand, the raw material rosin is purified by means of a vacuum distillation method, a steam distillation method, an extraction method, a recrystallization method or the like from the viewpoints of heat slump resistance, suppression of solder ball generation, color tone of flux residue, (Hereinafter referred to as purified rosin) is preferably used.

The conditions of the above-mentioned refining means are not particularly limited. For example, in the case of the vacuum distillation method, the temperature is usually about 200 to 300 DEG C and about 0.01 to 3 kPa. In the case of the steam distillation method, the steam is blown into the reaction system at a temperature of about 200 to 300 DEG C and pressurized to about 0.1 to 1 MPa at normal pressure. In the case of the extraction method, the rosin is extracted with an aqueous alkali solution, the undissolved product which is not dissolved in the aqueous solution is extracted with various organic solvents, and the remaining aqueous layer is neutralized. In the recrystallization method, the desired rosin can be obtained by dissolving the rosin in an organic solvent as a good solvent, then removing the organic solvent by distillation to produce a concentrated solution, and further adding an organic solvent as a poor solvent. Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; Ketones such as acetone and methyl ethyl ketone; aliphatic hydrocarbons such as n-hexane, n-heptane and isooctane; Alicyclic hydrocarbons such as cyclohexane and decalin, and the like.

The Diels-Alder reaction can be obtained by reacting the above-mentioned?,? Unsaturated dicarboxylic acids and rosin at a temperature of usually 180 to 240 占 폚 for about 1 to 9 hours. The amount of the two components to be used may be appropriately determined in consideration of the content of the component (a-1) in the component (A), but usually the amount of the?,? Unsaturated dicarboxylic acids Is about 30 to 100 mol%, preferably 55 to 70 mol%. Further, in order to suppress the coloring of the desired Diels Alder reaction product and improve the color tone of the flux residue film, it is preferable that the reaction vessel is made to have a closed structure and an inert gas stream such as nitrogen is spread. In the reaction, various known catalysts can be used, for example, Lewis acids such as zinc chloride, iron chloride and tin chloride, Bronsted acids such as para-toluenesulfonic acid and methanesulfonic acid, Is usually about 0.01 to 10% by weight.

The component (A) can be obtained by hydrogenating the diels-alder reactant obtained in the above by various known methods. Specifically, an electric Diels-Alder reaction product is hydrogenated in the presence of a hydrogenation catalyst at a temperature of about 100 to 300 DEG C (preferably 150 to 260 DEG C) at about 1 to 25 MPa (preferably 5 to 20 MPa) Hydrogenation may be carried out under pressure. Examples of the hydrogenation catalyst include supported catalysts such as palladium carbon, rhodium carbon, ruthenium carbon and platinum carbon; metal powders such as nickel and platinum; and oxides such as oxo and iron oxides. The amount of the hydrogenation catalyst used is usually about 0.01 to 10% by weight, preferably 0.1 to 5% by weight based on the Diels Alder reaction. On the other hand, if necessary, the organic solvent may be used as a reaction solvent. On the other hand, the component (A) is preferably further purified by the above-mentioned purification means from the viewpoint of prevention of flux scattering and the like.

The component (A) usually has a melt viscosity of about 100 to 1,000 mPa 占 퐏 180 占 폚, preferably 200 to 600 mPa 占 퐏 180 占 폚, from the viewpoints of heat slump, flux scattering and cracking resistance of flux residue. The melt viscosity can be controlled by, for example, the content of the component (a-1) in the component (A). On the other hand, the "melt viscosity" refers to a value measured by a B-type viscometer while the component (A) is melted at 180 ° C.

The content of the component (a-1) in the component (A) is usually 30% by weight or more, preferably 40 to 75% by weight in consideration of heat slump resistance, flux scattering inhibition and cracking resistance of the flux residue. The component (A) may also contain other resin acids such as dihydroabietic acid (hereinafter sometimes referred to as component (a-2)), and the content thereof is usually 70 By weight, preferably from 10 to 25% by weight. Examples of the resin acids other than the component (a-1) and the component (a-2) include abietic acid and maleopimaric acid, and the content thereof is usually less than 70% by weight, preferably 50% %.

