KR20080086362A - Polymerized resin, polymerized resin ester and hydride thereof, and method for producing the same;flux for soldering, solder paste, adhesion-imparting resin, adhesion-imparting resin emulsion and adhesive agent composition - Google Patents

Abstract

A polymerized rosin is provided to realize excellent (heating) stability even when storing under a heating condition, to enable hydrogenation even after storing for a long time, and to obtain a hydrogenated polymerized rosin having a good color tone. A polymerized rosin(A1) is obtained by desulfurizing a polymerized rosin(A) prepared by using a sulfuric acid-based catalyst and having a sulfur content of less than 100 ppm except for the sulfur content in an antioxidant. A hydrogenated polymerized rosin is obtained by hydrogenating the polymerized rosin(A1) and has a sulfur content of less than 100 ppm except for the sulfur content in an antioxidant. A polymerized rosin ester is obtained by reacting the polymerized rosin(A), the polymerized rosin(A1) and an alcohol(B).

Description

Polymerized rosin, polymerized rosin esters and their hydrides and preparation methods thereof, soldering fluxes, solder pastes, tackifier resins, tackifier resin emulsions and point-adhesive formulations (polymerized resin, polymerized resin ester and hydride) and method for producing the same; flux for soldering, solder paste, adhesion-imparting resin, adhesion-imparting resin emulsion and adhesive agent composition}

The present invention relates to a polymerized rosin, a polymerized rosin ester, and a hydride thereof and a method for manufacturing the same, a solder flux, a solder paste, a tackifier resin, a tackifier resin emulsion, and a spot / adhesive composition. To

Polymerized rosin is a resin obtained by polymerizing rosin and has a high softening point compared to rosin and the like, and thus is stabilized as it is or by hydrogenation, and is widely used as a soldering flux or a tackifier.

Conventionally, as a method for producing a polymerized rosin, a method using zinc chloride or sulfuric acid has been adopted because of its excellent productivity, but various methods have been studied in order to find a more productive and simpler method.

In Patent Document 1, for example, a technique using a polymer having a pendant sulfonic acid group as a catalyst is disclosed. Patent Document 2 discloses a technique using aliphatic sulfonic acid as a catalyst.

By the way, Patent Document 3 discloses a technique related to a method for producing a colorless polymerization rosin. Such a production method uses purified rosin, but is a method for producing a colorless polymerization rosin by hydrogenation or disproportionation of conventional polymerization rosin containing sulfur content, and has an effect of improving color tone.

In addition, although polymerization rosin has recently been used as the flux for soldering, there is a merit that the appearance can be improved by using a soldering flux using a polymerization rosin having a good color tone, and the cleaning process can be omitted, and the color tone (after heating) And a good polymerization rosin. Patent Literature 4 discloses a technique related to a method for producing a colorless polymerization rosin ester. This production method is a method for producing colorless rosin esters by hydrogenating or disproportionating conventionally polymerized rosin esters containing sulfur, and has an effect of improving color tone.

Patent Document 1 US Patent Publication 4414146

Japanese Patent Application Laid-Open No. 2006-45396

Japanese Patent Application Laid-Open No. 2002-201433

Patent Document 4 Publication No. 2002-201434

However, since the techniques described in Cited References 1 and 2 are all produced using an acidic catalyst such as sulfuric acid as a method of good productivity, the resulting resin has a problem that sulfur content, which is thought to be due to the catalyst or a decomposition product of the catalyst, remains. (See Table 1 of Patent Document 2). In addition, the polymerization rosin obtained in this way has a problem that, if stored under heating, remarkably coloring or storing for a long period of time (about 2 months or more) cannot be sufficiently pale even after hydrogenation. Moreover, there exists a similar problem also about the polymerization rosin ester obtained using this polymerization rosin.

In addition, since the colorless polymerization rosin obtained by the techniques described in Cited Reference 3 and Cited Reference 4 performs hydrogenation or disproportionation, there is a problem that the use cannot be modified, for example, with unsaturated carboxylic acid or the like. In addition, such a method is to purify rosin, polymerize, esterify, and hydrogenate. In the case of using the polymerized rosin in advance and preserving it for a long time, the coloration may be insufficient. The use of such a polymerization rosin or the like also deteriorates the color tone and thermal stability of the point-adhesive agent.

The present invention has been made in view of the above problems, and the color tone is good, and even when stored under heating, the (heating) stability is good, and after storage for a long time, hydrogenation (bleaching) can be performed without any problem. Can be. Polymerized rosin and polymerized rosin esters and color tone, hydrogenated polymerized rosin and polymerized rosin ester with good heat stability, lead-free solder flux and solder paste with good color tone, color tone, good heat stability point, adhesive composition and water point It aims at providing an adhesive composition.

The present inventors have pursued the cause of not being sufficiently pale when hydrogenated after long-term storage, and as a result, sulfur content due to the remaining of the catalyst used in the production of the polymerized rosin is the cause of the polymerization rosin or the polymerized rosin ester. It has been found that the above problem can be solved by reducing the sulfur content included, and the present invention has been completed.

That is, the present invention is a polymerization rosin (A1) having a sulfur content of 100 ppm or less from the sulfur content of the antioxidant obtained by desulfurizing the polymerization rosin (A) obtained by using a sulfuric acid catalyst; Hydrogenated polymerization rosin whose content of the sulfur content which removed the sulfur content of the antioxidant obtained by hydrogenating the said polymerization rosin (A1) is 100 ppm or less; Polymerized rosin ester whose content of the sulfur content which removed the sulfur content of the antioxidant obtained by making the said polymerization rosin (A) and the said polymerization rosin (A1) and alcohols (B) react is 100 ppm or less; Polymerized rosin ester whose content of the sulfur content which removed the sulfur content of the antioxidant obtained by making superposition | polymerization rosin (A1) and alcohols (B) react is 100 ppm or less; Hydrogenation polymerization rosin ester whose content of the sulfur content which removed the sulfur content of the antioxidant obtained by hydrogenating the said polymerization rosin ester is 100 ppm or less; Method for producing the polymerization rosin (A1), characterized in that for desulfurizing the polymerization rosin (A); The desulfurization treatment is carried out at 100 to 300 in the presence of a desulfurization catalyst. A process for producing the hydrogenated polymerization rosin, characterized in that the polymerization rosin (A1) is hydrogenated; A method for producing a hydrogenated polymerized rosin having a content of sulfur of removing sulfur content of an antioxidant obtained by desulfurizing a hydrogenated polymerized rosin obtained by hydrogenating the polymerization rosin (A); The desulfurization treatment is carried out at 100 to 300 in the presence of a desulfurization catalyst. A method for producing the polymerization rosin ester, wherein the polymerization rosin (A1) is reacted with alcohols (B); A method for producing a hydrogenated polymerization rosin ester, wherein the polymerization rosin ester obtained by the above production method is hydrogenated; A soldering flux containing the polymerization rosin or the hydrogenation polymerization rosin; The brazing flux having a content of 6 to 55% by weight of the polymerization rosin or the hydrogenation polymerization rosin; The brazing flux, in which an activator (B), an additive (C) and a solvent (D) are also contained; A solder paste containing the solder flux and solder powder; A tackifier containing the polymerization rosin ester or the hydrogenation polymerization rosin ester; A tackifying resin emulsion in which the tackifier is emulsified; The point-adhesive composition in which the said tackifier was contained; It relates to the water-based point and adhesive composition which the said tackifying resin emulsion contained.

According to the present invention, even when stored under heating conditions, the (heating) stability is good, and even after preservation for a long time, hydrogenation can be carried out without any problem even if a treatment such as hydrogenation is performed. Polymerization rosin and polymerization rosin ester with good color tone and hydrogenation polymerization rosin and hydrogenation polymerization rosin ester with good color tone and heat stability can be provided.

Further, the polymerization rosin and the hydrogenation polymerization rosin obtained by the present invention have a good color tone and a low sulfur content, and therefore can be suitably used as a flux for soldering. Moreover, color tone and heat stability are favorable, and it can use it suitably also as a tackifying resin.

The polymerization rosin (A1) (hereinafter referred to as component (A1)) of 100 ppm or less of the sulfur content (except for the part by antioxidant) used in the present invention is to reduce the sulfur content of the known polymerization rosin. . When the content of the sulfur content exceeds 100 ppm, partly pale colorization may not be possible even if hydrogenated after long-term storage, and the heating stability is deteriorated. In addition, in this invention, the quantity of sulfur content is the value measured by the fluorescence X-ray analysis (ZSK100e, the Science and Electrical Industry Co., Ltd. product).

Production of polymerization rosin (A) (hereinafter referred to as component (A)) is obtained by polymerizing rosin by a known method. Rosin can be used, such as wood rosin, tall oil rosin, gum rosin. Although these may be used unrefined, in order to obtain the polymerization rosin ester (Gardner color number 8 or less) with favorable color tone, it is preferable to refine and use rosin. In the present invention, the color tone (Gardner color number) is a value determined by colorizing 10 g of a target resin into a test tube and colorizing it with a Gardner color number standard solution manufactured by Kishida Chemical Co., Ltd. under nitrogen gas flow. (Gardner color number) is the value measured by this method.) Purification of rosin refers to the removal of the high molecular weights believed to have occurred from the peroxides contained in the crude rosin as the starting material, and the insensitive matters originally contained in the rosin. it means. Specifically as the purification method, for example, distillation, recrystallization, extraction or the like may be performed. Industrially, purification by distillation is preferable. In the case of distillation, it is usually appropriately selected in consideration of distillation time from a temperature of 200 to 300 ° C and a pressure of 130 to 1300 Pa. In the case of recrystallization, for example, crude rosin may be dissolved in both solvents, followed by removing the solvent to form a thick solution, and adding a poor solvent to this solution. Examples of the good solvent include aromatic solvents such as benzene, toluene, and xylene, halogenated hydrocarbons such as chloroform, lower alcohols, ketones such as acetone, and sulfuric acid esters such as ethyl sulfate. Examples of the solvent include hydrocarbon solvents such as n-hexane, n-heptane, cyclohexane, and isooctane. Further, in the above purification, the crude rosin is referred to as an alkaline aqueous solution using alkaline water, and the resulting insoluble insolubilizer is extracted with an organic solvent, followed by neutralization of the aqueous layer to obtain purified rosin.

The polymerization rosin used in the present invention is obtained by reacting the rosin in the presence of a sulfuric acid catalyst, usually in an organic solvent, at about 40 to 160 ° C. for about 1 to 10 hours. Examples of the sulfuric acid catalyst include sulfuric acid, p-toluenesulfonic acid, Copolymer sulfonates such as methanesulfonic acid and styrenedivinylbenzene; and the like. In addition to sulfuric acid catalysts, formic acid, hydrogen fluoride, zinc chloride, aluminum chloride, titanium tetrachloride, etc. may be used in combination, but zinc chloride and sulfuric acid are preferably used since the side reactions such as decarboxylation of rosin are small and the reaction activity is good. Do. Moreover, toluene, xylene, a halogenated hydrocarbon, etc. are mentioned as an organic solvent. In order to remove a catalyst after completion | finish of reaction, various well-known methods, such as washing | cleaning and filtration, can be employ | adopted normally. In addition, unreacted rosin and decomposition products can be removed by vacuum distillation.

