KR20090027568A - A process for manufacturing rubber-like polymer for electronic materials, and rubber-like polymer for electronic materials - Google Patents

Abstract

A process for manufacturing rubber-like polymer for electronic materials is provided to ensure excellent polymerization stability and thermal stability in collecting monomers by using a specific nonionic surfactant as an emulsifier. A process for manufacturing rubber-like polymer for electronic materials comprises a step of manufacturing a latex copolymer through the emulsion polymerization by using polyoxyethylene alkylether represented by the chemical formula 1 which has HLB of 13.5-17.0 and the cloud point of the solution of 70 °C or more, as an emulsifier; and a step of obtaining the rubber-like polymer by heating the latex copolymer in the presence of electrolyte. In the chemical formula 1, R is a C8-12 aliphatic hydrocarbon group and n shows the average condensation number of ethylenoxide of 5-20.

Description

Manufacturing method of rubber-like polymer for electronic materials, and rubber-like polymer for electronic materials {A PROCESS FOR MANUFACTURING RUBBER-LIKE POLYMER FOR ELECTRONIC MATERIALS, AND RUBBER-LIKE POLYMER FOR ELECTRONIC MATERIALS}

The present invention relates to a method for producing a rubbery polymer for an electronic material and a rubbery polymer for an electronic material, and more particularly, to a rubbery polymer for an electronic material having excellent stability in an emulsion polymerization step and a monomer recovery step and having a low metal content. The manufacturing method of the rubbery polymer for electronic materials which can be manufactured with high yield, and the rubbery polymer for electronic materials manufactured by the manufacturing method of such a rubbery polymer for electronic materials.

Conventionally, as an emulsifier used when preparing a (co) polymer by emulsion polymerization, an anionic surfactant containing an alkali metal as a counter ion is widely used, and also in the step of separating the produced (co) polymer latex. As a coagulant, metal compounds such as sodium chloride and calcium chloride are used. Therefore, metal ion remained in the polymer obtained, and it was difficult to obtain the polymer with low metal ion content.

Therefore, when a paint, an adhesive, a sealing agent, etc. is manufactured using the polymer obtained by normal emulsion polymerization as a raw material, and coating it etc. on a metallic object, the metal surface is made to contain the metal surface by the metal ion contained in a polymer. There was a problem of corrosion.

On the other hand, a polymer containing almost no metal ions is coagulated by heating a (co) polymer latex obtained by using a nonionic surfactant as an emulsifier used in emulsion polymerization, by heating to a temperature above a cloud point without using a coagulant. The manufacturing method is disclosed (for example, refer patent document 1 below). However, in this method, it is necessary to make the temperature of emulsion polymerization and the temperature at the time of monomer collection below the cloud point of the said nonionic surfactant, and there existed a problem that manufacturing conditions were limited. In addition, the (co) polymer latex usually has a problem that it becomes unstable because it becomes a high temperature in the monomer recovery process.

In addition, a method of obtaining a polymer by using an anionic surfactant at least as an emulsifier for emulsion polymerization and adding an electrolyte containing no nonionic surfactant and a metal to the obtained (co) polymer latex and heating is disclosed. (See, for example, Patent Document 2 below). Furthermore, after the (co) polymer latex is produced by emulsion polymerization, a method for producing a polymer is disclosed in which a nonionic surfactant is added, followed by heating to solidify (see, for example, Patent Document 3 below). ).

[Patent Document 1] Japanese Unexamined Patent Publication No. 59-170390

[Patent Document 2] Japanese Patent Application Laid-Open No. 62-74908

[Patent Document 3] Japanese Unexamined Patent Publication No. 8-100030

The invention described in Patent Document 2 secures the stability of the (co) polymer latex under high temperature in the monomer recovery process and the like, and further, by heating and coagulating the (co) polymer latex above the cloud point of the nonionic surfactant, the metal ions are almost It is to prepare a polymer that does not contain. However, the invention described in Patent Literature 2 uses an anionic surfactant as an emulsifier used in emulsion polymerization, so that the stability at high temperature of the (co) polymer latex is high, and after the addition of the nonionic emulsifier, heating above cloud point Even if it is difficult to completely precipitate the rubber, there was a problem that the yield is low. Moreover, since the invention described in patent document 3 uses an anionic surfactant as an emulsifier used for emulsion polymerization, there existed a problem similar to patent document 2.

This invention is made | formed in view of the above-mentioned problem, The manufacturing method of the rubbery polymer which is excellent in stability in an emulsion polymerization process and a monomer recovery process, and can manufacture the rubbery polymer for electronic materials with few metal contents in high yield, And a rubbery polymer for an electronic material produced by the method for producing a rubbery polymer for an electronic material.

In order to achieve the said subject, this invention provides the following manufacturing methods of the rubbery polymer for electronic materials, and the rubbery polymer for electronic materials.

[1] butadiene-acrylonitrile copolymer, butadiene-acrylonitrile-methacrylic acid copolymer, butadiene- (meth) acrylic acid ester copolymer, butadiene- (meth) acrylic acid ester-methacrylic acid copolymer, butadiene- 1 type of copolymer selected from the group which consists of a styrene- (meth) acrylic acid ester copolymer and a butadiene-styrene- (meth) acrylic acid ester-methacrylic acid copolymer, and contains Na metal ion content, K metal ion content, and The rubbery polymer for electronic materials whose total amount of Ca metal ion content is 1-50 ppm.

[2] The rubbery polymer for an electronic material according to [1], wherein the content of the repeating unit derived from butadiene is 67.2 to 81.4 mol% based on the entire copolymer.

[3] Emulsion polymerization is carried out using polyoxyethylene alkyl ether represented by the following formula (1) having a HLB of 13.5 to 17.0 and a clouding point of a 1.0 mass% aqueous solution of 70 DEG C or more, to prepare a copolymer latex. A method for producing a rubbery polymer for an electronic material, wherein the copolymerized latex is heated in the presence of an electrolyte to obtain a rubbery polymer.