The component (A) may contain a low-molecular-weight component (hereinafter referred to simply as a low-molecular-weight component) having a molecular weight of usually 280 or less, such as impurities derived from various catalysts or raw material rosin, But is usually 3% by weight or less from the viewpoint of suppressing the scattering of the flux.

The content of various resin acids and low molecular weight components in the component (A) can be specified by various known analytical methods, for example, by maleomorphomalic anhydride (GPC) or gas chromatography (GC). For example, in the case of GPC, the content (X% by weight) of resin acids can be obtained by the following formula.

X = [(area of the peak belonging to the resin acid to be measured) / (peak area of the entire resin acid component containing the resin acid)] x 100

The structure of the component (a-1) and other resin acids in the component (A) can be identified by various known means, for example, the IR method or the NMR method.

The other physical properties of the component (A) are not particularly limited. For example, the theoretical acid value based on the tertiary carboxyl group is usually about 130 to 160 mgKOH / g, and preferably 134 to 154 mgKOH / g. By using the component (A) of the theoretical acid value, effects such as suppression of heat slump, suppression of flux scattering, and crack resistance of the flux residue film can be obtained in a balanced manner. On the other hand, the "theoretical acid value based on the tertiary carboxyl group" is a calculated value representing the number of mg of potassium hydroxide reacting equivalently with the tertiary carboxyl group derived from various resin acids in the component (A).

Further, (A) component (hereinafter referred to as unit a carboxyl group molar concentration) the molar concentration based on the carboxyl group is usually ^{2.2 × 10 -3 ~3.2 × 10 -3} mol / g , preferably about 2.4 × 10 ^-3 ~ 3 x 10 <" ³ > mol / g. The molar concentration of the unit carboxyl group means the number of moles of the carboxyl group (-COOH) per 1 g of the component (A) (in terms of solid content). By using the component (A), heat slump suppression, flux scattering suppression, It is possible to obtain a balanced effect such as sex. The molar concentration of the unit carboxyl group is an actual value and is determined as follows.

Molar concentration of the unit carboxyl group (mol / g) = Y - (Y - Z) 2

(Y calculation method)

0.3 g of the component (A) is dissolved in 50 ml of acetone to prepare an acetone solution. Next, 25 ml of an aqueous solution of potassium hydroxide (concentration 1.0 × 10 ^-4 mol / ml; reagent for capacity analysis, Wako Junyaku Kogyo Co., Ltd.) was added to the above acetone solution, stirred, left for 10 minutes do. Then, a few drops of phenolphthalein were added to the acetone solution after being left standing, and neutralization titration was carried out using an aqueous hydrochloric acid solution (concentration 1.0 × 10 ^-4 mol / ml) to reach an equivalent point (point at which the solution changed from magenta to colorless) Record an appropriate amount (ml). Then, Y is calculated by the following equation (1).

(Mol / g) = ([Amount of aqueous solution of potassium hydroxide (ml) - amount of hydrochloric acid (ml)] × concentration of aqueous solution of potassium hydroxide (mol / ml)} /

(Calculation of Z)

Ethanol and toluene were mixed at a weight ratio of 1: 2 to prepare an ethanol / toluene solvent. Then, 1 g of the component (A) is dissolved in the ethanol / toluene solvent to prepare a toluene-ethanol solution of the component (A). Then, a few drops of a phenolphthalein solution were added to the solution, and an ethanolic potassium hydroxide solution (concentration 5.0 × 10 ^-4 mol / ml; reagent for capacity analysis, Wako Junyaku Kogyo Co., Ltd.) , And the titration amount (ml) at which the equivalent point (the point at which the solution was changed from colorless to magenta) was recorded. Then, Z is calculated by the following equation (2).

(G) (mol / g) = (amount of the ethanolic potassium hydroxide solution (ml) x concentration of the ethanolic potassium hydroxide solution (mol / ml)

From the viewpoints of thermal slump resistance, flux scattering inhibition and cracking resistance of the flux residue, the softening point of the component (A) (the value measured by the rolling method specified in JIS K 59202) And is generally about 100 to 150 캜, preferably 110 to 130 캜.

In particular, from the viewpoint of the color tone of the flux residue, the color tone of the component (A) is usually Gardner 2 or less, preferably Gardner 1 or less to Hazen 50. (Hazen color tone is JIS K 0071-1, Gardner color tone is This is the value measured by JIS K 0071-2.)