The component (A) thus obtained is usually a mixture of rosin (monomer) as an unreacted product, a dimer component in which the rosin dimerizes, a component having a molecular weight larger than that of the dimer component, and the color tone (Gardner color number) is 4-7. It is enough. Since the content rate of the dimer component in the polymerization rosin varies depending on the reaction temperature, reaction time, catalyst species and conditions for removing unreacted purified rosin from the polymerization reaction product during the polymerization reaction, the reaction conditions so as to achieve the desired dimer component content rate. What is necessary is just to select suitably. The dimer component content rate in (A) component used by this invention is not specifically limited, What is necessary is just to determine according to the use of the hydrogenation polymerization rosin or its ester finally obtained. Usually, it is about 10 to 85 weight%, Preferably it is 20 to 80 weight%. In addition, the polymerization rosin obtained in this way does not contain a heavy metal powder normally (total or less detected by fluorescence X-ray analysis), chlorine content is 100 ppm or less, and sulfur content is about 200 ppm or more. The sulfur content is considered to be bonded to the rosin or the like by the reaction of the sulfuric acid-based catalyst or the decomposition product thereof used in the polymerization reaction with the rosin or the like, and is considered to be impossible to remove by ordinary washing, distillation or the like.

The method for removing the sulfur content reacted with the rosin or the like (desulfurization treatment) is not particularly limited, and a known method can be employed. For example, a method of heating the component (A) in the presence of a desulfurization catalyst in a hydrogen atmosphere of usually 0.1 to 5 MPa, preferably 0.1 to 3 MPa is mentioned. The heating time is not particularly limited, but is usually about 0.1 to 5 hours, preferably 0.3 to 3 hours. By maintaining the pressure and the heating time in the range, hydrogenation of the carbon-carbon double bond present in the component (A) can be suppressed, and thus, various modifications can be made to the component (A1) obtained. It does not specifically limit as a desulfurization catalyst, A well-known thing can be used. For example, complex catalysts such as palladium carbon, rhodium carbon, ruthenium carbon, platinum carbon, metal powder catalysts such as nickel and platinum, nickel molybdenum type or cobalt molybdenum type Metal complex oxide catalysts, such as metal complex sulfide catalysts, Oxide catalysts, such as oxo and iron oxide, are mentioned. Although the usage-amount of a desulfurization catalyst is not specifically limited, Usually, about 0.01-5.0 weight part with respect to 100 weight part of (A) component, Preferably it is 0.01-2.0 weight part. By setting it as the range, sulfur content can be removed efficiently and hydrogenation of the carbon-carbon double bond which exists in (A) component can be suppressed. Moreover, heating is about 100-300 degreeC normally, Preferably you may be 150-270 degreeC. By setting the heating temperature in the range, sulfur content can be efficiently removed and hydrogenation of carbon-carbon double bonds present in the polymerization rosin can be suppressed.

The (A1) component thus obtained has a sulfur content of 100 ppm or less, and when a crude rosin is used as a raw material, the color tone is about 6 to 11 G (Gardner color number) according to the softening point (round ball method, JIS K5902). It is a value measured by the method.) Is about 90 to 160 ° C. Moreover, when refined rosin is used as a raw material, a hue is about 4-7 (Gardner color number), and a softening point is about 90-160 degreeC.

The (A1) component obtained by the said method can be set as the hydrogenation polymerization rosin which further improved heating stability by hydrogenating.

The hydrogenation is not particularly limited and a known method can be employed. Specifically, for example, in the presence of a hydrogenation catalyst, it is usually about 0.5 to 7 hours under hydrogen pressurization of usually 1 to 25 MPa, preferably 5 to 20 MPa. The method of heating a component for 1 to 5 hours is mentioned. As a hydrogenation catalyst, various well-known things, such as only catalysts, such as palladium carbon, a rhodium carbon, ruthenium carbon, and a platinum carbon, metal powders, such as nickel and platinum, an oxide of oxo, iron iodide, etc., can be used. It is 0.01-5 weight part normally with respect to 100 weight part of polymerization rosin, Preferably it is 0.01-3.0 weight part. In addition, hydrogenation temperature is 100-350 degreeC, Preferably it is 150-300 degreeC.

The hydrogenated polymerization rosin thus obtained has a content of sulfur of 100 ppm or less. In particular, when refined rosin was used in the preparation of component (A), the color tone (Gardner color number) was 2 or less, and the hazen number (APHA method: Japan Chemicals Association Standard Maintenance Analysis Method 2.2.1.4-1996). The color tone (the number of colors) is a value measured by the present method.) 30 to 300, preferably 30 to 200, and a softening point of 90 to 160 ° C, preferably 95 to 150 ° C. The weight average molecular weight (polystyrene equivalent value by gel permeation chromatography method) is about 350 to 650, preferably 400 to 600, and is based on acid value (JIS K5902). Is 130 to 160 mgKOH / g, preferably 135 to 155 mgKOH / g. The dimer component content in the hydrogenation polymerization rosin is usually about 10 to 85% by weight, preferably 20 to 80% by weight. In addition, even if the (A1) component is desulfurized and hydrogenated, the polymer content rate hardly changes before and after desulfurization and hydrogenation.

The polymerization rosin ester of which content of sulfur (but removes the part by antioxidant) of 100 ppm or less esterifies the above-mentioned (A1) component and alcohol (B) (henceforth (B) component). It is obtained by carrying out the desulfurization treatment which will be described later, or a polymerization rosin ester obtained by reacting the method or (A) component and (B) component.

As (B) component used for manufacture of polymerization rosin ester, if it is a compound which has a hydroxyl group, a well-known thing can be used. Specifically, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butyl alcohol, pentanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decyl alcohol (dedyl alcohol) monohydric alcohols such as alcohol) and lauryl alcohol, dihydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, cyclohexane dimethanol, glycerin, trimethyl Trihydric alcohols such as ethanol and trimethylolpropane, tetrahydric alcohols such as pentaerythritol and diglycerin, and pentahydric alcohols such as dipentaerythritol and the like.

These may be used individually by 1 type, or may mix and use 2 or more types.

The polymerization rosin ester of this invention is obtained by making said (A1) component and (B) component react. Although the usage-amount of (A1) component and (B) component can be suitably selected according to the polymerization rosin ester made into the objective, it is normal that molar ratio of the hydroxyl group / (A1) component in (B) component is about 0.5-1.5. desirable. Although esterification reaction is not specifically limited, A well-known method can be employ | adopted, The water which produces | generates normally for about 2 to 20 hours (preferably 3 to 16 hours) at about 200-300 degreeC (preferably 240-280 degreeC) The reaction may be performed while removing. In addition, you may use an esterification catalyst for the reaction as needed. As the esterification catalyst, metal oxides such as calcium hydroxide, magnesium oxide such as acid catalyst calcium hydroxide such as sulfuric acid, and the like can be used. In addition, it is not preferable to use a catalyst containing sulfur as the acid catalyst because it may adversely affect the heating stability of the resulting polymerized rosin ester.

In addition, the polymerization rosin ester of this invention is obtained also by performing above-mentioned desulfurization process after making (A) component and (B) component react. Reaction of (A) component and (B) component can be performed similarly to reaction of (A1) component and (B) component mentioned above. That is, it is preferable to make (A) component and (B) component the molar ratio of the carboxyl group in the hydroxyl group / (A) component in (B) component normally about 0.5-1.5. The esterification reaction is not particularly limited, and a known method can be employed, but water which is usually produced at about 200 to 300 ° C. (preferably 240 to 280 ° C.) for about 2 to 20 hours (preferably 3 to 16 hours) The reaction may be performed while removing. In the present method, since the desulfurization treatment is carried out later, a catalyst containing sulfur may be used during esterification. The polymerization rosin ester obtained by making (A) component and (B) component react in this way makes content of a sulfur content into 100 ppm or less in the above-mentioned desulfurization process.

The polymerization rosin ester thus obtained has sulfur content of 100 ppm or less, and when crude rosin is used as a raw material, the color tone is about 6 to 11 (Gardner color number) and the softening point is about 100 to 190 ° C. Moreover, when refined rosin is used as a raw material, a hue is about 5-7 (Gardner color number), and a softening point is about 100-190 degreeC.

The desulfurization polymerization rosin ester obtained by the said method is hydrogenated, and can be set as the hydrogenation polymerization rosin ester which further improved heating stability. The sulfur content of this hydrogenation polymerization rosin ester needs to be 100 ppm or less. When sulfur content exceeds 100 ppm, heating stability will worsen.

Hydrogenation can employ | adopt the same conditions as the case of hydrogenating the above-mentioned polymerization rosin.

The hydrogenated polymerization rosin ester obtained has a color tone (Gardner color number) of 2 or less, particularly 30 to 300, preferably 30 to 200, preferably 30 to 200, and a softening point of 100 when using a purified rosin during the production of the polymerization rosin. It is about -190 degreeC, Preferably it is 120-180 degreeC. The weight average molecular weight (polystyrene conversion value by gel permeation chromatography) is about 1,000 to 5,000, preferably 1,200 to 3,000, and an acid value is 30 mgKOH / g or less, preferably 20 mgKOH / g or less.

In addition, even if depolymerization and hydrogenation of the polymerized rosin ester, the polymer content rate hardly changes before and after hydrogenation. Moreover, various additives, such as a well-known phenolic antioxidant, lean antioxidant, and sulfur type antioxidant, can be added to the polymerization rosin, hydrogenation polymerization rosin, polymerization rosin ester, and hydrogenation polymerization rosin ester of this invention.

The polymerization rosin and / or hydrogenation polymerization rosin of the present invention (for the description of the use of the flux for soldering, the desulfurization polymerization rosin and / or the hydrogenation polymerization rosin of the present invention is referred to simply as the base resin (1).) In addition, since the sulfur content is particularly small, it can be suitably used for lead-free soldering flux.

The base resin 1 is usually used in an amount of about 6 to 55 parts by weight, preferably 9 to 45 parts by weight, and particularly preferably 18 to 40 parts by weight with respect to 100 parts by weight of the lead-free soldering flux. By setting it as the range, since a void can be reduced easily and generation | occurrence | production of a solder ball, etc. can be prevented, it is preferable.

In addition, as the lead-free soldering flux of the present invention, monoalcohol esters obtained by reacting monoalcohol with base resin (1), synthetic resin having an acid value of about 100 to 300, and the like can be used in combination. The synthetic resin is not particularly limited as long as it is usually used for lead-free solder flux. Specifically, for example, epoxy resin, acrylic resin, polyimide resin, polyamide resin (nylon resin), polyester resin, polyacrylonitrile resin, vinyl chloride resin, vinyl sulfate resin, polyolefin resin , Fluorine-based resin or ABS resin can be exemplified by mixing a single or a plurality. In addition, a plurality of elastomers such as isoprene rubber, styrene butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber or nylon rubber, or elastomers such as nylon elastomers or polyester elastomers may be used alone or in plurality. You may use together. When using components other than these base resin (1), it is good to use normally in the range of about 0-20 weight part with respect to 100 weight part of base resin (1).

The lead-free soldering flux of the present invention usually contains an activator (2), an additive (3) and a solvent (4) in addition to the base resin (1).

As the activator 2, any activator that can be used for the lead-free soldering flux can be used without particular limitation. Specifically, an organic acid compound activated by a preheat of a reflow process, a halide activated by a main heat, or a compound exhibiting an active force from the preheat to the main heat can be used. As the organic acid compound, for example, succinic acid, benzoic acid, adipic acid, abietic acid, glutaric acid, palmitic acid, stearic acid, formic acid or Azelaic acid etc. can be illustrated. Moreover, as the halogen compound, for example, ethylamine hydrochloride, methylamine hydrochloride, ethylamine bromate, diethylamine bromate, methylamine bromate, propenediol hydrochloride, allylamine hydrochloride, 3-amino-1-propene hydrochloride, N- (3-aminopropyl) methacrylamide hydrochloride, O-anisine hydrochloride, n-butylamine hydrochloride, P - phenol hydrochloride, etc. can be illustrated. Moreover, quaternary ammonium, lauryl trimethylammonium chloride, alkyl benzyl dimethyl ammonium chloride, etc. are mentioned as an active agent which shows the active force from the preheat to the main heat, These may be used together suitably. The content of the activator 2 is usually about 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the lead-free soldering flux.