(In Formula 1, R represents an aliphatic hydrocarbon group having 8 to 12 carbon atoms, n represents an ethylene oxide average condensation number of 5 to 20)

[4] A copolymer latex is produced by the emulsion polymerization, and the copolymer contained in the copolymer latex is a butadiene-acrylonitrile copolymer, butadiene-acrylonitrile-methacrylic acid copolymer, butadiene- (meth) Group consisting of acrylic ester copolymer, butadiene- (meth) acrylic acid ester-methacrylic acid copolymer, butadiene-styrene- (meth) acrylic acid ester copolymer, and butadiene-styrene- (meth) acrylic acid ester-methacrylic acid copolymer The manufacturing method of the rubbery polymer for electronic materials as described in [3] which is 1 type chosen from.

According to the manufacturing method of the rubbery polymer for electronic materials of this invention, it is possible to make high polymerization stability and thermal stability at the time of monomer recovery by using a specific nonionic surfactant as an emulsifier used for emulsion polymerization, and also a specific nonionic By using a type surfactant, the heat coagulation | solidification property after addition of a cloud point depressant is high (high yield), and it has the characteristics. In addition, since a general metal ion-based coagulant is not used at the time of coagulation, the amount of metal ions in the rubber is very small. Moreover, according to the rubbery polymer for electronic materials of this invention, since there is little Na metal ion content, K metal ion content, and Ca metal ion content, the coating material, adhesive agent, and sealing compound containing the rubbery polymer for electronic materials of this invention. When coating etc. on metal objects etc., corrosion of a metal surface is suppressed.

EMBODIMENT OF THE INVENTION Hereinafter, although the best form for implementing this invention is demonstrated concretely, this invention is not limited to the following embodiment, It is suitably based on common knowledge of those skilled in the art in the range which does not deviate from the meaning of this invention. It is to be understood that changes in the design, improvements, etc., may be made.

(1) emulsion polymerization (copolymer latex production) process:

The manufacturing method of the rubbery polymer for electronic materials (henceforth a "rubber-like polymer" of this invention) of this invention, First, HLB is 13.5-17.0, The said chemical formula 1 whose clouding point of 1.0 mass% aqueous solution is 70 degreeC or more. Emulsion polymerization is carried out using polyoxyethylene alkyl ether represented by? As an emulsifier to prepare a copolymer latex. The resulting copolymer latex is obtained by dispersing fine particles of a rubbery polymer in water. Thus, since polyoxyethylene alkyl ether which is a nonionic surfactant is used, it becomes possible to reduce the metal ion contained in the rubbery polymer obtained. In addition, since emulsion polymerization is carried out using HLB and a polyoxyethylene alkyl ether having a cloud point as the emulsifier, the polymerization stability can be enhanced to increase the thermal stability at the time of monomer recovery.

Here, high polymerization stability means that the amount of precipitation rubber contained in the latex after completion | finish of polymerization is 1% or less. In addition, HLB (Hydrophile-Lipophile Balance) is a hydrophilic lipophilic balance and is a value computed by the Griffin method. In addition, a cloud point is the value measured using 1% aqueous solution. The cloud point is a temperature at which a cloudy state is first generated when the aqueous solution of the nonionic surfactant is heated, and is a characteristic phenomenon occurring in the aqueous solution of the nonionic surfactant. Therefore, when the temperature of the nonionic surfactant aqueous solution of a certain composition is raised, it will become cloudy at the temperature more than cloud point, and the solution will separate two layers. Therefore, when performing emulsion polymerization or a monomer recovery, it is necessary to carry out below cloud point of an emulsifier.

HLB of the polyoxyethylene alkyl ether which is a nonionic surfactant used as an emulsifier is 13.5-17.0, It is preferable that it is 14.0-16.8, It is more preferable that it is 15.0-16.5. By carrying out HLB of an emulsifier in such a range, it can superpose | polymerize stably, without gelatinizing and generating a large amount of precipitate during superposition | polymerization, and also the stability at the time of heating in a monomer recovery process becomes favorable. If the HLB is less than 13.5, the polymerization raw material may be emulsified, gelled during polymerization, or a large amount of precipitate may occur. When HLB exceeds 17.0, the water solubility of an emulsifier is too high, and it becomes difficult to form a stable emulsion, and polymerizable property falls as mentioned above.

The cloud point of the 1.0 mass% aqueous solution of polyoxyethylene alkyl ether used as an emulsifier is 70 degreeC or more, It is preferable that it is 75-90 degreeC, It is more preferable that it is 78-88 degreeC. By making the cloud point of 1.0 mass% aqueous solution of an emulsifier into a high value of 70 degreeC or more, the polymerization temperature in emulsion polymerization can be selected in a wide range, and it becomes possible to superpose | polymerize stably. In addition, the thermal stability in the monomer recovery step can be ensured. If the clouding point is less than 70 ° C, the selection range of the polymerization temperature in the emulsion polymerization is narrowed, so that the polymerization cannot be stably performed, and the latex destabilizes during monomer recovery and precipitation of rubber occurs, which is not preferable.

In the polyoxyethylene alkyl ether represented by the above formula (1), R is preferably an aliphatic hydrocarbon group having 10 carbon atoms. In addition, it is preferable to select n so that cloud point of HLB and 1.0 mass% aqueous solution may be a value within a predetermined range according to the kind of R. n is an ethylene oxide average condensation number of 5-20, and "the ethylene oxide average condensation number of 5-20" is M calculated | required Mw by the molecular weight measurement of the polyoxyethylene alkyl ether which has a specific R, and n computed from structural formula Is the value of.

Examples of the polyoxyethylene alkyl ether emulsifier include emulgen 109P (polyoxyethylene lauryl ether) manufactured by Kao Corporation, emulgen 120 (polyoxyethylene lauryl ether), emulgen 123P (polyoxyethylene lauryl ether), and Mulgen 147 (polyoxyethylene lauryl ether) and SD-80 (polyoxyethylene isodecyl ether) by Dai-ichi Kogyo Seiyaku Co., Ltd., SD-110 (polyoxyethylene isodecyl ether), SD-150 (polyoxyethylene iso Decyl ether).