The flux of the present invention may contain a thixotropic agent (B) (hereinafter referred to as component (B)) and a flux solvent (C) (hereinafter referred to as component (C)) in addition to the component (A) (Hereinafter referred to as component (E)) and various additives (hereinafter referred to as component (F)) other than the active agent (D) and the component (A) .

Examples of the component (B) include an amphoteric thixotropic agent such as hardened castor oil, beeswax and carnauba wax, or an amide thixotropic agent such as stearic acid amide and hydroxystearic acid ethylene bisamide. May be used alone or in combination of two or more.

Examples of the component (C) include alkylene glycol monoethers such as diethylene glycol monohexyl ether and diethylene glycol monobutyl ether; Other alcohols such as hexyl glycol, octanediol, ethylhexyl glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2- (2-n-butoxyethoxy) ethanol and terpineol; Esters such as butyl benzoate, diethyl adipate, dioctyl sebacate and 2- (2-n-butoxyethoxy) ethyl acetate; Hydrocarbons such as dodecane and tetradecene; Pyrrolidone such as N-methyl-2-pyrrolidone, etc. These may be used singly or in combination of two or more. Of these, the alkylene glycol monoethers and / or esters are preferable. Particularly, considering the soldering temperature, components (C) (particularly, alkylene glycol monoethers and / or esters) having a boiling point in the range of about 150 to 300 캜, preferably 220 to 270 캜, are preferable.

Examples of the component (D) include hydrogen halides of amines such as ethylamine hydrobromide and cyclohexylamine hydrobromide; (Dodecanedioic acid, Dimer acid), which do not contain a halogen atom, such as succinic acid, benzoic acid, benzoic acid, adipic acid, glutaric acid, palmitic acid, stearic acid, picolinic acid, azelaic acid, sebacic acid, Aliphatic organic carboxylic acids; N, N'-bis (4-aminobutyl) -1,2-ethanediamine, triethylenetetramine, N, N ' ) Organic diamines such as piperazine; Bromoacetic acid, 2-bromo acetic acid, 2-bromo succinic acid, 2-bromo succinic acid, 2-bromo succinic acid, Bromodicarboxylic acids such as moiodiphenic acid; Propanol, 3-bromo-1-propanol, 3-bromo-1,2-propanediol, 1,4-dibromo-2-butanol , 1,3-dibromo-2-propanol, 2,3-dibromo-1-propanol, 1,4-dibromo-2,3-butanediol, 2,3- Bromo-diols such as butene diol and 2,3-dibromo-2-butene-1,4-diol; Bromoalkanes such as 1,2,3,4-tetrabromobutane and 1,2-dibromo-1-phenylethane; Methyl-1-butene, 1,4-dibromobutene, 1-bromo-1-propene, 2,3-dibromopropene, 1,2- Bromoalcane; Stearyloxybenzyl bromide, 4-stearylbenzyl bromide, 4-bromomethylbenzyl stearate, 4-stearoylaminobenzyl bromide, 2,4-bisbromomethyl 4-palmitoyloxybenzylbromide, 4-myristoyloxybenzylbromide, 4-lauroyloxyl bromide, 4-undecanoyloxybenzyl bromide and the like can be used alone or in combination.

Examples of the component (E) include the above-mentioned raw material rosin or a Diels-Alder reaction product obtained from the raw material rosin and an?,? Unsaturated monocarboxylic acid (acrylic acid, methacrylic acid, etc.), a hydride thereof, Acrylic resin, polyimide resin, polyamide resin (nylon resin), polyester resin (polyimide resin), polyamide resin (nylon resin), and the like, in addition to the rosin based materials other than the component (A), such as a raw material rosin hydride, disproportionated rosin, A synthetic resin such as a resin, a polyacrylonitrile resin, a vinyl chloride resin, a vinyl acetate resin, a polyolefin resin, a fluorine resin, and an ABS resin can be used. These resins can be used singly or in combination of two or more kinds .

Examples of the component (F) include additives such as antioxidants, anti-fogging agents, and gloss removing agents.

The amount of the component (A) to the component (D) to be used is not particularly limited, but is generally as follows in view of the heating slump, flux scattering, crack resistance of the flux residue coating, etc. Do not.)