As the additive 3, a known additive which can be used for the lead-free soldering flux can be used. Specifically, various known antioxidants, thixotropic agents and the like can be used. Examples of the antioxidant include tributylamine, tetrabutylammonium bromide, 2,6-di-t-butyl-p-cresol, para-tert-amylphenol, 2,2'-methylenebis (4-methyl-6 -tert-butylphenol), trans-2, 3-dibromo-2-butene-1, 4-diol, etc. can be illustrated. Examples of thixotropic agents include castor oil, hardened castor oil, honeylow, carnauba wax, stearic acid amide, hydroxy stearate ethylene bisamide, and the like. In addition, as an additive, covering with bosotsuki (or bassuki) or leather (the solder ball reacts with the activator in the flux, etc. during the storage of the solder paste, the viscosity is changed, or the paste surface becomes hard as the leather is pasted or creamed. To change over time, such as loss of overall viscosity), 3-methyl-1-butyn3-ol, 3-methyl-1-pentin-3-ol, 3,5-dimethyl-1- Hexyn3-ol, 2,5-dimethyl-3-hexine-2,5-diol, 2,4,7,9-tetramethyl-5-dicin-4,7-diol and 3,6-dimethyl-4- You may use an acetylene alcohol type compound (refer to Unexamined-Japanese-Patent No. 2000-263281), such as oaktin-3, 6- diol. Content of the additive 3 is about 0.1-10 weight part normally with respect to 100 weight part of soldering flux, Preferably it is 0.1-5 weight part, More preferably, it is 0.1-2 weight part. In addition, when using a thixotropic agent as an additive (3), about 3 to 10 weight% may be used, and when an acetylene alcohol type compound is used, it may use about 0.1 to 5 weight part.

It will not specifically limit, if it is various well-known solvent which can be used for the lead-free soldering flux as the solvent 4, A well-known thing can be used. Specifically, ethylene glycol monohexyl ether, diethylene glycol monobutyl ether, hexyl glycol, octanediol, ethylhexyl glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol 2- (2-n-butoxy) Alcohols such as oxyethanol and terpineol, esters such as butyl benzoate, diethyl adipic acid and 2- (2-n-butoxyethoxy) ethyl acetate; dodecane, tetradecene hydrocarbons such as (tetradecene), and pyrrolidones such as N-methyl2-pyrrolidone, etc. Also, since the melting temperature of lead-free solder is considerably high as described above, 150 to It is preferable to have a boiling point in the range of about 300 degreeC, Preferably it is 220-250 degreeC In addition, content of the solvent 4 in a flux is about 20-85 weight part normally with respect to 100 weight part of lead-free soldering flux. , Preferably 25 to 85 parts by weight, more preferably 30 to 80 parts by weight It is wealth.

The flux according to the present invention can be obtained by kneading the base resin (1), the activator (2), the additive (3), and the solvent (4) by known means. The conditions (temperature, pressure, etc.) at that time are not specifically limited. As the kneading means, for example, a planetary mill can be used.

The solder paste of the present invention is a creamy composition obtained by kneading the lead-free solder flux of the present invention and various known lead-free solder powders by known mixing means such as an oil-based printing press.

Examples of the lead-free solder powder include Sn solder powder, Sn-Ag solder powder, Sn-Cu solder powder, Sn-Zn solder powder and Sn-Sb solder powder. As the Sn-Ag solder powder, Sn-Ag solder powder, Sn-Ag-Cu solder powder, Sn-Ag-Bi solder powder, Sn-Ag-Cu-Bi solder powder, Sn-Ag-Cu-In solder Powder, Sn-Ag-Cu-S soldering powder, Sn-Ag-Cu-Ni-Ge soldering powder, etc. can be illustrated.

In addition, although the flux which concerns on this invention is intended for the lead-free soldering use, it can also provide for the conventional lead-process soldering use. Examples of the lead-process solder powder include Sn-Pb solder powder, Sn-Pb-Ag solder powder, Sn-Pb-Bi solder powder, In-Pb solder powder, Pb-Ag solder powder and the like.

In addition, in the solder paste of the present invention, the solid content weight ratio of the flux and the lead-free solder powder is usually made to be about 5:95 to 20:80 of the former. The same applies to the soft solder powder. Moreover, the said additive 3, the solvent 4, and other additive can be arbitrarily used further for the solder paste in the range concerned.

Polymerization rosin ester and hydrogenation polymerization rosin ester obtained by the above-mentioned method can be used suitably as a tackifier because heat stability is favorable.

Moreover, as a point and adhesive composition which the point and adhesive composition of this invention obtained using the said tackifier, an acrylic adhesive composition, a rubber adhesive composition, an ethylene-type hot melt adhesive composition etc. are mentioned, for example.

An acrylic pressure sensitive adhesive composition is obtained by mix | blending a tackifier with the acrylic polymer which is a base polymer.

An acrylic polymer does not have a restriction | limiting in particular, The various well-known homopolymer or copolymer used as an acrylic pressure sensitive adhesive can be used as it is. As a monomer used for an acryl-type polymer, various (meth) acrylic acid ester (in addition, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester, and the following (meta) has the same meaning). As a specific example of related (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. can be illustrated, for example, These are individual or It can be used in combination. In addition, in order to impart polarity to the obtained acrylic polymer, a small amount of (meth) acrylic acid may be used in place of a part of the (meth) acrylic acid ester. Moreover, (meth) acrylic-acid glycidyl, (meth) acrylic-acid 2-hydroxyethyl, N-methinol (meth) acrylamide, etc. can also be used together as a crosslinkable monomer. Furthermore, other copolymerizable monomers, for example, vinyl sulfate, styrene, etc. can be used together to the extent that it does not impair the adhesive characteristic of a (meth) acrylic acid ester polymer as desired.

Although the glass transition temperature of the acrylic polymer which has these (meth) acrylic acid ester as a main component in particular is not restrict | limited, Usually, it is good to set it as about -90-0 degreeC, Preferably it is the range of -80-10 degreeC. When the glass transition temperature significantly exceeds 0 ° C., the tuck decreases, and when the glass transition temperature is significantly below −90 ° C., the adhesive force tends to decrease. Moreover, although molecular weight is not specifically limited, Usually, it is preferable that a weight average molecular weight is about 200,000-1 million, and is about 300,000-900,000. By making molecular weight into this range, a point and adhesive performance become favorable.

Moreover, what is necessary is just to employ | adopt various well-known methods for the manufacturing method of this acryl-type polymer, For example, radical polymerization methods, such as a bulk polymerization method, a solution polymerization method, and a suspension polymerization method, can be selected suitably. As a radical polymerization initiator, various well-known things, such as an azo system and a peroxide type, can be used, reaction temperature is about 50-85 degreeC normally, and reaction time is about 1 to 8 hours. In addition, as a solvent of an acryl-type polymer, generally polar solvents, such as ethyl sulfate and toluene, are used and a solution concentration will be about 40 to 60 weight% normally.

The acrylic pressure-sensitive adhesive composition of the present invention is used in an amount of about 1 to 40 parts by weight of the tackifying resin, preferably 5 to 30 parts by weight, based on 100 parts by weight of the acrylic polymer. When the addition amount of tackifying resin is less than 1 weight part, it becomes difficult to provide sufficient adhesive characteristic, and when it exceeds 40 weight part, it is unpreferable because not only a compatibility fall but also an adhesive composition hardens and adhesive force and turk fall.

In addition, the acrylic pressure-sensitive adhesive composition of the present invention may further improve cohesion and heat resistance by adding crosslinking agents such as a polyisocyanate compound, a polyamine compound, a melamine resin, a urea resin, and an epoxy resin to the acrylic polymer and the tackifying resin. Among these crosslinking agents, it is particularly preferable to use a polyisocyanate compound, and specific examples thereof include 1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, isohorone diisocyanate, xylene diisocyanate, toluene diisocyanate, and 4,4-di. Various well-known things, such as phenylmethane diisocyanate, are mentioned. Furthermore, the acrylic pressure sensitive adhesive composition of this invention can use a filler, antioxidant, a ultraviolet absorber, etc. suitably as needed. Moreover, the acryl-type pressure sensitive adhesive composition of this invention can also use together various well-known tackifying resin in the range which does not deviate from the objective of this invention.

As a rubber adhesive composition of this invention, a styrene conjugated diene type block copolymer adhesive composition, a natural rubber adhesive composition, etc. are mentioned, for example. These rubber adhesive compositions mix | blend the said tackifier, styrene conjugated diene type block copolymer, or natural rubber and oil.

The styrene conjugated diene block copolymer is a block copolymer in which styrenes such as styrene and methyl styrene and conjugated dienes such as butadiene and isoprene are appropriately selected and copolymerized according to the purpose of use. Usually, the weight ratio of styrenes / conjugated dienes is about 10 / 90-50 / 50. As a preferable specific example of such a block copolymer, SBS type block copolymer and styrene (S) / in which the weight ratio of styrene (S) / butadiene (B) exists in the range of 10/90-50/50, for example. SIS type block copolymer etc. in which the weight ratio of isoprene (I) exists in the range of 10 / 90-30 / 70 is mentioned. The styrene conjugated diene block copolymer of the present invention also includes a hydrogenated conjugated diene component of the block copolymer. Although it is hydrogenated, what is called a SEBS type block copolymer, a SEPS type block copolymer, etc. are mentioned as a specific example.

Examples of the oil include plasticized oils such as naphthenic oil, paraffinic oil and aromatic oil. Naphthenic oil and paraffinic oil are preferable from the point where there is little fall of cohesion force. Specifically, naphthenic process oil, paraffin process oil, liquid polybutene, etc. are mentioned.

The usage-amount of each component is about 15-210 weight part of tackifiers, about 4-200 weight part of styrene conjugated diene type block copolymers or natural rubber, and about 4-200 weight part of oils.

When the amount of the styrene conjugated diene-based block copolymer or natural rubber is less than 4 parts by weight, the holding force is insufficient, and when it exceeds 200 parts by weight, the melt viscosity of the pressure-sensitive adhesive composition obtained tends to increase. In addition, when the oil is less than 4 parts by weight, the melt viscosity of the pressure-sensitive adhesive composition is high, and when it exceeds 200 parts by weight, the holding force may be insufficient. Moreover, additives, such as a filler and antioxidant, can be added to the rubber-based adhesive composition of this invention as needed.

The ethylenic hot melt adhesive composition of the present invention is obtained by blending the tackifier in an ethylene copolymer.

An ethylene copolymer is a copolymer of ethylene and the monomer copolymerizable with ethylene, and what has conventionally been used for a hot melt adhesive can be used. Examples of the monomer copolymerizable with ethylene include vinyl sulfate, methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate. Although copolymerizable content, such as vinyl sulfate, is not restrict | limited, Usually, it is about 20 to 45 weight%. Moreover, as for molecular weight, it is preferable that melt index (190 degreeC, load 2160g, 10 minutes) is about 10-400 g / 10min.

As a wax, what is used for a hot melt adhesive can be used, Specifically, synthetic waxes, such as petroleum waxes, such as paraffin wax and a microcrystal wax, Fischer- trofusch wax low molecular weight polyethylene wax, are mentioned.