As an emulsifier, the said polyoxyethylene alkyl ether may be used individually by 1 type, and multiple types in the said polyoxyethylene alkyl ether may be mixed and used. When using several types of polyoxyethylene alkyl ether, it is preferable that cloud point of HLB and 1.0 mass% aqueous solution with respect to the whole mixed polyoxyethylene alkyl ether becomes the said predetermined range.

As an emulsifier, you may use together other emulsifiers other than the said polyoxyethylene alkyl ether. As another emulsifier, a nonionic surfactant, an ionic surfactant, etc. are mentioned. Polyoxypropylene alkyl ether etc. are mentioned as nonionic surfactant. Examples of the ionic surfactants include sodium dodecylbenzene sulfonate. As for the compounding ratio of polyoxyethylene alkyl ether and other surfactant, it is preferable that other surfactant is 0.1-20 mass parts with respect to 100 mass parts of polyoxyethylene alkyl ether, and it is more preferable that it is 0.5-10 mass parts. By setting it as such a range, superposition | polymerization, recovery of a monomer, and heat coagulation operation can be performed stably. As another emulsifier, as an ionic surfactant, NeoPelex G-25 (sodium dodecylbenzenesulfonate) manufactured by Kao Corporation, Palex, SS-L (sodium alkyldiphenyl ether disulfonate), and nonionic surfactant are Daiichi Kogyo Co., Ltd. Seiyaku Co., Ltd. TDX-100D (polyoxyalkylene isotridecyl ether), TDX-120D (polyoxyalkylene isotridecyl ether), XL-50, XL-60, XL-6190, XL-70, XL-80 , XL-100, XL-140, XL-160, XL-400, XL-1000F (all are polyoxyethylene branched decyl ether). The said emulsifier may be used individually by 1 type, and may mix and use multiple types.

Although it will not specifically limit, if a copolymer is obtained as a monomer used for emulsion polymerization, Butadiene, an acrylonitrile, (meth) acrylic acid, (meth) acrylic acid ester, styrene, etc. are mentioned. As a copolymer obtained, butadiene-acrylonitrile copolymer, butadiene-acrylonitrile-methacrylic acid copolymer, butadiene- (meth) acrylic acid ester copolymer, butadiene- (meth) acrylic acid ester-methacrylic acid copolymer, butadiene One kind selected from the group consisting of -styrene- (meth) acrylic acid ester copolymer and butadiene-styrene- (meth) acrylic acid ester-methacrylic acid copolymer is preferable. Among these, butadiene-acrylonitrile copolymer and butadiene-acrylonitrile-methacrylic acid copolymer are more preferable. It is preferable that the compounding quantity of each monomer makes content of the repeating unit derived from butadiene into 67.2-81.4 mol% with respect to the whole copolymer in the rubbery polymer for electronic materials obtained.

Although it does not specifically limit as a method of manufacturing copolymer latex by emulsion polymerization, For example, the following methods are mentioned.

A predetermined monomer and the polyoxyethylene alkyl ether are added and emulsified to water as a solvent, a catalyst and a molecular weight modifier are added if necessary, and emulsion polymerization is performed at a predetermined temperature. In addition, the order, timing, etc. of adding each raw material are not limited to the said order, timing, etc.

When the compounding quantity of an emulsifier is 100 mass parts of whole monomers, it is preferable that it is 2-20 mass parts, and it is more preferable that it is 5-15 mass parts. By setting it as such a range, stable polymerization, monomer recovery, and heat coagulation can be performed. When the compounding quantity of an emulsifier is less than 2 mass parts, it may gelatinize during polymerization and many precipitates may generate | occur | produce. When more than 20 mass parts, heat coagulation property may fall.

It is preferable that it is 20-70 mass parts with respect to 100 mass parts of water, and, as for the compounding quantity of a monomer, it is more preferable that it is 30-60 mass parts. By setting it as such a range, superposition | polymerization can be performed stably. When the compounding quantity of a monomer is less than 20 mass parts, the density | concentration of the rubbery polymer in copolymer latex may become low, and productivity may fall. If it is more than 70 parts by mass, it may not be possible to form a stable emulsion and gelate during polymerization, or a large amount of precipitates may occur, and polymerization may not be performed stably.

As a polymerization initiator, a peroxide, an azo catalyst, a persulfate salt, a redox catalyst, etc. are mentioned. It is preferable that it is 0.005-2 mass parts with respect to 100 mass parts of monomers, and, as for the addition amount of a polymerization initiator, it is more preferable that it is 0.01-1 mass part. By setting it as such a range, it becomes possible to stably manufacture the rubbery polymer of desired molecular weight. If the amount of the catalyst added is less than 0.005 parts by mass, the polymerization may not proceed to the desired reaction rate, while if it is more than 2 parts by mass, the rubbery polymer of the desired molecular weight may not be obtained.

As a molecular weight modifier, t-dodecyl mercaptan, terpinolene, etc. are preferable. As addition amount of a molecular weight modifier, the quantity which can obtain a desired molecular weight can be determined suitably. For example, the amount of about 0.1-2 mass parts can be added with respect to 100 mass parts of monomers.

As other additives, an electrolyte, a pH adjuster, or the like may be added.

Emulsion polymerization can be performed by a well-known emulsion polymerization method, and it is preferable to superpose | polymerize, stirring emulsified liquid mixture which mixed raw materials, forming an emulsion liquid in the reactor from which oxygen was removed, and stirring. As an emulsification operation, it is preferable to emulsify the mixed liquid of the raw material with an emulsifier. A homomixer etc. can be used as an emulsifier. It is preferable that polymerization temperature is lower than the cloud point of 1.0 mass% aqueous solution of an emulsifier, It is more preferable that it is 0-50 degreeC, It is especially preferable that it is 5-25 degreeC. Since polyoxyethylene alkyl ether used as an emulsifier is a nonionic surfactant, it becomes poorly soluble in water at the temperature above cloud point, and loses activity as surfactant. Therefore, if the emulsion formed by emulsifying the raw material before or during the polymerization is at a temperature equal to or higher than the cloud point of the emulsifier, the emulsifying function of the emulsifier is lost, and gelation during polymerization or a large amount of precipitates may occur. Therefore, it is preferable to make the cloud point of the 1.0 mass% aqueous solution of an emulsifier into the upper limit of polymerization temperature, and to superpose | polymerize at lower temperature than this. Moreover, the rubbery polymer of desired molecular weight can be obtained more stably by performing emulsion polymerization in the range of 0-50 degreeC. When polymerization temperature is lower than 0 degreeC, it will become melting | fusing point of water which is a solvent, and may not be able to maintain a uniform polymerization system. Moreover, when it is higher than 50 degreeC, superposition | polymerization of high molecular weight rubber may not be possible stably.