(A): about 30 to 75% by weight, preferably about 40 to 55% by weight,

(B): about 0.1 to 10 wt%, preferably about 3 to 10 wt%

(C): about 20 to 69.9% by weight, preferably about 30 to 56.9% by weight,

(D): about 0 to 10% by weight, preferably about 0.1 to 5% by weight,

The amounts of the component (E) and the component (F) in the flux of the present invention are not particularly limited, but are generally as follows.

Component (E): less than 30% by weight, preferably less than 25% by weight

Component (F): less than 10% by weight, preferably less than 5% by weight

The solder paste of the present invention is obtained by mixing the flux and the solder powder of the present invention with various known means (planetary mill, etc.), and the amount thereof is usually about 5 to 20 parts by weight and 80 to 95 parts by weight It is about degree.

Examples of the solder powder include conventional soldering powder such as Sn-Pb solder powder, Sn solder powder, Sn-Ag based solder powder, Sn-Cu based solder powder, Sn-Zn based solder powder, Sn- Ag-Cu-S based solder powder, Sn-Ag-Cu-S based solder powder, Sn-Ag-Cu-based solder powder, Sn-Ag- Solder powder such as solder powder, Sn-Ag-Cu-Ni-Ge-based solder powder, and the like. On the other hand, the flux that influences the present invention works very well even at the melting temperature of the solder not containing lead, and it is possible to suppress the generation of the heated slump, the solder ball, cracks of the flux residue, Is preferably a solder powder not containing lead, particularly a solder powder not containing Sn-based lead.

<Examples>

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

Further, the "melt viscosity" in each production example is a value obtained by a commercially available B8M-type viscometer (trade name "VISCOMETER", TOKIMEC Co., Ltd., rotor No. HM-1), "content of maleopimaric anhydride" And "content of low molecular weight components" were measured using a commercially available gel permeation chromatograph (product name: "High-speed GPC system HLC-8220", Tosoh Corporation, column name "TSK-GEL G1000HXL" (Tetrahydrofuran), and the "content of dihydroabietin acid" means a value calculated by a commercially available gas chromatograph (product name: GC7890, manufactured by Agilent).

&Lt; Preparation of component (A) >

Production Example 1

Process (1): Purification

The crude gum rosin (measured acid value 171 mgKOH / g, unit carboxyl group mole concentration 3.2 x ^10-3 mol / g, softening point 74 deg. C, Gardner 6, made in China) was placed in a vacuum distillation vessel and under reduced pressure of 0.4 kPa Distilled to obtain purified rosin (measured acid value 177 mgKOH / g, softening point 80 캜, Gardner 3).

Step (2): Diels-Alder reaction

Then, 700 g of the above-mentioned purified rosin and 154 g of maleic anhydride were placed in another distillation distillation vessel and reacted at 220 ° C. for 4 hours while stirring in a nitrogen gas stream. The unreacted material was then removed under a reduced pressure of 4 kPa to obtain a rosin derivative A theoretical acid value of 144 mgKOH / g, a molar concentration of the unit carboxyl group of 2.7 x ^10-3 mol / g, a softening point of 121 deg. C, Gardner 8).

Step (3): Hydrogenation reaction

Next, 500 g of the rosin derivative and 6.0 g of 5% palladium carbon (moisture content: 50%) were placed in a 1 liter rotary autoclave, oxygen in the system was removed, the pressure was increased to 10 MPa with hydrogen, And hydrogenated at the same temperature for 3 hours to obtain a rosin derivative hydride (theoretical acid value of 144 mgKOH / g, a molar concentration of the unit carboxyl group of 2.7 × 10 ^-3 mol / g and a softening point of 120 ° C.).

Step (4): Purification

Then, 400 g of the above rosin derivative hydride and 200 g of xylene were placed in a reaction vessel, heated and dissolved, and 150 g of xylene was distilled off. Then, 150 g of cyclohexane was added, and the mixture was cooled to room temperature. When the amount of crystals reached about 40 g, the supernatant was transferred to another reaction vessel and further recrystallized at room temperature. Then, after adding to remove the supernatant and washed with 20g of cyclohexane, by distilling off the cyclohexane melt viscosity 361 mPa · s / 180 ℃, theoretical acid value of 144 mgKOH / g, a carboxyl unit molar concentration of 2.7 × 10 ^-3 (a-1) is about 66% by weight, the content of dihydroabietic acid (a-2) is about 17% by weight, the content of maleic anhydride (Hereinafter referred to as (A-1) component) of a rosin derivative hydride (A-1) having a composition of 0.7% by weight. Physical properties and the like are shown in Table 1.