The ethylenic hot melt adhesive composition of the present invention is one containing 100 parts by weight of the ethylene copolymer 100 to 150 parts by weight of the tackifier of the present invention and 10 to 100 parts by weight of the wax.

When the tackifier is less than 50 parts by weight, sufficient adhesive strength may not be obtained, and when the tackifier is more than 150 parts by weight, sufficient holding force may not be obtained. Moreover, when the wax is less than 10 weight part, the melt viscosity of the adhesive composition obtained becomes too high, and when it exceeds 100 weight part, since sufficient holding force cannot be obtained, it is unpreferable. Moreover, additives, such as a filler and antioxidant, can be further added to the ethylenic hot melt adhesive composition of this invention as needed.

In addition, this tackifier can be used also as a tackifying resin emulsion by disperse | distributing in water in presence of an emulsifier.

The tackifying resin emulsion of this invention can be obtained by mixing and emulsifying polymerization rosin ester and / or hydrogenation polymerization rosin ester. In emulsification, an emulsifier is usually used. It does not specifically limit as an emulsifier to be used, A well-known emulsifier can be used. Specifically, the polymer emulsifier obtained by superposing | polymerizing a vinyl monomer, a low molecular weight anionic emulsifier, a low molecular weight nonionic emulsifier, etc. are mentioned. Especially in this invention, a polymeric emulsifier is mentioned. The use of is preferable because it can improve adhesion performance (particularly holding force) and mechanical stability.

A polymer emulsifier is a polymer having an emulsifying ability obtained by copolymerizing a vinyl monomer, but particularly anionic monomer (a) (hereinafter referred to as component (a)) 10 to 80% by weight, styrenes and / or (meth) Obtained by polymerizing 10-50 weight% of alkyl acrylate ester (b) (henceforth (b) component) and reactive emulsifier (c) (henceforth (c) component). It is preferable to use a polymer emulsifier because it can improve the adhesive performance (especially the holding force).

As the component (a), any monomer having an anionic functional group such as a vinyl group, a carboxyl group, a phosphoric acid group, or a sulfonic acid group in the molecule is not particularly limited, and a known one can be used. Specifically, for example, acrylic acid, methacrylic acid, crotonic acid carboxylic acids such as monocarboxylic acid such as croton, maleic acid, maleic anhydride, fumaric acid, dicarboxylic acid such as itaconic acid and muconic acid; Organic sulfonic acids such as vinylsulfonic acid, styrenesulfonic acid and 2-acrylamide-2-methylpropanesulfonic acid; Phosphoric acid vinyl monomers such as 2- (meth) acryloyloxyethyl acid phosphate; And alkali metal salts such as sodium salts and potassium salts of these various organic acids, alkaline earth metal salts, ammonium salts and salts of organic bases. These (a) components may be used independently and may use multiple together. Among these (a) components, methacrylic acid and styrenesulfonic acid are preferable, and styrenesulfonic acid is preferable at the point of emulsification of the polymer emulsifier obtained and affinity with tackifying resin.

As (b) component, styrene, (alpha) -methylstyrene, vinyltoluene etc. are mentioned as styrene, for example. Among these, styrene and (alpha) -methylstyrene are preferable at the point of affinity with tackifying resin. Moreover, as (meth) acrylic-acid alkylester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate And 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. These may be used independently and may use multiple together. Among these, methyl (meth) acrylate is preferable at the point of affinity with tackifying resin.

(c) A component is a surfactant which has a hydrophilic group and a hydrophobic group, has a carbon-carbon double bond in a molecule | numerator, and means that it is not contained in the said (a) component and (b) component. As a carbon-carbon double bond, For example, (meth) aryl group, 1-propenyl group, 2-methyl-1- propenyl group, vinyl group, isopropenyl group, (meth) acryloyl group, etc. A functional group is mentioned. Specific examples of the component (c) include, for example, a polyoxyethylene alkyl ether having at least one functional group in a molecule, a sulfobacteric acid ester salt of a polyoxyethylene alkyl ether having at least one functional group in a molecule, and the functional group in a molecule. Sulfate ester salt of polyoxyethylene alkyl ether which has at least one, Polyoxyethylene phenyl ether which has the said functional group in a molecule at least 1, The sulfobacteric acid ester salt of the polyoxyethylene phenyl ether which has at least 1 the said functional group in a molecule, The said Sulfuric acid ester salts of polyoxyethylenephenyl ethers having at least one functional group in a molecule, polyoxyethylene alkylphenyl ethers having at least one functional group in a molecule, and polyoxyethylene alkylphenyl ethers having at least one functional group in a molecule Sulfo succinic acid ester salts, Sulfuric acid ester salt of polyoxyethylene alkylphenyl ether having at least one functional group in a molecule, polyoxyethylene aralkyl phenyl ether having at least one functional group in a molecule, polyoxyethylene aralkyl having at least one functional group in a molecule Sulfobacteric acid ester salt of phenyl ether, sulfate ester salt of polyoxyethylene aralkyl phenyl ether having at least one of the above functional groups in the molecule, or phosphate ester salt of polyoxyethylene alkylphenyl ether having at least one of the above functional groups in the molecule, Aliphatic or aromatic carboxylates of polyoxyethylene alkylphenyl ethers having at least one functional group in a molecule, acidic phosphoric acid (meth) acrylic acid ester-based emulsifiers, and acid anhydride modified products of rosin glycidyl ester acrylates (Japanese Patent Application Laid-Open No. 4-256429) Japanese Patent Laid-Open No. 63-23725, Japanese Patent Laid-Open No. 63-240931 And various kinds such as emulsifiers described in Japanese Patent Application Laid-Open No. 62-104802. In addition, a block copolymerized or random copolymerized polyoxyethylene or polyoxyethylene and polyoxypropylene of polyoxyethylene in the reactive emulsifier Alternatives are also mentioned. In the present invention, such a reactive emulsifier can be used without particular limitation.

As a commercial item of the said (c) component, it is a (brand name: KAYAMER PM-1, Nippon Kayaku Co., Ltd.), (brand name: KAYAMER PM-2, Nippon Kayaku Co., Ltd.), (brand name: KAYAMER PM- 21, Nippon Kayaku Co., Ltd., (brand name: SE-10N, ADEKA Co., Ltd.), (brand name: NE-10, ADEKA Co., Ltd.), (brand name: NE-20, ADEKA Co., Ltd. ), (A brand name: NE-30, product made in ADEKA), (a brand name: New Frontier A229E, a Cheil Industry Pharmaceutical Co., Ltd.), (a brand name: New Frontier N-117E, a Cheil Industry Pharmaceutical Co., Ltd. product), (Brand name: New Frontier N-250Z, Cheil Industrial Pharmaceuticals Co., Ltd.), (brand name: Aquaron RN-10, Cheil Industrial Pharmaceuticals Co., Ltd.), (brand name: Aquaron RN-20, Cheil Industrial Pharmaceuticals Co., Ltd. ), (Brand name: Aquaron RN-50, product of Cheil Industry Co., Ltd.), (product name: Aquaron HS-10, product of Cheil Industry Pharmaceutical Co., Ltd.), (brand name: ereminole JS-2, Samyang Hwasung Industrial Co., Ltd., (brand name: Latemru K-180, Hwawang Co., Ltd.), etc. are mentioned as a representative example. Among the reactive emulsifiers, polyoxyethylene phenyl ethers are preferred in terms of polymerizability and emulsification properties of the obtained polymer emulsifier, and as commercially available products (trade name: Aquaron RN-10, manufactured by Jeil Ind. Pharmaceutical Co., Ltd.), (trade name: Aquaron RN-20, Jeil Industry Pharmaceutical Co., Ltd.), and (brand name: Aquaron RN-50, Jeil Industry Pharmaceutical Co., Ltd. product) are preferable.

The polymer emulsifier is about 10 to 80% by weight of component (a), preferably about 20 to 70% by weight of component (b) and about 10 to 50% by weight of component (b), preferably 15 to 40% by weight of component (c) It is obtained by copolymerizing about 10% by weight, preferably 10 to 40% by weight. Since the emulsification property is improved by making (a) component 10 weight% or more, it is preferable, and since water resistance improves by making it less than 80 weight%, it is preferable. Moreover, since affinity with tackifying resin improves by making (b) component 10 weight% or more, it is preferable, and since emulsification property improves by making it 50 weight% or less, it is preferable. Moreover, since emulsification property improves by making (c) component 10 weight% or more, it is preferable, and since water resistance improves by making it 50 weight% or less, it is preferable.

As a polymerization method of a polymer emulsifier, various well-known methods, such as solution polymerization, emulsion polymerization, suspension polymerization, can be employ | adopted as it is. The component (a) may be partially neutralized or completely neutralized before polymerization to form a salt, or may be partially neutralized or completely neutralized after polymerization to form a salt.

Examples of the solvent used for solution polymerization include aromatic solvents such as benzene, toluene and xylene, hydrocarbon solvents such as hexane and cyclohexane, alcohol solvents such as methyl alcohol, ethyl alcohol and isopropyl alcohol, and ester solvents such as ethyl sulfate. Solvents, ketone solvents such as acetone and methyl isobutyl ketone, ether solvents such as dioxane, dimethylformamide, dimethyl sulfoxide and the like can be used.

In the case of emulsion polymerization, since the component (c) has an emulsifying ability, it is not particularly necessary to use an emulsifier, but an emulsifier usually used for emulsion polymerization other than the component (c) may be used. Examples of the emulsifiers involved include dialkyl sulfo acid ester salts, alkanesulfonate salts, α-olefin sulfonate salts, polyoxyethylene alkyl ether sulfo acid ester salts, polyoxyethylene styryl phenyl ether sulfo acid ester salts and naphthalene sulfonic acid formalin. Anionic emulsifiers such as condensates, polyoxyethylene alkyl ether sulfate ester salts, polyoxyethylene alkylphenyl ether sulfate ester salts, polyoxyethylene alkyl ethers, polyoxyethylene styrylphenyl ethers, polyoxyethylene sorbitan fatty acid esters, and the like. And nonionic emulsifiers. These emulsifiers may be used alone or in combination of two or more. The usage-amount is normally about 10 weight% or less with respect to the total amount of the said (a) component, (b) component, and (c) component, Preferably it is about 0.1 to 10 weight%.

It does not specifically limit as a polymerization initiator used at the time of the said superposition | polymerization, Various well-known things, such as persulfates, a peroxide, an azo compound, a redox system initiator, can be used. Since the molecular weight of the said (c) component directly correlates with the dispersibility of the emulsion of a tackifying resin, it is preferable to make weight average molecular weight about 1000-200000 normally. In addition, a well-known chain transfer agent may be used for adjustment of molecular weight. As a chain transfer agent, for example, isopropyl alcohol, carbon tetrachloride, ethylbenzene, isopropylbenzene, cumene, thioglycolic acid ester, alkyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene Etc. can be mentioned. The amount of the chain transfer agent used for producing the polymer emulsifier is usually about 0.5 to 30% by weight based on the total amount of the components (a) to (c).

Although the usage-amount of a polymer emulsifier is not specifically limited, Usually, it is about 1-10 weight part in solid content conversion with respect to 100 weight part of tackifying resin, Preferably it is 2-7 weight part. When it exceeds 10 parts by weight, the water resistance of the obtained water-based point-adhesive composition is lowered, and when it is less than 1 part by weight, the storage stability and mechanical stability of the resin emulsion during emulsification are deteriorated.