Moreover, it is preferable to perform emulsion polymerization until it becomes 50 to 95% of polymerization conversion, and it is more preferable to carry out until it becomes 60 to 90%. By setting the polymerization conversion ratio in such a range, the gelation between the polymers can be suppressed and the production can be performed in high yield. When the polymerization conversion rate is lower than 50%, there are many residual monomers and productivity may fall, and also the molecular weight of a rubbery polymer may not be made into a desired value. When the polymerization conversion rate is higher than 95%, gelation between polymers may occur. Here, the polymerization conversion rate was calculated by measuring the solid content (mass%) of the latex in the polymerization. The polymerization time is not particularly limited as long as it is a time required to be the reaction rate, but is preferably about 5 to 24 hours.

A monomer, a polyoxyethylene alkyl ether, a catalyst, a molecular weight modifier, etc. may be added whole quantity before a reaction start, and you may carry out the split addition arbitrarily added after reaction start. In addition, conditions, such as temperature and stirring, can be arbitrarily changed as needed during reaction. The polymerization system may be either continuous or batchwise.

(2) monomer recovery process:

In the manufacturing method of the rubbery polymer for electronic materials of this invention, it is preferable to collect the unreacted monomer in the obtained copolymer latex before solidifying the rubbery polymer in the obtained copolymer latex. The recovery method of an unreacted monomer is not specifically limited, A well-known method can be used. For example, the method of distilling and collect | recovering the unreacted monomer in the obtained copolymer latex by reduced pressure, and the method of recovering by steam distillation are mentioned. In order to remove unreacted monomer efficiently from copolymer latex by distillation, steam distillation, etc., the monomer recovery process may be accompanied by the temperature rise of copolymer latex. Since the manufacturing method of the rubbery polymer for electronic materials of this invention uses the polyoxyethylene alkyl ether whose HLB is 13.5-17.0, and the cloud point of 1.0 mass% aqueous solution is 70 degreeC or more, it recovers unreacted monomer stably. Can be done. Since the cloud point is at a high temperature of 70 ° C or higher, it is possible to increase the temperature in the range below the cloud point in operations such as distillation and steam distillation. Here, in operations, such as distillation and steam distillation, it is preferable that the temperature of copolymer latex is less than the cloud point of 1.0 mass% aqueous solution of an emulsifier, It is more preferable that it is 35-65 degreeC, It is especially preferable that it is 45-55 degreeC. . When the copolymer latex reaches a temperature equal to or higher than the cloud point of the emulsifier, the emulsifying function of the emulsifier is lost, and the particulate rubbery polymer dispersed in the copolymer latex cannot maintain the state of the fine particles, which may aggregate and coagulate. Therefore, it is preferable to make the cloud point of the 1.0 mass% aqueous solution of an emulsifier into an upper limit of the temperature in steam distillation etc., and to carry out steam distillation etc. at a temperature lower than this.

(3) solidification process:

The manufacturing method of the rubbery polymer for electronic materials of this invention heats the obtained copolymer latex in presence of a specific electrolyte, and obtains a rubbery polymer. It is preferable to use the ammonium salt which does not contain a metal structurally as electrolyte to add. For example, ammonium sulfate, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium acetate, etc. are mentioned. These electrolytes may be used alone or in combination of two or more thereof. By using such an electrolyte, the metal content of the rubbery polymer obtained can be reduced. Moreover, after removing the monomer in copolymer latex in the said monomer collection process, it is preferable to perform a coagulation process. In addition, a metal content rate is the value measured with the atomic absorption photometer.

As another additive, antioxidant, pH adjuster, etc. can also be added.

First, an electrolyte is added to the obtained copolymer latex. The electrolyte functions as a cloud point lowering agent of the emulsifier and can lower the required heating temperature when heating to solidify the rubbery polymer. Accordingly, in the monomer recovery process, it can contribute to the improvement of sufficient production efficiency and the reduction of energy consumption. The drop of cloud point by the electrolyte is about 5 to 15 ° C. As electrolyte, ammonium sulfate, ammonium nitrate, etc. can be used preferably. Moreover, 1-100 mass parts is preferable with respect to 100 mass parts of solid content in copolymer latex, 5-50 mass parts is more preferable, 10-40 mass parts is especially preferable. By setting it as such a range, a cloud point can be effectively lowered. When it is less than 1 mass part, cloud point may not fall enough, and when more than 100 mass parts, stability of latex may fall.

Next, a rubbery polymer is obtained by heating and coagulating copolymer latex containing an electrolyte. It is preferable that heating temperature is more than the cloud point of the emulsifier lowered by electrolyte, and it is more preferable that it is 10 degreeC or more higher than cloud point. Industrially, the rubber polymer can be precipitated instantaneously by introducing the latex with electrolyte added into the high pressure steam pipe. About the temperature at the time of solidification, 80-110 degreeC is preferable, 85-105 degreeC is more preferable, 90-100 degreeC is especially preferable. By heating the copolymer latex above the cloud point of the emulsifier dropped by the electrolyte, the emulsifying function of the emulsifier is lost, and the particulate rubbery polymer dispersed in the copolymer latex cannot maintain the state of the fine particles, causing it to aggregate and precipitate (coagulate). )do. Thereby, the rubbery polymer which precipitates in water efficiently and has solidified can be obtained.