Production Example 2

A rosin derivative hydrate (A-2) (hereinafter referred to as (A-2) component) was obtained in the same manner as in the step (2) of Production Example 1, except that the amount of maleic anhydride was changed to 77 g. Physical properties and the like are shown in Table 1.

Production Example 3

(A-3) (hereinafter referred to as (A-3)) was obtained in the same manner as in the step (3) of Production Example 1 except that 12.0 g of 5% palladium carbon (moisture content 50% Quot; component &quot;). Physical properties and the like are shown in Table 1.

Production Example 4

(A-4) (hereinafter referred to as (A-4)) was obtained in the same manner as in Production Example 2, except that 12.0 g of 5% palladium carbon (water content 50% Quot; component &quot;). Physical properties and the like are shown in Table 1.

Production Example 5

A rosin derivative hydrate (A-5) (hereinafter referred to as (A-5) component) was obtained in the same manner as in the step (2) of Production Example 1, except that the amount of maleic anhydride was changed to 160 g. Physical properties and the like are shown in Table 1.

Production Example 6

(A-6) (hereinafter, referred to as (A-6)) was obtained in the same manner as in Production Example 2, except that 12.0 g of 5% palladium carbon (water content 50% Quot; component &quot;). Physical properties and the like are shown in Table 1.

Production Example 7

A rosin derivative hydrate (A-7) (hereinafter referred to as component (A-7)) was obtained in the same manner as in Example 1 except that the crude rosin was not used in the step (2) ). Physical properties and the like are shown in Table 1.

Comparative Preparation Example 1

A rosin derivative hydride (X-1) (hereinafter referred to as a component (X-1)) was obtained in the same manner as in the step (2) of Production Example 1 except that 105 g of acrylic acid was used instead of 154 g of maleic anhydride. ). (X-1) are shown in Table 1. &lt; tb &gt;&lt; TABLE &gt;

&Lt; Preparation of flux &

Example 1

50 parts of the component (A-1), 5 parts of 12-hydroxystearic acid bisamide as the component (B) and 45 parts of diethylene glycol monohexyl ether as the component (C) were heated and dissolved to prepare a flux did.

Example 2

A flux was produced in the same manner as in Example 1 except that the component (A-2) was used in place of the component (A-1).

Example 3

A flux was produced in the same manner as in Example 1 except that the component (A-3) was used instead of the component (A-1).

Example 4

A flux was produced in the same manner as in Example 1 except that the component (A-4) was used instead of the component (A-1).

Example 5

A flux was produced in the same manner as in Example 1 except that the component (A-5) was used instead of the component (A-1).

Example 6

A flux was produced in the same manner as in Example 1 except that the component (A-6) was used instead of the component (A-1).

Example 7

A flux was produced in the same manner as in Example 1 except that the component (A-7) was used in place of the component (A-1).

Example 8

A flux was produced in the same manner as in Example 1 except that 17-hydroxystearic acid ethylenebisamide was used instead of 12-hydroxystearic acid ethylenebisamide as the component (B).

Example 9

A flux was produced in the same manner as in Example 1 except that cured castor oil was used instead of 12-hydroxystearic acid ethylene bisamide as the component (B).

Example 10

In addition to the flux obtained in Example 1, 5 parts of adipic acid as the component (D) was blended to prepare a flux.

Example 11

In addition to the flux obtained in Example 1, one part of trans 2, 3, dibromo-1,4-butanediol was blended as component (D) to prepare a flux.

Example 12

A flux was produced in the same manner as in Example 1 except that 3 parts of N, N-bis (3-aminopropyl) ethylenediamine was used as the component (D).

Comparative Example 1

A flux was produced in the same manner as in Example 1 except that the component (A-1) was replaced with the component (X-1).

Comparative Example 2

Except that the commercially available hydrogenated rosin (Arakawa Chemical Industries Ltd., "HiPeil CH", hereinafter referred to as (X-2) component) was used in place of the component (A-1) The flux was produced in the same manner. On the other hand, the physical properties and the like of the component (X-2) are shown in Table 1.