As the emulsifying method, a conventionally known high pressure emulsifying method, a reverse emulsifying method and the like can be adopted. Specifically, after dissolving the tackifier resin in a solvent such as benzene and toluene, adding the polymer emulsifier and soft water to emulsify using a high pressure emulsifier, and then removing the solvent under reduced pressure, a small amount of benzene and toluene in the tackifier resin. The solvent is continuously mixed, the emulsifier is kneaded, and the warm water is gradually added to proceed, and then the phase is emulsified to obtain an emulsion, and then the solvent is removed or used as it is under reduced pressure, the softening point of the resin under pressure or normal pressure. When the temperature rises above, the emulsifier is kneaded, and warm water is gradually added, the method of emulsifying by emulsifying the phase is mentioned.

Although solid content concentration of the tackifying resin emulsion obtained in this way is not specifically limited, Usually, it adjusts suitably so that it may be about 20 to 70 weight%. In addition, the average particle diameter of the obtained emulsion is about 0.2-2 micrometers normally, and most are disperse | distributing uniformly as a particle | grains of 0.5 micrometer or less. Moreover, the emulsion shows the appearance of white to milky white, and has a pH of about 2-9.

The tackifying resin emulsion of the present invention is blended with an acrylic polymer emulsion, which is a base resin, and / or a latex for pressure-sensitive adhesives to impart adhesion characteristics such as turk to various water-based point and adhesive compositions, and at the same time, mechanical sharing of the water-based point and adhesive compositions. improve (share) As the acrylic polymer emulsion, those generally used for various acrylic pressure-sensitive adhesives can be used, and a method of adding a (meth) acrylic acid ester in one batch to polymerize, followed by addition polymerization in order of monomers, addition polymerization in order of emulsion monomers, and seed (seed) It can manufacture easily by well-known emulsion polymerization methods, such as the polymerization method.

As (meth) acrylic acid ester used, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate etc. are mentioned, These are used individually or in mixture of 2 or more types. In addition, in order to provide storage stability to the obtained emulsion, you may use a small amount of (meth) acrylic acid instead of the said (meth) acrylic acid ester. In addition, in order not to impair the adhesive properties of the (meth) acrylic acid ester polymer as desired, for example, copolymerizable monomers such as vinyl sulfate and styrene can be used in combination. The glass transition temperature of the polymer containing these (meth) acrylic acid esters as a main component is usually about -70 to 0 ° C, preferably -60 to -10 ° C. When it exceeds 0 degreeC, turk falls remarkably and is not preferable. As the emulsifier used in the acrylic polymer emulsion, an anionic emulsifier, partially kenned polyvinyl alcohol, and the like can be used, and the amount thereof is usually used in an amount of about 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the polymer. to be.

The use ratio of the acrylic polymer emulsion and the tackifier resin emulsion is preferably about 5 to 30 parts by weight (in terms of solid content) with respect to 100 parts by weight of the acrylic polymer emulsion (in terms of solid content). In the case where the tackifier resin emulsion is less than 5 parts by weight, most modifications by adding the tackifier resin are not recognized, and when it exceeds 30 parts by weight, the cohesive force tends to be lowered.

Examples of the latex for pressure-sensitive adhesives include natural rubber latex, styrene-butadiene copolymer latex, chloroprene latex, and the like. The natural rubber latex can be a known one used in a waterborne adhesive composition, either depolymerized or not depolymerized. Styrene-butadiene copolymer latex and chloroprene latex can also use what is marketed normally for an adhesive. In addition, styrene butadiene copolymer latex and chloroprene latex may be a carboxy-modified one.

The use ratio of the latex for pressure-sensitive adhesives and the tackifier resin emulsion is preferably about 5 to 150 parts by weight (in terms of solid content) of the tackifier resin emulsion with respect to 100 parts by weight (in terms of solids) of the latex for pressure-sensitive adhesives. When the tackifier resin emulsion is less than 5 parts by weight, most of the modifications by adding the tackifier resin are not recognized, and when it exceeds 150 parts by weight, the cohesive force tends to decrease.

The water-based point adhesive composition of this invention can also use together an acryl-type polymer emulsion and an adhesive latex as a base resin, and can also use antifoamer, a thickener, a filler, antioxidant, a water-resistant agent, a film forming agent, etc. as needed.

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In addition,% in each example is based on a weight. In addition, the softening point (recirculation method) is JIS K5902, the acid value is JIS K5902, and the Gardner color number of a hue is the thing which made 10 g of the resin of interest into a test tube, heat-melted it under nitrogen stream, and is a Gardner color number standard liquid made by Kishida Chemical Co., Ltd. It is decided by colorimetric. Hue (Gardner color number) below is the value measured by this method, and hagen number is the value determined by APHA method (by Japan Oil Chemical Association standard maintenance analysis method 2.2.1.4-1996). In addition, the amount of sulfur is the value measured by fluorescence X-ray analysis (ZSK100e, the science and electronics industry make).

Example 1

(1) refining

Crude rosin (Chinese gum rosin) having an acid value of 170.0 mgKOH / g, a softening point of 78 ° C., and Hue Gardner 6 was distilled under a reduced pressure of 400 Pa under a nitrogen chamber, and the liquor shown in Table 1 was referred to as a purified rosin. The refined rosin had an acid value of 178.4 mgKOH / g, a softening point of 88 ° C, and a color tone (Gardner color number) 3.

Table 1

Outflow temperature (℃) Inside temperature (℃) Yield (%) Acid value (mg / KOH) beestings Less than 195 Less than 210 4.4 51.2 oiling 195-250 210-280 88.2 178.4 Bujan 250 seconds 280 seconds 7.4 45.6

(2) polymerization reaction

900 g of purified rosin, xylene 900 g, 40 g of zinc chloride and 6.0 g of sulfuric acid were added to a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a decompression device, and polymerization reaction was performed at 100 ° C. under nitrogen stream for 6 hours. Was performed. 1845.9 g of the xylene solution of the reaction product was washed with 7 g of concentrated hydrochloric acid and 500 g of warm water, and further washed twice with each 500 g of warm water. The xylene solution after washing is distilled xylene under the condition of the liquid temperature of less than 200 ℃, reduced pressure 1300 Pa, and then further into the decomposition product of the purified rosin and unreacted purified under the conditions of the liquid temperature of 200 ~ 275 ℃, reduced pressure 400 Pa 70 g of total ginseng were distilled off and 471 g of refined polymerization rosin with an acid value of 135.3 mgKOH / g, a softening point of 146 ° C, and a color tone (Gardner color number) 5 were obtained. It was recognized by GPC measurement that the content of the polymer in the purified polymerization rosin was 71.3%, the monomer (purified rosin) was 27.2% and the decomposition product was 1.6%. The amount of sulfur in the purified polymerization rosin was determined by fluorescence X-ray measurement. It was recognized that it was 203 ppm.

(3) Desulfurization reaction

Subsequently, 150 g of purified polymerization rosin obtained in (2), 3.0 g of desulfurization catalyst (N-113, manufactured by Nikki Chemical Co., Ltd.) and 150 g of cyclohexane were added to an autoclave reaction apparatus to remove oxygen from the system. After pressurizing the system to hydrogen at 3 MPa, the temperature was raised to 240 ° C. under stirring, and desulfurization reaction was carried out at the same temperature for 1 hour, and the desulfurization polymerization reactor having an acid value of 137.0 mgKOH / g, a softening point of 145 ° C., and a color tone (Gardner color number) 5 was obtained. Got a gin. It was recognized by GPC measurement (area ratio) that the content of the polymer in the desulphurized polymerization rosin was 71.0%, the monomer (tablet rosin) was 27.5%, and the decomposition product was 1.5%. It was recognized that the sulfur content in the polymerization rosin was 95 ppm.

Example 2

150 g of the desulphurized polymerization rosin obtained in Example 1, 1.5 g of 5% feradidium carbon (50% water content) and 150 g of cyclohexane were added to the autoclave reaction apparatus to remove oxygen in the system, and then the system was removed. After pressurizing with 9 MPa in hydrogen, the temperature was raised to 240 ° C. under stirring, and a hydrogenation reaction was performed at the same temperature for 3 hours to obtain a colorless polymerization rosin having an acid value of 145.2 mgKOH / g, a softening point of 140 ° C., and a color tone (hagen color number) 50. By GPC measurement, it was recognized that the content of the polymer in the colorless polymerization rosin was 70.3%, the monomer (hydride of the refined rosin) was 27.7%, and the decomposition product was 2.0%. It was recognized that sulfur content of was 62ppm

Example 3

The polymerization rosin was carried out in the same manner as in Example 2 except that the polymerization rosin obtained in the same manner as in Example 1 was used in place of the polymerization rosin obtained in Example 1, and then stored in the atmosphere for 2 months at room temperature to undergo a hydrogenation reaction to give colorless polymerization. Got rosin. The colorless polymerization rosin obtained was an acid value of 144.4 mgKOH / g, a softening point of 138 ° C, and a color tone (hagen color number) 80. It was recognized by GPC measurement that the content of the polymer in the colorless polymerization rosin was 71.4%, the monomer (hydrogenated product of refined rosin) was 26.4%, the decomposition product was 2.2%, and the colorless polymerization rosin was determined by fluorescent X-ray measurement. The amount of sulfur in it was recognized that it is 66 ppm.

Ester of Example 1

Example 4

(1) esterification reaction

Into a reactor equipped with a thermometer, a high stage, a nitrogen introduction tube, and a decompression device, 1,200 g of the deflow-refining polymerized resin rosin obtained in Example 1, 135.2 g of pentaerythritol, and 6.7 g of glycerin were added to the reactor at 250 ° C. under a nitrogen stream. The esterification reaction was performed at 2 hours and 280 degreeC for 10 hours, and the purified polymerization rosin ester of acid value 17.9KOH / g, softening point 161 degreeC, and color tone (Gardner-color number) 6 was obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the polymerization rosin ester was 83 ppm.

(2) Hydrogenation reaction

Subsequently, 150 g of desulfurized and purified polymerization rosin ester obtained in (1), 1.5 g of 5% ferdium carbon (water content of 50%) and 150 g of cyclohexane were added to the autoclave reaction apparatus to remove oxygen in the system, and then the system was removed. After pressurizing to 5 MPa to hydrogen, the temperature was raised to 240 DEG C under stirring, and after the temperature was raised, the hydrogen pressure was increased to 9 MPa to carry out hydrogenation reaction at the same temperature for 3 hours. A colorless polymerization rosin ester of was obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the colorless polymerization rosin ester was 45 ppm.

Example 5

The hydrogenation reaction was carried out in the same manner as in Example 4 (2) except that the polymerization rosin ester to be used was changed to that stored in the room temperature for 2 months after the desulphurization polymerization rosin ester obtained in Example 4 (1). It carried out and obtained the colorless polymerization rosin ester of 19.0 mgKOH / g in acid value, the softening point of 160 degreeC, and color tone (hagen color number) 100. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the colorless polymerization rosin ester was 48 ppm.

Example 6

In Example 4 (1), ester was prepared in the same manner as in Example 1 (4) except that the polymerization rosin to be used was changed to one stored at room temperature for 2 months after the desulfurization purification polymerization rosin obtained in Example 1 was prepared. The desulfurization polymerization rosin ester having an acid value of 16.8 mgKOH / g, a softening point of 163 ° C, and a color tone (Gardner color number) 7 was obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the desulfurization purification polymerization rosin ester was 88 ppm.

Subsequently, a hydrogenation reaction was carried out in the same manner as in Example 4 (2) to give a colorless polymerization rosin ester having an acid value of 17.5 mgKOH / g, a softening point of 161 ° C, and a color tone (hagen color number) 100. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the colorless polymerization rosin ester was 51 ppm.