(4) washing and drying process:

Next, the obtained rubbery polymer can be washed and dried to finally obtain a rubbery polymer for an electronic material. It is preferable to perform washing | cleaning using water, and a washing | cleaning method is not specifically limited, It can wash | clean by a well-known method. For example, the method of carrying out filtration after putting a rubbery polymer in water, and stirring is mentioned. It does not specifically limit as a drying method, For example, hot air drying, a vacuum dryer, etc. are mentioned.

About the molecular weight of the rubbery polymer for electronic materials of this invention obtained, it can determine suitably according to the kind, use, etc. of a rubbery polymer.

Rubber-like polymers for electronic materials of the present invention include butadiene-acrylonitrile copolymer, butadiene-acrylonitrile-methacrylic acid copolymer, butadiene- (meth) acrylic acid ester copolymer, butadiene- (meth) acrylic acid ester-methacryl 1 type of copolymer selected from the group which consists of an acid copolymer, butadiene-styrene- (meth) acrylic acid ester copolymer, and butadiene-styrene- (meth) acrylic acid ester-methacrylic acid copolymer, and contains Na metal ion content , The total amount of K metal ion content and Ca metal content is 1 to 50 ppm. Although the rubbery polymer for electronic materials of this invention may contain polymers other than the said copolymer, it is preferable not to contain polymers other than the said copolymer.

Since the total amount of Na metal ion content, K metal ion content, and Ca metal ion content is as small as 1-50 ppm of the rubbery polymer for electronic materials of this invention as mentioned above, the rubbery polymer for electronic materials of this invention When coating a metal object with a coating material, an adhesive, a sealing agent, etc. containing the same, the corrosion of the metal surface is suppressed.

Moreover, it is preferable that content of the repeating unit derived from butadiene of the rubbery polymer for electronic materials of this invention is 67.2-81.4 mol% with respect to the said whole copolymer. Since the repeating unit derived from butadiene is contained in such a range, the effect of having sufficient rubber elasticity and flexibility is exhibited.

Content of components other than the repeating unit derived from butadiene in each copolymer is as follows. In the butadiene-acrylonitrile-methacrylic acid copolymer, the content of the repeating unit derived from acrylonitrile is preferably 15 to 30 mol%, and the content of the repeating unit derived from methacrylic acid is preferably 1 to 10 mol%. Do. In the butadiene- (meth) acrylic acid ester-methacrylic acid copolymer, the content of the repeating unit derived from the (meth) acrylic acid ester is preferably 10 to 20 mol%, and the content of the repeating unit derived from methacrylic acid is 1 to 10. Mol% is preferred. In the butadiene-styrene- (meth) acrylic acid ester copolymer, the content of the repeating unit derived from styrene is preferably 5 to 20 mol%, and the content of the repeating unit derived from the (meth) acrylic acid ester is preferably 10 to 20 mol%. Do. In the butadiene-styrene- (meth) acrylic acid ester-methacrylic acid copolymer, the content of the repeating unit derived from styrene is preferably 5 to 20 mol%, and the content of the repeating unit derived from the (meth) acrylic acid ester is 10 to 20. Mol% is preferable and, as for content of the repeating unit derived from methacrylic acid, 1-10 mol% is preferable.

The rubbery polymer for an electronic material of this invention can be manufactured by the manufacturing method of the rubbery polymer for electronic materials of this invention mentioned above.

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples. In addition, "part" and "%" in a following example and a comparative example are a mass reference | standard unless there is particular notice.

Each evaluation method for an Example and a comparative example is shown below.

1. Evaluation of Polymerization Stability:

The copolymer latex after emulsion polymerization was filtered through a nylon mesh (mesh size; 200 mesh) to recover the precipitated wet rubber. The recovered rubber was dried early with a blow dry set at 90 ° C., and the mass of the dried rubber was measured. The polymerization stability was evaluated by the mass. When the mass of the recovered dry rubber was 2.0% or less of the total amount of rubber, the polymerization stability was good, and when it exceeded 2.0%, the polymerization stability was poor. Here, "the total amount of rubber" is the amount of rubber components in solid content contained in the used latex.

2. Evaluation of stability in monomer recovery process:

In evaluating the polymerization stability, steam was blown into the copolymer latex, which was filtered through a nylon mesh and confirmed that it did not contain a precipitate until the liquid temperature reached 55 ° C to 60 ° C, and the steam was stopped for 15 minutes. It was. Thereafter, the filtrate was filtered through a nylon mesh (mesh size; 200 mesh) to recover the precipitated wet rubber. The recovered rubber was dried in a blow dryer set at 90 ° C., and the mass of the dried rubber was measured. From the mass, the stability in the monomer recovery process (stability at the time of monomer recovery) was evaluated. When the mass of the recovered dry rubber was 5.0% or less of the total amount of rubber, the stability in the monomer recovery step was considered to be good, and when it exceeded 5.0%, the stability in the monomer recovery step was considered to be poor.

3. Evaluation of coagulation:

When the yield of the obtained rubbery polymer is 85% or more, the coagulation | solidification property shall be favorable, and when the yield is less than 85%, it shall be poor. The yield was computed from the rubber component amount (mass) in latex computed from the solid content (%) of latex, and the rubber mass after drying.

(Example 1)

Synthesis of Rubbery Polymer (A-1):

10 parts of polyoxyethylene isodecyl ether (made by Daiichi Kogyo Seiyaku Co., Ltd., brand name: SD-110) and 2 parts of sodium dodecylbenzene sulfonate (made by Kao Corporation, brand name: Neopelex G-25) as water 200 parts An aqueous solution (emulsifier solution) dissolved, 75 parts (74.6 mol%) of butadiene and 25 parts (25.4 mol%) of acrylonitrile, 0.2 parts of t-dodecyl mercaptan as a molecular weight regulator, and a redox catalyst were added to the autoclave. After adding and adjusting the temperature at 10 degreeC, 0.01 part of paramentane hydroperoxides were added as a polymerization initiator, and emulsion polymerization was performed to 75% of a polymerization conversion rate. HLB of the polyoxyethylene isodecyl ether (SD-110) used was 15.5, and the cloud point of 1.0 mass% aqueous solution was 80 degreeC or more. HLB is the value computed by the Griffin method, and the cloud point is the value measured by the following method. The 1% aqueous solution of the nonionic emulsifier is heated to gradually increase the temperature, and when it reaches a certain temperature, the nonionic emulsifier is precipitated, and the aqueous solution that has been transparent until then appears cloudy. The temperature which started to become cloudy was made into a cloud point. The amount of addition was 0.1 part using paramentane hydroperoxide as a polymerization initiator. The polymerization conversion was calculated by solid content measurement.