Comparative Example 3

(Hereinafter referred to as (X-3) component) obtained in the step (1) of Production Example 1 was used instead of the component (A-1) . On the other hand, the physical properties and the like of the component (X-3) are shown in Table 1.

Comparative Example 4

Except that the rosin derivative (hereinafter referred to as the (X-4) component) obtained in the step (2) of Production Example 1 was used in place of the component (A-1) . On the other hand, the physical properties and the like of the component (X-4) are shown in Table 1.

Comparative Example 5

(Ronjisu R., distillation, un-digestion, hereinafter referred to as "component (X-5)") was obtained in the same manner as in Example 1, except that the disproportionated rosin (Arakawa Chemical Industries, ) Was used as a dispersing agent to prepare a flux. On the other hand, the physical properties and the like of the component (X-5) are shown in Table 1.

Comparative Example 6

(Araday R-140), distilled and un-distilled, hereinafter referred to as (X-6) component (A-1) was obtained in the same manner as in Example 1 except that a commercially available polymerization rosin (Arakawa Chemical Industries, ) Was used in place of the above-mentioned flux. On the other hand, the physical properties and the like of the component (X-6) are shown in Table 1.

Comparative Example 7

("CG-WW", product of Arakawa Chemical Industries, Ltd., distillation, un-distillation, hereinafter referred to as "component (X-7)") was obtained in the same manner as in Example 1, ) Was used instead of the above-mentioned flux. On the other hand, the physical properties and the like of the component (X-7) are shown in Table 1.

materials Melting point (mPa 占 퐏 / 180 占 폚) Molar concentration of unit carboxyl group (mol / g) Theoretical acid value (mg KOH / g) Softening point
(° C) hue (a-1)
(weight%) (a-2)
(weight%) Low molecular weight component
(weight%) (B) (C) (D) Example 1 (A-1) 361 2.7 × 10 ^-3 144 120 H150 66 17 0.7 12-HSBA DEGMHE - Example 2 (A-2) 125 2.9 × 10 ^-3 158 111 H150 36 17 1.9 12-HSBA DEGMHE - Example 3 (A-3) 340 2.7 × 10 ^-3 143 121 H150 64 15 1.1 12-HSBA DEGMHE - Example 4 (A-4) 130 2.9 × 10 ^-3 157 112 H150 38 25 1.8 12-HSBA DEGMHE - Example 5 (A-5) 850 2.6 x 10 ^-3 139 130 H150 78 12 1.5 12-HSBA DEGMHE - Example 6 (A-6) 830 2.6 x 10 ^-3 138 128 H150 78 15 1.4 12-HSBA DEGMHE - Example 7 (A-7) 350 2.6 x 10 ^-3 140 122 H300 63 18 3.7 12-HSBA DEGMHE - Example 8 (A-1) 361 2.7 × 10 ^-3 144 120 H150 66 17 0.7 17-HSBA DEGMHE - Example 9 (A-1) 361 2.7 × 10 ^-3 144 120 H150 66 17 0.7 C-WAX DEGMHE - Example 10 (A-1) 361 2.7 × 10 ^-3 144 120 H150 66 17 0.7 12-HSBA DEGMHE AA Example 11 (A-1) 361 2.7 × 10 ^-3 144 120 H150 66 17 0.7 12-HSBA DEGMHE DBBD Example 12 (A-1) 361 2.7 × 10 ^-3 144 120 H150 66 17 0.7 12-HSBA DEGMHE BAPED Comparative Example 1 (X-1) 750 4.3 × 10 ^-3 152 133 H100 0 24 2.0 12-HSBA DEGMHE - Comparative Example 2 (X-2) 70 3.2 × 10 ^-3 170 77 G4 0 10 4.5 12-HSBA DEGMHE - Comparative Example 3 (X-3) 65 3.2 × 10 ^-3 177 80 G3 0 5 2.5 12-HSBA DEGMHE - Comparative Example 4 (X-4) 650 2.7 × 10 ^-3 144 121 G8 67 12 1.0 12-HSBA DEGMHE - Comparative Example 5 (X-5) 75 2.9 × 10 ^-3 156 80 G6 0 63 6.4 12-HSBA DEGMHE - Comparative Example 6 (X-6) 5800 2.6 x 10 ^-3 147 140 G6 0 38 3.7 12-HSBA DEGMHE - Comparative Example 7 (X-7) 70 3.2 × 10 ^-3 169 77 G6 0 4 4.4 12-HSBA DEGMHE -

In Table 1, the symbols have the following meanings.