Example 7

In Example 6, the hydrogenation reaction was carried out in the same manner as in Example 4 (2) except that the desulfurized and purified polymerized rosin ester used in Example 6 was changed to one stored at room temperature for 2 months. And the acid value 18.0 mgKOH / g, the softening point 160.5 degreeC, and the colorless polymerization rosin ester of the color tone (hagen color number) 125 were obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the colorless polymerization rosin ester was 50 ppm.

Example 8

In Example 4 (1), except for changing the polymerization rosin to be used as the undesulphurization polymerization rosin obtained in Example 1 (2), the esterification was carried out in the same manner, and the subsequently obtained desulfurization polymerization rosin The ester was subjected to desulfurization reaction in the same manner as in Example 1 (3) to give a desulphurized polymerization rosin ester having an acid value of 18.5 mgKOH / g, a softening point of 161 占 폚, and a color tone (Gardner color number) 7. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the desulfurization purification polymerization rosin ester was 91 ppm.

The desulphurized polymerization rosin ester thus obtained was stored at room temperature for 2 months in the same manner as in Example 4 (2), and subjected to a hydrogenation reaction to give a colorless polymerization of an acid value of 19.5 mgKOH / g, a softening point of 160 ° C., and a color tone (hagen color number) 175. Rosin ester was obtained. By fluorescent X-ray measurement, it was recognized that the sulfur content in the colorless polymerization rosin ester was 55 ppm.

Example 9

In Example 4 (1), the esterification was carried out in the same manner as in Example 4 (1) except that the alcohol (mixture of pentaerythritol and glycerin) used was changed to 120.0 g of glycerin, and the acid value was 10.8 mgKOH / g. And a desulphurization polymerization rosin ester having a softening point of 151 ° C and a color tone (Gardner color number) 6 were obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the desulfurization purification polymerization rosin ester was 78 ppm.

Subsequently, a hydrogenation reaction was carried out in the same manner as in Example 4 (2) to give a colorless polymerization rosin ester having an acid value of 12.4 mgKOH / g, a softening point of 148 ° C, and a color tone (hagen color number) 60. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the colorless polymerization rosin ester was 45 ppm.

Example 10

In Example 9, the hydrogenation reaction was carried out in the same manner as in Example 4 (2) except that the desulphurized polymerized rosin ester used in Example 9 was changed to one stored at room temperature for 2 months. A colorless polymerization rosin ester having an acid value of 12.3 mgKOH / g, a softening point of 149 ° C, and a color tone (hagen color number) 100 was obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the colorless polymerization rosin ester was 46 ppm.

Example 11

In Example 9, esterification was carried out in the same manner as in the polymerization rosin to be used, except that the desulfurized and purified polymerization rosin obtained in Example 1 (3) was stored at room temperature for 2 months, and the acid value was 11.5 mgKOH / g, The desulphurization polymerization rosin ester of softening point 150 degreeC and color tone (Gardner color number) 6 was obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the desulphurized polymerization rosin ester was 77 ppm.

Subsequently, a hydrogenation reaction was carried out in the same manner as in Example 4 (2) to obtain a colorless polymerization rosin ester having an acid value of 13.1 mgKOH / g, a softening point of 148.5 ° C, and a color tone (hagen color number) 80. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the colorless polymerization rosin ester was 48 ppm.

Example 12

In Example 9, the hydrogenation reaction was carried out in the same manner as in Example 4 (2) except that the polymerization rosin ester to be used was changed to that stored in the desulphurization polymerization rosin ester used in Example 11 at room temperature for 2 months. A colorless polymerization rosin ester having an acid value of 12.8 mgKOH / g, a softening point of 149 ° C, and a color tone (hagen color number) 100 was obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the colorless polymerization rosin ester was 51 ppm.

Example 13

In Example 9, esterification was carried out in the same manner as in Example 9 except that the polymerization rosin to be used was changed to the fine desulfurization purification polymerization rosin obtained in Example 1 (2), and then the obtained desulfurization purification polymerization was obtained. The desulfurization reaction was carried out in the same manner as in Example 1 (3) to obtain a desulphurized polymerization rosin ester having an acid value of 10.8 mgKOH / g, a softening point of 151 ° C, and a color tone (Gardner color number) 7. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the desulphurized polymerization rosin ester was 83 ppm.

Subsequently, the obtained desulphurized polymerization rosin ester was stored at room temperature for 2 months, and then subjected to a hydrogenation reaction in the same manner as in Example 4 (2), to an acid value of 12.3 mgKOH / g, a softening point of 149.5 ° C, and a colorless color (hagen color number) 125. The polymerization rosin ester was obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the colorless polymerization rosin ester was 43 ppm.

Comparative Example 1 (Hydride of Crude Polymerization Rosin)

The polymerization rosin obtained by Example 1 (desulfurized) was polymerized in the same manner as in Example 1 without distilling the crude polymerization rosin (raw rosin), except that the polymerization rosin obtained (desulfurization) was obtained. And hydrogenation polymerization rosin was prepared in the same manner as in Example 2. The hydrogenation polymerization rosin had an acid value of 138.3 mgKOH / g, a softening point of 140 ° C. and a color tone (Gardner color number) 4. The hydrogenation polymerization rosin was measured by GPC. It was recognized that the content of the polymer in the mixture was 70.7%, the monomer (hydride of the refined rosin) was 26.8%, and the decomposition product was 2.5%, and the amount of sulfur in the hydrogenated polymerization rosin was 112 ppm by fluorescence X-ray measurement.

Comparative Example 2 (Hydride of Fine Desulphurization Polymerization Rosin)

In place of the polymerization rosin (desulfurized) obtained in Example 1 used in Example 2 except that the polymerization rosin (non-desulfurized) obtained in Example 1 (2) was stored at room temperature for 2 months in the air. In the same manner as in Example 2, a hydrogenation polymerization rosin was prepared. The hydride had an acid value of 142.3 mgKOH / g, a softening point of 140 ° C, and a color tone (Gardner color number) 3. By GPC measurement, it was recognized that the content of the polymer in the hydrogenated polymerization rosin was 71.8%, the monomer (hydride of the refined rosin) was 25.9%, and the decomposition product was 2.3%. It was recognized that the sulfur content in the gin was 110 ppm.

Comparative Example 3

In Example 4 (1), the polymerization rosin used was the same except that the purification of Example 1 (1) and the crude fine desulfurization polymerization rosin without performing the desulfurization treatment of Example 1 (3) were used. The esterification was carried out to obtain a crude undesulfurized polymerization rosin ester having an acid value of 16.0 mgKOH / g, a softening point of 163 ° C, and a color tone (Gardner color number) 10. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the crude undesulfurized polymerization rosin ester was 190 ppm.

Subsequently, a hydrogenation reaction was carried out in the same manner as in Example 4 (2) to give an acid value of 18.3 mgKOH / g, a softening point of 160 ° C., and a hydrogenation polymerization rosin ester having a color tone (Gardner color number) 5. By fluorescent X-ray measurement, it was recognized that the sulfur content in the hydrogenation polymerization rosin ester was 114 ppm.

Comparative Example 4

In Example 4 (1), it was esterified in the same manner except having changed the polymerization rosin to be used into the undesulfurization polymerization rosin obtained in Example 1 (2), and the acid value is 18.2 mgKOH / g and the softening point of 161 degreeC. , De-sulfurized tablet polymerization rosin ester of hue (Gardner color number) 7 was obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the undesulfurized purified polymerization rosin ester was 186 ppm.

Subsequently, the obtained undesulphurized purified polymerization rosin ester was stored at room temperature for 2 months, and then subjected to a hydrogenation reaction in the same manner as in Example 4 (2), with an acid value of 19.2 mgKOH / g, a softening point of 159.5 ° C, and a color tone (Gardner color number) 3 The hydrogenation polymerization rosin ester of was obtained. By fluorescent X-ray measurement, it was recognized that the sulfur content in the hydrogenated polymerization rosin ester was 113 ppm.

Comparative Example 5

In Example 4 (1), esterification was carried out in the same manner except that the polymerization rosin to be used was changed to that in which the undesulfurized purified polymerization rosin obtained in Example 1 (2) was stored at room temperature for 2 months, and the acid value was 17.5. mgKOH / g, the softening point 162 degreeC, and the desulfurization refine | purified polymerization rosin ester of hue (Gardner color number) 9 were obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the undesulfurized purified polymerization rosin ester was 184 ppm.

Then, the hydrogenation reaction was performed like Example 4 (2), and the hydrogenation polymerization rosin ester of acid value 18.3 mgKOH / g, the softening point 160.5 degreeC, and color tone (Gardner color number) 4 was obtained. By fluorescent X-ray measurement, it was recognized that the sulfur content in the hydrogenation polymerization rosin ester was 106 ppm.

Comparative Example 6

In Example 9, the acid value of 10.6 mgKOH / g, the softening point of 151 ° C, and the color tone (Gardner color number) 7 were the same, except that the polymerization rosin to be used was the undesulfurized purified polymerization rosin obtained in Example 1 (2). Fine desulfurization purification polymerization rosin ester was obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the undesulfurized purified polymerization rosin ester was 180 ppm.

Subsequently, the undesulfurized purified polymerization rosin ester obtained was stored at room temperature for 2 months, and then subjected to a hydrogenation reaction in the same manner as in Example 4 (2), with an acid value of 11.7 mgKOH / g, a softening point of 150 ° C., and a color tone (Gardner color number) 3 Hydrogenation polymerization rosin ester was obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the hydrogenated polymerization rosin ester was 105 ppm.

Comparative Example 7

In Example 9, the polymerization value to be used was the same except that the undesulfurized purified polymerization resin obtained in Example 1 (2) was stored at room temperature for 2 months, and the acid value was 11.8 mgKOH / g, a softening point of 150 ° C. The non-desulfurization refined polymerization rosin ester of hue (Gardner color number) 9 was obtained. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the undesulfurized purified polymerization rosin ester was 181 ppm.

Subsequently, a hydrogenation reaction was carried out in the same manner as in Example 4 (2) to obtain an acid value 13.1 mgKOH / g, a softening point of 149 ° C., and a hydrogenated polymerization rosin ester having a color tone (Gardner color number) 3. By fluorescent X-ray measurement, it was recognized that the amount of sulfur in the hydrogenated polymerization rosin ester was 107 ppm.

(Performance evaluation) The performance of various polymerization rosin obtained by each Example and the comparative example was evaluated on condition of the following. The results are shown in Tables 2, 3, and 4. In addition, in Comparative Examples 8-10, the following tackifying resin is used. Comparative Example 8: Pencell D-160 (manufactured by Hwangcheon Chemical Industry Co., Ltd.), Comparative Example 9: Fine Crystal KE-311 (manufactured by Hwangcheon Chemical Industry Co., Ltd.), Comparative Example 10: Fine Crystal KE-100 (Hancheon Chemical Industry Co., Ltd.) (subject). The results are shown in Tables 5-8.

(Heating Stability) 10 g of the sample was placed in a test tube having an inner diameter of 1.5 cm and a height of 15 cm, and was left still in a pure air dryer at 180 ° C. without being covered with a lid. The change in color tone (Gardner color number) with time was observed.

(Solvent solubility) Add 10g of polymerized rosin and normal hexyl diglycol (HeDG) obtained in each example and comparative example to the screw tube (30% by weight, 40% by weight, and 50% by weight of the polymerized rosin). .) Prepare samples of each sample concentration. The prepared sample was shaken with a shaker for 2 hours, and the solubility to HeDG of the sample after shaking was evaluated.