Next, 0.1 part of reaction terminator N, N-diethylhydroxylamine was added, and the copolymer latex was obtained. Thereafter, steam was blown into the copolymer latex to remove unreacted raw material monomer at a liquid temperature of 50 ° C. or lower under reduced pressure, and then allowed to cool to room temperature. Next, after adding 20 parts of ammonium sulfate (cloud point depressant) and confirming that it melt | dissolved completely, the rubber polymer was precipitated by blowing steam and making liquid temperature 90 degreeC or more. The rubber-like polymer (A-1) was isolated by washing the precipitated rubbery polymer with water, dewatering and drying with a blow dryer set at 90 ° C. The viscosity was measured with a Mooney tester about the rubbery polymer (A-1), and the result was 60ML _{1 +4} (100 ° C). In addition, using an atomic absorption photometer, the alkali metal ion content contained in the rubbery polymer (A-1) was analyzed, and Na; 10 ppm, K; 8 ppm, Ca; 1 ppm. When content of a metal ion is 50 ppm or less in total, it was made favorable. The same applies to the following. Moreover, 1.0% in the polymerization stability evaluation, 3.5% about the stability at the time of monomer recovery, and 90% in the coagulation | solidification evaluation were all favorable results. The results are shown in Table 1 below.

(Example 2)

Synthesis of rubbery polymer (A-2):

5 parts of polyoxyethylene isodecyl ether (made by Dai-ichi Kogyo Seiyaku Co., Ltd. brand name: SD-110), 5 parts of polyoxyethylene isodecyl ether (made by Daiichi Kogyo Seiyaku Co., brand name SD-150), and alkyldiphenyl An aqueous solution in which 1 part of sodium disulfonate (manufactured by Kao Corporation, trade name: PLEX SS-L) was dissolved in 200 parts of water, 65 parts (67.2 mol%) of butadiene, 25 parts (26.3 mol%) of acrylonitrile as a raw material monomer, and 10 parts of methacrylic acid (6.5 mol%), 1.2 parts of terpinolene (manufactured by Wako Pure Chemical Industries, Ltd.), and a redox catalyst were added to the autoclave, and the temperature was adjusted to 10 ° C. 0.02 part of tan hydroxide was added and emulsion polymerization was performed to 75% of a polymerization conversion rate. HLB of the polyoxyethylene isodecyl ether (SD-110) used was 15.5, and the cloud point of 1.0 mass% aqueous solution was 80 degreeC or more. In addition, HLB of polyoxyethylene isodecyl ether (SD-150) was 16.5 and the cloud point of 1.0 mass% aqueous solution was 80 degreeC or more. The amount of addition was 0.1 part using paramentane hydroperoxide as a polymerization initiator. The polymerization conversion was calculated by solid content measurement.

Next, 0.1 part of reaction terminator N, N-diethylhydroxylamine was added, and the copolymer latex was synthesize | combined. Thereafter, steam was blown into the copolymer latex to remove unreacted raw material monomer at a liquid temperature of 50 ° C. or lower, and then allowed to cool to room temperature. Next, after adding 20 parts of ammonium sulfate (cloud point depressant) and confirming that it melt | dissolved completely, the rubber polymer was precipitated by blowing steam and making liquid temperature 90 degreeC or more. The precipitated rubbery polymer was washed with water and dehydrated and dried in a blow dryer set at 90 ° C to isolate the rubbery polymer (A-2). The rubber-like polymer (A-2) was measured by a Mooney viscosity tester with respect to the bar, it was 68ML _{1 +4} (100 ℃). In addition, the content of alkali metal ions contained in the rubbery polymer (A-2) was analyzed using an atomic absorption photometer, Na; 14 ppm, K; 8 ppm, Ca; 1 ppm. In addition, in the polymerization stability evaluation, it was 1.1%, 3.0% about the stability at the time of monomer collection, and 88% in the coagulation | solidification evaluation, and all brought favorable results. The results are shown in Table 1.

(Example 3)

Synthesis of rubbery polymer (A-3):

A rubbery polymer (A-3) was synthesized and isolated in the same manner as in Example 1, except that 60 parts (81.4 mol%) of butadiene and 40 parts (18.6 mol%) of hydroxybutyl methacrylate were used as raw material monomers. . The viscosity was measured with a Mooney tester about the rubbery polymer (A-3), and it was 75ML _{1 + 4} (100 degreeC). In addition, using an atomic absorption photometer, the alkali metal ion content contained in the rubbery polymer (A-3) was analyzed, and Na; 22 ppm, K; 10 ppm Ca; 1 ppm. Moreover, 1.3% in polymerization stability evaluation, 3.4% about stability at the time of monomer collection, and 89% in the coagulation | solidification evaluation were all favorable results. The results are shown in Table 1.

(Example 4)

Synthesis of Rubbery Polymer (A-4):

As a raw material monomer, it carried out similarly to Example 2 except having used 60 parts (79.9 mol%) of butadiene, 35 parts (15.9 mol%) of hydroxybutyl methacrylate, and 5 parts (4.2 mol%) of methacrylic acid, A free polymer (A-4) was synthesized and isolated. The viscosity was measured by a Mooney tester with respect to the rubbery polymer (A-4), and found to be 77 ML _{1 +4} (100 ° C.). In addition, using an atomic absorption photometer, the content of alkali metal ions contained in the rubbery polymer (A-4) was analyzed, and Na; 19 ppm, K; 8 ppm, Ca; 1 ppm. Moreover, 1.0% in the polymerization stability evaluation, 3.2% about the stability at the time of monomer recovery, and 90% in the coagulation | solidification evaluation were all favorable results. The results are shown in Table 1.