H: Hazel Color

G: Gardner color

12-HSBA: 12-hydroxystearic acid ethylene bisamide

17-HSBA: 17-hydroxystearic acid ethylene bisamide

C-WAX: hardened castor oil

DEGMHE: diethylene glycol monohexyl ether

AA: adipic acid

DBBD: trans 2,3 dibromo 1,4-butanediol

BAPED: N, N-bis (3-aminopropyl) ethylenediamine

In addition, the components (X-3) to (X-7) are not all hydrides.

The molar unit carboxyl group of the components (X-1) to (X-7) is an actual value obtained based on the method described in paragraphs [0023] to [0027] of this specification.

Comparative Example 8

A mixture (45 parts) of the component (X-1) and 5 parts of the alcohol-modified dicyclopentadiene resin hydride (softening point: 120 占 폚, color tone H200, trade name: KR- 1842 &quot;, Arakawa Chemical Industries, Ltd., hereinafter referred to as (X-8) component).

(Preparation of solder paste)

10 parts of the flux of Example 1 and 90 parts of lead-free solder powder (Sn-Ag-Cu alloy; 96.5% by weight / 3% by weight / 0.5% by weight and average particle diameter of 25 to 38 탆) were stirred in a beaker Solder paste. The fluxes of Examples 2 to 12 and Comparative Examples 1 to 8 were also carried out in the same manner to produce a solder paste.

<Performance evaluation>

(Heating slump test)

The printed board obtained by screen printing the solder paste influencing Example 1 in a row in a row in a line was subjected to a slump test in accordance with "JIS Z3284 Annex 8 Heating" on a copper substrate. The printed board was heated in a nitrogen reflux furnace for 160 seconds Preheating condition: 180 占 폚 for 100 seconds, heating condition: 240 占 폚 for about 60 seconds), and the degree of the heating slump was confirmed by visually confirming the change of the shape of the solder paste. The solder paste affecting Examples 2 to 12 and Comparative Examples 1 to 8 was evaluated in the same manner.

4: very difficult to slump; Less than 0.6 mm gap

3: It is difficult to slump; 0.6 mm or more and less than 0.7 mm

2: It is somewhat susceptible to slump; 0.7 mm or more to less than 0.8 mm

1: easy to slump; Not more than 0.8 mm

(Solderability)

The solderability (wettability) of each of the solder pastes of Examples 1 to 12 and Comparative Examples 1 to 8 was evaluated in accordance with "Wettability and dewetting test according to JIS Z3284 Annex 10" (1 or 2). &Quot; 3 &quot; is shown in Tables 2 and 3.

(Flux scattering, solder balls, cracks, color tone)

The solder paste according to Example 1 was screen-printed on a copper substrate, and the soldering area was observed with a microscope VW-6000 (Keyens: 30 times) to determine the degree of flux scattering, generation of solder balls, and flux residue The presence of cracks and the color tone of the flux residue were visually determined based on the following criteria. On the other hand, the occurrence of the solder balls was in accordance with &quot; JIS Z3284 Annex 11 Solder Ball Test &quot;. The solder paste relating to Examples 2 to 12 and Comparative Examples 1 to 8 was evaluated in the same manner.

3: No scattering

2: There is a little scattering

1: There is a lot of scattering

2: good; Less than 10 solder balls

1: poor; More than 10 solder balls

3: No crack

2: There is a little crack

1: There are many cracks

3: Colorless transparent

2: A little coloration

1: In color

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 materials (A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) (X-1) (X-2) Heating slump 4 3 4 3 4 4 3 One One Solderability 3 3 3 3 3 3 3 3 3 Flux scattering 3 3 3 3 3 3 2 3 One Solder ball 2 2 2 2 2 2 2 2 2 crack 3 3 3 3 2 2 3 One 3 hue 3 3 3 3 3 3 3 3 One

In Examples 1 to 7, since the flux of the present invention uses a hydride of a rosin derivative containing maleopimaric anhydride as a main component as a substrate, good results can be obtained in either evaluation. On the other hand, rosin derivatives and rosins not containing maleopimaric anhydride, such as Comparative Example 1 (acrylic acid modified rosin hydride) and Comparative Example 2 (hydrogenated rosin), may be heated slump, flux scattering, It can be seen that it is inferior in the sex and color tone.