(Circle): melt | dissolved completely, (triangle | delta): It melt | dissolves and the remainder is 1 g or less,

Ⅹ: Melt and the remaining amount exceeds 1 g.

(Crystalline) 2.5 g of polymerization rosin obtained by each Example and a comparative example and 7.5 g of HeDG were put into the test tube of 1.5 cm inside diameter and 15 cm height, and after heat-dissolving, the test tube was enclosed and the precipitation of crystal | crystallization was observed.

(Circle): No crystal precipitation, Ⅹ: A crystal precipitates or becomes cloudy.

Table 2

Hue (Gardner color depth) Before heating After 6 hours heating Example 1 5 6+ Example 2 1> 2- Example 3 1> 2- Comparative Example 1 4 5 Comparative Example 2 3 4 Desulfurization Polymerization Rosin 5 7

In the table, undesulfurized polymerization rosin means a polymerization rosin which does not undergo desulfurization treatment obtained in Example 1 (2).

Table 3

Solubility 30 wt% 40 wt% 50 wt% Example 1 ○ ○ Ⅹ Example 2 ○ ○ △ Example 3 ○ ○ △ Comparative Example 1 ○ ○ Ⅹ Comparative Example 2 ○ ○ Ⅹ Desulfurization Polymerization Rosin ○ △ Ⅹ

In the table, undesulfurized polymerization rosin means a polymerization rosin which does not undergo desulfurization treatment obtained in Example 1 (2).

Table 4

Crystallinity Early 2 months later Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Comparative Example 1 ○ Ⅹ Comparative Example 2 ○ ○ Desulfurization Polymerization Rosin ○ Ⅹ

In the table, undesulfurized polymerization rosin means a polymerization rosin which does not undergo desulfurization treatment obtained in Example 1 (2).

In this case, the sulfur content of more than 100 ppm is poor in heat stability than the sulfur content of 100 ppm or less, and the solubility in organic solvents and the like is obvious.

Table 5

Resin Tint (Gardner Color Count) Early After 6 hours heating Example 4 1 or less 3 Example 5 1 or less 3 Example 6 1 or less 3 Example 7 1 or less 3 Example 8 1 or less 3 Example 9 1 or less 4 Example 10 1 or less 4 Example 11 1 or less 4 Example 12 1 or less 4 Example 13 1 or less 4 Comparative Example 3 5 10 Comparative Example 4 3 6 Comparative Example 5 4 6 Comparative Example 6 3 6 Comparative Example 7 3 6

Evaluation Examples 1 and 2 and Comparative Evaluation Examples 1 and 2

The flux for soldering using the polymerization rosin which does not perform desulfurization treatment obtained in Example 1, 2, the comparative example 2, and Example 1 (2), and the solder paste was prepared and evaluated.

(Preparation of Solder Paste)

 Flux was prepared by the raw material formulation shown in Table 6 (the amount of each component in the table represents parts by weight). SnAgCu system braze metal powder (Sn96.5 weight%, Ag3 weight%, Cu0.5 weight%; brand name "Sn96.5 / Ag3 / Cu0.5", 11 weight part of flux obtained subsequently, Samjung Metal Mining Co., Ltd.) (89) 89 parts by weight were added and kneaded with a sulfur grinder for 1 hour to prepare a solder paste.

Soldering: Bump Bonding

 The solder paste obtained above was printed on the bump-forming test substrate (a substrate having a soldered land with a pitch of 220 µm), and soldered by nitrogen reflow, which was used as a test piece. The printing conditions are as follows. The bump diameter is about 100 μm.

<Printing conditions>

Metal mask: laser processed product of thickness 70㎛

Metal skid speed: 20mm / second

Plate separation speed: 0.1mm / second

<Reflow profile>

Preheat: 90 seconds at 150-160 degrees Celsius

Peak temperature at reflow: 235 ° C

Reflow condition: More than 220 degrees Celsius, approximately 30 seconds

Evaluation method of dregs color after reflow

○: colorless and transparent

(Triangle | delta): There is coloring to a residue

Table 6

Evaluation example Evaluation example Comparative Evaluation Example 1 Comparative Evaluation Example 2 Bis resin Example 1 46.4 Example 2 46.4 Comparative Example 2 46.4 Desulfurization Polymerization Rosin 46.4 Active agent Adipic acid One One One One Diethylamine silver One One One One Thixotropic agent Cured Castor Oil 8 8 8 8 solvent Hexylcarbitol 43.6 43.6 43.6 43.6 Afterglow △ ○ △ Ⅹ

In the table, undesulfurized polymerization rosin means a polymerization rosin which does not undergo desulfurization treatment obtained in Example 1 (2).

(Adhesion performance)

The rosin-type resin prepared by the said Example and the comparative example is used as a tackifier, and it is a post-addition method (it is an adhesive agent composition obtained by the method of mixing a base acrylic polymer composition and tackifying resin, and it is a post addition method below). In this case, it is based on the method.) The adhesive adhesion performance was evaluated by the acryl emulsion system. The results are shown in Table 7.

Furthermore, the adhesive adhesion performance only of the acrylic emulsion was evaluated, without adding a tackifier as a reference example.

(Preparation method of resin emulsion)

After dissolving 100 parts of the resin obtained in Examples and Comparative Examples at 80 parts of toluene for about 1 hour at 80 hours, 3 parts of emulsifier (DKS Discot N-14, manufactured by Cheil Industries) is added in terms of solid content and 160 parts of water. And it stirred at 200 rpm at 80 degreeC for 1 hour, and performed preliminary emulsification. The preliminary emulsion obtained was emulsified at a pressure of 400 MPa by a high pressure emulsifier (APV manufactured by Wes Corporation) to obtain an emulsion. Subsequently, 200 parts of electric emulsions were put into the vacuum distillation apparatus, and it distilled under reduced pressure for 6 hours on 50 degreeC and 13 kPa conditions, and obtained 123 parts of resin emulsions (50% of solid content).

Table 7

Compatibility (% T) Holding power (hours) Adhesive force (g / 25㎜) Turk Probe (g / 5mmφ) Ball (No.) Example 4 86.4 > 24 720 610 7 Example 7 86.6 > 24 710 614 7 Example 9 86.6 > 24 700 602 7 Example 12 86.6 > 24 690 604 7 Comparative Example 3 86.3 > 24 710 603 7 Comparative Example 4 86.4 > 24 720 600 7 Comparative Example 6 86.6 > 24 700 611 7 Comparative Example 8 86.8 > 24 770 642 7 Comparative Example 9 87.5 2.1 610 588 7 Comparative Example 10 87.4 3.9 640 612 8 Reference Example 87.6 > 24 420 536 11

(Creation of sample film for performance evaluation)

A commercially available acrylic emulsion (ultrazoru W-105, manufactured by Gantz Chemical Co., Ltd.) and a resin emulsion prepared so as to have a solid content of 90/10 parts by weight, are mixed well, and then applied to a 38 µm thick PET film and 100 µm thick applique. The sample film was produced by coating directly in an applicator, drying for 5 minutes in 105 degreeC pure air drying. The thickness of the sample film was 30 micrometers.

Evaluation of the point and adhesive characteristic of an acrylic polymer composition was performed with the following method.

(Compatibility)

500 nm of light was irradiated to the adhesive film, and the transmittance | permeability (% T) was measured. The transmittance | permeability was measured using the U-3210 type magnetic spectrophotometer and Ellipse Co., Ltd. product.

(Holding power)

In accordance with PSTC7 (Creep Method), a sample film (25 mm x 25 mm) was attached to a stainless plate, and a time (h) until the sample film fell by applying a load of 1 kg at 60 ° C. to the sample film was measured.

(Adhesion)

 A sample film (150 mm long and 25 mm long) was attached to a polypropylene plate (PE) and a stainless plate (SUS), respectively, and peeled in the tape length direction of 180 ° at a peel rate of 300 mm / min in accordance with PSTC-1. The adhesive force (g / 25mm) around 25 mm of the tape gun was measured.

Turk Castle

 The ball turk test uses the J.DOW method described in JIS Z 0237 to obtain the maximum number of balls stopped on the sample film length of 10 cm by rolling the adhesive surface of the sample film in a column of 10 cm inclined distance at an angle of 30 °. Do it.

 Probe Turk test is carried out using NS Probe Turk Tester in accordance with ASTM D2979, probe AA # 40 polishing, load 100g / cm2, deer time 1 second.

The rosin-type resin prepared by the said Example and the comparative example was used as a tackifier, and the adhesive type adhesive performance was evaluated in the solvent type acrylic polymer composition by the post addition method. Below, the preparation method and performance evaluation method of the used solvent type acrylic polymer composition are demonstrated, and the result is shown in Table 8.

In addition, the adhesive adhesion performance only of the solvent type acrylic polymer composition was evaluated, without adding a tackifier as a reference example.

(1) described in (Preparation of solvent-type acrylic polymer composition) in four separate flasks equipped with a thermometer, a stirrer, a cooling tube, a dropping rod and a nitrogen introduction tube, and the temperature was raised to 80 ° C. under a nitrogen stream. Then, the mixed solution of (2) and (3) is dripped over 3 hours. Then, it heated at 80 degreeC for 2 hours, added (4) and cooled, and obtained the acrylic polymer composition (solid content 50%).

(Preparation of solvent type acrylic polymer composition)

(1) dissolved in 60 parts by weight of ethyl sulfate

(2) the following mixture

    Butyl acrylate 48.5 parts by weight

    48.5 parts by weight of 2-ethylhexyl acrylate

    3.0 parts by weight of acrylic acid

(3) 0.1 part by weight of a polymerization initiator (AIBN, Daeche Chemical Co., Ltd.) was dissolved in 10.0 parts by weight of ethyl sulfate.

(4) 30.0 parts by weight of ethyl sulfate

(Creation of Sample Film for Performance Evaluation)

The resulting acrylic polymer (50% solids), the resin dissolved in ethyl sulfate (50% solids), and the crosslinking agent (Polonate L, manufactured by Japan Polyurethane Industry) are blended and mixed well so as to have a solid content of 90/10 / 1.8 parts by weight. After coating directly with a 150-micrometer applicator on a 38-micrometer-thick PET film, and drying for 5 minutes in a 105 degreeC pure air dryer, it cured for 1 week at 23 degreeC, and created the sample film. The thickness of the sample film was 40 micrometers.

(Performance Evaluation Method)

The performance evaluation method of the point-adhesive property is the same as that of an emulsion type acrylic polymer composition.

Table 8

Compatibility (% T) Holding power (hours) Adhesive force (g / 25㎜) Turk Probe (g / 5mmφ) Ball (No.) Example 4 74.4 > 24 730 1007 7 Example 7 74.5 > 24 730 1002 7 Example 9 74.5 > 24 720 1012 7 Example 12 74.5 > 24 720 1004 7 Comparative Example 3 74.4 > 24 710 998 7 Comparative Example 4 74.5 > 24 720 1000 7 Comparative Example 6 74.7 > 24 710 1011 7 Comparative Example 8 75.4 > 24 740 1060 7 Comparative Example 9 87.8 3.5 660 766 7 Comparative Example 10 87.8 5 640 765 14 Reference Example 86.1 > 24 500 785 14

(Weather resistance)

First, weather resistance was evaluated using the sample film for performance evaluation prepared. Below, the detail is demonstrated and a result is shown to Table 9, 10.