(Example 5)

Synthesis of Rubbery Polymer (A-5):

A rubbery polymer was prepared in the same manner as in Example 2 except that 60 parts (79.5 mol%) of butadiene, 10 parts (6.9 mol%) of styrene and 30 parts (13.6 mol%) of hydroxybutyl methacrylate were used as the raw material monomers. A-5) was synthesized and isolated. The rubber-like polymer (A-5) was measured by a Mooney viscosity tester with respect to the bar, it was 72ML _{1 +4} (100 ℃). In addition, using an atomic absorption photometer, the alkali metal ion content contained in the rubbery polymer (A-5) was analyzed, and Na; 18 ppm, K; 8 ppm, Ca; 1 ppm. Moreover, 1.5% in the polymerization stability evaluation, 4.0% about the stability at the time of monomer collection, and 91% in the coagulation | solidification evaluation were all favorable results. The results are shown in Table 1.

(Example 6)

Synthesis of rubbery polymer (A-6):

Except having used butadiene 55 parts (74.7 mol%), styrene 10 parts (7.1 mol%), hydroxybutyl methacrylate 30 parts (13.9 mol%), and methacrylic acid 5 parts (4.3 mol%) as a raw material monomer. In the same manner as in Example 2, the rubbery polymer (A-6) was synthesized and isolated. The rubber-like polymer (A-6) a measure of the viscosity by the Mooney testing machine for bar, was 78ML _{1 +4} (100 ℃). In addition, the content of alkali metal ions contained in the rubbery polymer (A-6) was analyzed using an atomic absorption photometer, Na; 20 ppm, K; 8 ppm, Ca; 1 ppm. Moreover, it was a favorable result as 1.4% in polymerization stability evaluation, 3.8% about the stability at the time of monomer collection, and 89% in the coagulation evaluation. The results are shown in Table 1.

(Example 7)

Synthesis of Rubbery Polymer (A-7):

As an emulsifier aqueous solution, 10 parts of polyoxyethylene nonyl phenyl ether (made by Kao Corporation, brand name: Emulgen 911), and 2 parts of sodium dodecylbenzene sulfonate (made by Kao Corporation, brand name: Neopelex G-25) are dissolved in 200 parts of water. A rubbery polymer (A-7) was synthesized and isolated in the same manner as in Example 1 except that the aqueous solution was used. The viscosity was measured with a Mooney tester about rubbery polymer (A-7), and it was 63ML _{1 + 4} (100 degreeC). Further, the content of alkali metal ions contained in the rubbery polymer (A-7) was analyzed using an atomic absorption photometer, Na; 15 ppm, K; 9 ppm Ca; 1 ppm. It was 1.5% in polymerization stability evaluation, 6.2% about stability at the time of monomer recovery, and 75% in the coagulation | solidification evaluation, resulting in inferior stability and solidification at the time of monomer recovery. The results are shown in Table 1.

(Example 8)

Synthesis of rubbery polymer (A-8):

5 parts of polyoxyethylene nonyl phenyl ether (made by Kao Corporation, brand name: Emulgen 911), 5 parts of polyoxyethylene nonyl phenyl ether (made by Kao Corporation, brand name: Emulgen 920) as an emulsifier aqueous solution, and sodium alkyldiphenyl ether disulfonate A rubbery polymer (A-8) was synthesized and isolated in the same manner as in Example 2, except that an aqueous solution obtained by dissolving 1 part of Kao Corporation; brand name Plexx SS-L was used in 200 parts of water. The viscosity was measured by a Mooney tester with respect to the rubbery polymer (A-8) and found to be 68ML _{1 +4} (100 ° C). In addition, using an atomic absorption photometer, the alkali metal ion content contained in the rubbery polymer (A-8) was analyzed, and Na; 14 ppm, K; 8 ppm, Ca; 1 ppm. In polymerization stability evaluation, it was 1.6%, 8.5% about the stability at the time of monomer recovery, and 87% in the coagulation evaluation, and the result at the time of monomer recovery was inferior. The results are shown in Table 1.

(Example 9)

Synthesis of rubbery polymer (A-9):

10 parts of polyoxyethylene isodecyl ether (made by Daiichi Kogyo Seiyaku Co., Ltd., brand name: SD-70) and 2 parts of sodium dodecyl benzene sulfonate (made by Kao Corporation, brand name: Neopelex G-25) as an emulsifier aqueous solution 200 parts of water A rubbery polymer (A-9) was synthesized and isolated in the same manner as in Example 1, except that the aqueous solution dissolved in was used. HLB of polyoxyethylene isodecyl ether (SD-70) was 13.2, and the cloud point of 1.0 mass% aqueous solution was 64 degreeC. The viscosity was measured by a Mooney tester about rubbery polymer (A-9), and it was 63ML _{1 + 4} (100 degreeC). In addition, using an atomic absorption photometer, the content of alkali metal ions contained in the rubbery polymer (A-9) was analyzed, and Na; 17 ppm, K; 10 ppm Ca; 1 ppm. In the polymerization stability evaluation, a large amount of wet rubber precipitated as 2.9% and 92.5% about the stability at the time of monomer recovery. It also became 40% also about the evaluation of the coagulation | solidification, and the result was inferior to stability. The results are shown in Table 1.