Example 8 Example 9 Example 10 Example 11 Example 12 materials (A-1) (A-1) (A-1) (A-1) (A-1) Heating slump 4 4 4 3 4 Solderability 3 3 3 3 3 Flux scattering 3 3 3 3 2 Solder ball 2 2 2 2 2 crack 3 3 3 3 2 hue 3 3 3 3 3

Since the flux of the present invention uses the component (A) in Examples 8 to 12, good results can be obtained even when the flux is changed to another flux material.

Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 materials (X-3) (X-4) (X-5) (X-6) (X-7) (X-1)
(X-8) Heating slump 4 2 2 One 2 2 Solderability 3 3 3 3 3 3 Flux scattering One 3 One 3 One 3 Solder ball 2 One 2 One 2 One crack 3 3 3 One 3 One hue 2 One One One One 3

Comparative Example 5 (disproportionated rosin), Comparative Example 6 (polymerized rosin), and Comparative Example 7 (disproportionated rosin), Comparative Example 3 (non-hydrogenated refined rosin) , It can be seen that when these rosin base materials are not hydrogenated, it is difficult to achieve both the suppression of the heating slump and the prevention of the flux scattering, and the performance is also poor.

Further, in the result of Comparative Example 8, it can be seen that if a part of the rosin-based substrate is replaced with a petroleum resin-based substrate, the heating slump is somewhat improved, but cracks easily occur in the residue.

Claims (15)

A rosin derivative hydride (A) comprising maleopimaric acid anhydride (a-1) represented by the following formula (1), wherein the rosin derivative hydride (A) has a melt viscosity of 100 to 1,000 mPa · s / A rosin-based flux for a solder comprising a derivative hydride (A):
[Chemical Formula 1]

(In the formula 1,
The dashed line means that carbon-carbon bonds may be present at that position).
The method according to claim 1,
A rosin-based flux for solder characterized in that the content of the component (a-1) in the component (A) is 30% by weight or more.
3. The method of claim 2,
Wherein the component (A) further contains less than 70% by weight of dihydroabietic acid (a-2).
The method according to claim 1,
Wherein the content of the low molecular weight component having a molecular weight of 280 or less in the component (A) is 3 wt% or less.
The method according to claim 1,
Wherein the molar concentration based on the component carboxyl group of the component (A) is 2.2 x ^{10-3 to} 3.2 x ^10-3 mol / g moles.
The method according to claim 1,
Wherein the component (A) has a softening point of 100 to 150 占 폚.
The method according to claim 1,
Wherein the Gardner color tone of the component (A) is 2 or less.
The method according to claim 1,
Further comprising a thixotropic agent (B), a flux solvent (C) and an activator (D).
9. The method of claim 8,
Wherein the component (B) is at least one member selected from the group consisting of an animal and plant thixotropic agent and an amide thixotropic agent.
9. The method of claim 8,
Wherein the component (C) is at least one member selected from the group consisting of alkylene glycol monoethers having a boiling point of 150 to 300 캜 and esters having a boiling point of 150 to 300 캜.
9. The method of claim 8,
Wherein the activator (D) is at least one selected from the group consisting of an aliphatic organic carboxylic acid containing no halogen atom, an organic diamine, a bromodicarboxylic acid and a bromodiol.
The method according to any one of claims 8 to 11,
Wherein the rosin flux for soldering comprises the following components (A) to (D) in the following weight percentages:
(A): 30 to 75 wt%
(B): 0.1 to 10 wt%
Component (C): 20 to 69.9 wt%
Component (D): 0 to 10% by weight.
12. A solder paste containing the rosin-based flux for solder according to any one of claims 1 to 11 and a solder powder.
14. The method of claim 13,
Wherein the solder powder is a solder powder not containing lead.
15. The method of claim 14,
Wherein the solder powder not containing lead is a solder powder not containing an Sn-based lead.