Weatherability Evaluation Method

Firstly, the sample film for performance evaluation was irradiated with UV using a UV tester (SUV-F11, manufactured by DAKYO Electric Co., Ltd.) (irradiation 80 mW Ⅹ 2 cm, irradiation temperature 60 ° C) Weather resistance was evaluated by the turbidity of the later sample film and the yellowness of the sample film visually.

◎: Colorless transparent

○: less than 10% yellowing

(Triangle | delta): Yellowing part 105-0%

Ⅹ: More than 50% yellowing

(Turkiness evaluation method)

The performance evaluation method of the weather resistance is the same as the evaluation method of turk property (probe turk) by an emulsion system and a solvent system.

Table 9

water system Solvent system  Compatibility (% T)  Turk (Probe Turk)  Compatibility (% T)  Turk (Probe Turk) Elapsed time (hours) Elapsed time (hours) 0 2 4 0 2 4 Example 4 86.4 610 445 321 74.4 1007 680 578 Example 7 86.6 614 444 318 74.5 1002 676 573 Example 9 86.6 602 443 315 74.5 1012 710 594 Example 12 86.6 604 441 313 74.5 1004 703 589 Comparative Example 3 86.1 603 431 299 74.1 998 644 540 Comparative Example 4 86.2 600 440 310 74.3 1000 668 560 Comparative Example 6 86.6 611 445 313 74.7 1011 700 582 Comparative Example 8 86.8 642 190 109 75.4 1060 364 200 Comparative Example 9 87.5 588 311 150 87.8 766 282 30 Comparative Example 10 87.4 612 311 130 87.9 765 164 46 Reference Example 87.6 536 489 480 86.1 785 701 662

Table 10

water system Solvent system Sample film color tone Sample film color tone Elapsed time (hours) Elapsed time (hours) 0 2 4 0 2 4 Example 4 ◎ ◎ ◎ ◎ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ ◎ ◎ Example 9 ◎ ◎ ◎ ◎ ◎ ◎ Example 12 ◎ ◎ ◎ ◎ ◎ ◎ Comparative Example 3 △ △ Ⅹ △ △ Ⅹ Comparative Example 4 △ △ △ △ △ △ Comparative Example 6 △ △ △ △ △ △ Comparative Example 8 Ⅹ Ⅹ Ⅹ Ⅹ Ⅹ Ⅹ Comparative Example 9 ◎ ◎ ○ ◎ ◎ ○ Comparative Example 10 ◎ ◎ ○ ◎ ◎ ○ Reference Example ◎ ◎ ◎ ◎ ◎ ◎

Hydrogenated polymerization rosin esters resulted in significantly improved weather resistance compared to polymerization rosin esters (Comparative Examples 6) which did not undergo hydrogenation and desulfurization (Comparative Examples 9 and 10). . In addition, it can be said that the colorless polymerization rosin ester can be used suitably for a transparent base material without deterioration of the color tone of the sample film over time.

(Polymerization inhibitory)

Assuming that the rosin-based resin prepared according to the above Examples and Comparative Examples is used as a tackifier, a polymer composition is prepared by using the initiator as a whole addition method (mixing the acrylic monomer and the tackifying resin before polymerization and then using the initiator. Method) to prepare an emulsion type, a solvent type and an ultraviolet curing acrylic polymer composition, and evaluated the polymerization inhibition. Below, such a detail is demonstrated in order and a result is shown in Table 11. FIG.

In addition, an emulsion type, a solvent type, and an ultraviolet curing acrylic polymerization composition were prepared without adding a tackifier as a reference example.

(Preparation method of emulsion type acrylic polymer composition)

Equipped with thermometer, stirring device, cooling tube, dropping rod and nitrogen introduction tube (4) and 21.4 parts by weight of water were added dropwise in sequence to (1) and (2) described in (Preparation of Emulsion Acrylic Polymer Composition) among 4 flasks that can be separated. . The resulting mixture was ultrasonically irradiated and dispersed while stirring to obtain a monomer emulsion. Next, 16.3 weight part of water was put into the four flasks which can be separated as mentioned above, and after temperature rising to 80 degreeC under nitrogen gas airflow, 0.075 weight part of (3) was added and dissolved. Then, the said monomer emulsion and 0.45 weight part of (3) were dripped polymerization over 3 hours. After completion of the dropwise addition, the residue was further kept warm for 1.5 hours while dividing 0.02 parts by weight of the remainder (3), followed by polymerization. Thereafter, the mixture was cooled, ammonia water and water were added, the nonvolatile components were adjusted to 60% by weight, and pH = 78, followed by filtration to obtain an acrylic polymer composition. In addition, as the reference example 1, it superposed | polymerized by the above-mentioned method without using a tackifier, and prepared the acrylic polymer.

(Preparation of emulsion type acrylic polymer composition)

(1) 48.00 parts by weight of butyl acrylate

    2-ethylhexyl acrylate 48.00 parts by weight

    3.00 parts by weight of methyl methacrylate

    1.00 parts by weight of acrylic acid

    10.0 parts by weight of rosin-based resin

(2) 1.0 part by weight of a chain transfer agent (n-dodecyl mercaptan)

(3) 0.545 parts by weight of a polymerization initiator (ammonium persulfate, manufactured by Samsung Gas Chemical Co., Ltd.)

(4) 1.0 part by weight of anionic emulsifier (Aqua Ron KH-10, manufactured by Cheil Industries Pharmaceutical Co., Ltd.)

1.2 parts by weight of nonionic emulsifier (Aqua Ron RN-2025, manufactured by Jeil Ind. Pharmaceutical Co., Ltd.)

(Molecular Weight)

Gel permeation chromatography (manufactured by Iso Co., Ltd., HLC-8120, column used: TSKgel Surper HML Ⅹ 3, developing solvent: tetrahydro franc) was carried out under conditions of a flow rate of 1.00 ml / min and a measurement temperature of 40 ° C to obtain a weight average molecular weight. It measured by polystyrene conversion value.

(Preparation method of a solvent type acrylic polymer composition)

In four separable flasks equipped with a thermometer, stirring device, cooling tube, dropping rod, and nitrogen introduction tube, (1) described in (Preparation of a solution-type acrylic polymer composition) was placed at a temperature of 80 ° C. under a nitrogen stream. It raises and continues, and the mixed solution of (2) and (3) is dripped over 3 hours. Then, it kept warm at 80 degreeC for 2 hours, added (4) and cooled, and obtained the acrylic polymer composition.

(Preparation of solution type acrylic polymer composition)

(1) Dissolve 10 parts by weight of the rosin-based resin in 50 parts by weight of ethyl sulfate

(2) the following mixture

    48.5 parts by weight of butyl acrylate

    48.5 parts by weight of 2-ethylhexyl acrylate

    3.0 parts by weight of acrylic acid

(3) 0.1 part by weight of a polymerization initiator (AIBN, manufactured by Daechung Chemical Co., Ltd.) was dissolved in 10.0 parts by weight of ethyl sulfate.

(4) 30.0 parts by weight of ethyl sulfate

(Preparation method of ultraviolet curable acrylic polymer composition)

A solution obtained by mixing (1) (3) indicated in (Preparation of UV-curable acrylic polymer composition) was added dropwise onto a glass plate, and a polycarbonate film was covered thereon to have a film thickness of 200 µm and to block oxygen. The acrylic polymer was prepared by performing irradiation 10 times of irradiation amount 80mJ / cm <2> using the 120W high pressure mercury lamp (Ultraviolet curing apparatus, the product made from Takeden) in the state. As a reference example, the acrylic polymer was prepared by the same method, without mix | blending rosin-type resin.

(Preparation of UV-curable acrylic polymer composition)

(1) 100 parts by weight of butyl acrylate

(2) 2.5 weight part of polymerization initiators (Tarocure 1173, Nippon Tigai Co., Ltd. product)

(3) 25 parts by weight of the rosin-based resin

Table 11

water system UV system Solvent system Molecular Weight (Mw) Example 4 560,000 35,000 550,000 Example 7 560,000 35,000 550,000 Example 9 570,000 35,000 350,000 Example 12 570,000 35,000 350,000 Comparative Example 3 520,000 33,000 330,000 Comparative Example 5 550,000 34,500 330,000 Comparative Example 6 540,000 34,500 320,000 Comparative Example 8 120,000 18,500 83,000 Comparative Example 9 420,000 28,700 184,000 Comparative Example 10 400,000 30,100 185,000 Reference Example 800,000 45,800 550,000

In the table, the molecular weight (Mw) represents the weight average molecular weight.

As mentioned above, as shown in Table 11, the acryl-type polymer obtained by mixing the tackifier of this invention can obtain the thing polymerized compared with the comparative example (8-10), and the tackifier of this invention inhibits polymerization. It was confirmed that the sex was very low.

Claims (20)

The polymerization rosin (A1) characterized by the content of the sulfur content which removed the sulfur content of the antioxidant obtained by desulfurizing the polymerization rosin (A) obtained using a sulfuric acid-type catalyst is 100 ppm or less. The hydrogenated polymerization rosin characterized by the content of the sulfur content which removed the sulfur content of the antioxidant obtained by hydrogenating a polymerization rosin (A1) is 100 ppm or less. The content of the sulfur content which removed the sulfur content of the antioxidant obtained by making a polymerization rosin (A1) and alcohol (B) react with polymerization rosin (A) is 100 ppm or less, The polymerization rosin ester characterized by the above-mentioned. The content of the sulfur content which removed the sulfur content of the antioxidant obtained by making superposition | polymerization rosin (A1) and alcohols (B) react is 100 ppm or less, The polymerization rosin ester characterized by the above-mentioned. The content of the sulfur content which removed the sulfur content of the antioxidant obtained by hydrogenating a polymerization rosin ester is 100 ppm or less, The hydrogenation polymerization rosin ester characterized by the above-mentioned. Process for producing a polymerization rosin (A1), characterized in that the polymerization rosin (A) is desulfurized. The method for producing a polymerization rosin (A1) according to claim 6, wherein the desulfurization treatment is performed at 100 to 300 ° C in the presence of a desulfurization catalyst. A method for producing a hydrogenated polymerization rosin, characterized in that the polymerization rosin (A1) is hydrogenated. A method for producing a hydrogenated polymerized rosin, characterized in that the content of the sulfur content obtained by desulfurizing the hydrogenated polymerized rosin obtained by hydrogenating the polymerized rosin (A) is 100 ppm or less. The method for producing a hydrogenated polymerization rosin according to claim 9, wherein the desulfurization treatment is performed at 100 to 300 ° C in the presence of a desulfurization catalyst. A method for producing a polymerization rosin ester, wherein the polymerization rosin (A1) is reacted with alcohols (B). A process for producing a hydrogenated polymerization rosin ester, wherein the polymerization rosin ester obtained by the production method according to claim 11 is hydrogenated. The soldering flux containing the polymerization rosin of Claim 1 or the hydrogenation polymerization rosin of Claim 2. The soldering flux according to claim 13, wherein the polymerization rosin of claim 1 or the hydrogenated polymerization rosin of claim 2 is 6 to 55% by weight. The soldering flux according to claim 13 or 14, further comprising an activator (B), an additive (C) and a solvent (D). A solder paste comprising the soldering flux and the solder powder according to any one of claims 13 to 15. The polymerization rosin ester of Claims 3 and 4, or the hydrogenation polymerization rosin ester of Claim 5 is contained, The tackifier characterized by the above-mentioned. A tackifying resin emulsion, wherein the tackifier according to claim 17 is emulsified. The tackifier of Claim 17 is contained, The adhesive agent composition characterized by the above-mentioned. A water-based adhesive agent composition comprising the tackifying resin emulsion according to claim 18.