(Comparative Example 1)

Synthesis of rubbery polymer (A-10):

A rubbery polymer (A-9) was prepared in the same manner as in Example 1 except that an aqueous solution in which two parts of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation, trade name: Neopelex G-25) was dissolved in 200 parts of water was used as an emulsifier aqueous solution. ) Was synthesized. Since only anionic emulsifier was used as an emulsifier, 20 parts of ammonium sulfate were added, and after confirming that it was completely dissolved, steam was blown in and it was confirmed that a rubbery polymer did not precipitate even if liquid temperature was 90 degreeC or more. On the other hand, latex was thrown into the aqueous solution which melt | dissolved 10 parts of calcium chloride as a coagulant, and the rubber polymer precipitated. The precipitated rubbery polymer was washed with water and dehydrated and dried in a blow dryer set at 90 ° C to isolate the rubbery polymer (A-10). The rubber-like polymer (A-10) of measuring the viscosity by a Mooney testing machine for bar, was 65ML _{1 +4} (100 ℃). In addition, using an atomic absorption photometer, the alkali metal ion content contained in the rubbery polymer (A-10) was analyzed, and Na; 20 ppm, K; 10 ppm. However, about Ca, it turned out that it contains 1500 ppm by the fluorescent X-ray method. In the polymerization stability evaluation, it became 1.2% about the stability at the time of 1.2% and monomer collection, and was 90% also about the coagulation evaluation. The results are shown in Table 1.

(Comparative Example 2)

Synthesis of Rubbery Polymer (A-11):

As an emulsifier aqueous solution, it carried out similarly to Example 1 except having used the aqueous solution which melt | dissolved 3 parts of sodium salts (the Kao Corporation make, brand name: demol RN-L) of the formalin condensate of (beta) -naphthalenesulfonic acid formalin, and 200 parts of water. A-9) was synthesized. Since only anionic emulsifier was used as an emulsifier, 20 parts of ammonium sulfate were added, and after confirming that it was completely dissolved, steam was blown in and it was confirmed that a rubbery polymer did not precipitate even if liquid temperature was 90 degreeC or more. On the other hand, latex was thrown into the aqueous solution which melt | dissolved 10 parts of calcium chloride as a coagulant, and the rubber polymer precipitated. The rubbery polymer (A-11) was isolated by washing and dehydrating the precipitated rubbery polymer and drying with a blow dryer set at 90 ° C. And bar was 63ML _{1 +4} (100 ℃) of measuring the viscosity by a Mooney testing machine for rubber-like polymer (A-11). In addition, the content of alkali metal ions contained in the rubbery polymer (A-10) using an atomic absorption photometer was found to be Na; 100 ppm, K; 20 ppm. However, about Ca, it turned out that it contains 1200 ppm by the fluorescent X-ray method. In the polymerization stability evaluation, it became 32% about 1.0% and the stability at the time of monomer collection, and it was 90% also about the coagulation evaluation. The results are shown in Table 1.

From the evaluation results, the method for producing the rubbery polymers of Examples 1 to 6 includes polymerization stability and monomer recovery by using polyoxyethylene alkyl ethers having an HLB of 13.5 to 17.0 and a cloud point of 1.0 mass% aqueous solution of 70 ° C. or less as an emulsifier. It can be seen that the stability and coagulation properties are excellent.

Moreover, from the evaluation result, the manufacturing method of the rubbery polymer of Example 7 is polyoxyethylene nonyl phenyl ether (The Chao Corporation make, brand name: HLB is 13.7 as cloud emulsifier, and cloud point of 1.0 mass% aqueous solution is 74 degreeC.). Since Mulgen 911 was used as a nonionic surfactant, it can be seen that stability and coagulation properties are poor at the time of monomer recovery. Moreover, also in the manufacturing method of the rubbery polymer of Example 8, since polyoxyethylene nonyl phenyl ether (Kao Corporation make, brand name: Emulgen 911) was used as a nonionic emulsifier, it turns out that stability is inferior at the time of monomer recovery. have. In addition, the manufacturing method of the rubbery polymer of Example 9 uses polyoxyethylene isodecyl ether (SD-70) as a nonionic emulsifier, Since HLB is 13.2 and cloud point of 1.0 mass% aqueous solution is 64 degreeC, It can be seen that stability and coagulation properties are poor at the time of monomer recovery. In Comparative Examples 1 and 2, since no nonionic emulsifier is used, the rubber cannot be precipitated by heating solidification using cloud point drop. Therefore, since it solidified using calcium chloride, it contains a large amount of Ca ions.

The rubbery polymer for electronic materials of the present invention does not corrode metal and can be suitably used as a raw material such as paints, adhesives, and sealing agents. The manufacturing method of the rubbery polymer for electronic materials of this invention can be conveniently used for manufacture of such a rubbery polymer for electronic materials.

Claims (4)

Butadiene-acrylonitrile copolymer, butadiene-acrylonitrile-methacrylic acid copolymer, butadiene- (meth) acrylic acid ester copolymer, butadiene- (meth) acrylic acid ester-methacrylic acid copolymer, butadiene-styrene- (meth 1) a copolymer selected from the group consisting of an acrylic acid ester copolymer and a butadiene-styrene- (meth) acrylic acid ester-methacrylic acid copolymer, containing Na metal ion content, K metal ion content and Ca metal ion content Rubber-like polymer for electronic materials whose total amount is 1-50 ppm. The rubber-like polymer for electronic materials according to claim 1, wherein the content of the repeating unit derived from butadiene is 67.2 to 81.4 mol% based on the entirety of the copolymer. Using the polyoxyethylene alkyl ether represented by the following general formula (1) whose HLB is 13.5-17.0 and cloud point of 1.0 mass% aqueous solution is 70 degreeC or more as an emulsifier, emulsion polymerization is performed and the copolymer latex is produced and the obtained copolymer latex is obtained. The manufacturing method of the rubbery polymer for electronic materials obtained by heating in presence of electrolyte and obtaining a rubbery polymer. <Formula 1>

(In Formula 1, R represents an aliphatic hydrocarbon group having 8 to 12 carbon atoms, n represents an average condensation number of ethylene oxide of 5 to 20) The copolymer latex is prepared by the emulsion polymerization, and the copolymer contained in the copolymer latex is butadiene-acrylonitrile copolymer, butadiene-acrylonitrile-methacrylic acid copolymer, butadiene- As (meth) acrylic acid ester copolymer, butadiene- (meth) acrylic acid ester-methacrylic acid copolymer, butadiene-styrene- (meth) acrylic acid ester copolymer, and butadiene-styrene- (meth) acrylic acid ester-methacrylic acid copolymer The manufacturing method of the rubbery polymer for electronic materials which is 1 type chosen from the group which consists of.