JP2002212228A - Aqueous solution of amine salt of poly(meth)acrylic acid and method for preparing the same - Google Patents
Aqueous solution of amine salt of poly(meth)acrylic acid and method for preparing the sameInfo
- Publication number
- JP2002212228A JP2002212228A JP2001005619A JP2001005619A JP2002212228A JP 2002212228 A JP2002212228 A JP 2002212228A JP 2001005619 A JP2001005619 A JP 2001005619A JP 2001005619 A JP2001005619 A JP 2001005619A JP 2002212228 A JP2002212228 A JP 2002212228A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- poly
- meth
- acrylic acid
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 50
- -1 amine salt Chemical class 0.000 title claims abstract description 25
- 229920002845 Poly(methacrylic acid) Polymers 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 229920000193 polymethacrylate Polymers 0.000 claims abstract description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- 239000003505 polymerization initiator Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- 150000002978 peroxides Chemical class 0.000 claims description 10
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 239000000243 solution Substances 0.000 abstract description 8
- 239000003999 initiator Substances 0.000 abstract description 2
- 125000005395 methacrylic acid group Chemical class 0.000 abstract 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 229940047670 sodium acrylate Drugs 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- ZFHOULOIWZOZQS-UHFFFAOYSA-N hexane;hydrogen peroxide Chemical compound OO.CCCCCC ZFHOULOIWZOZQS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- BESWQAXCVAOXFV-UHFFFAOYSA-N octyl hydroperoxide Chemical compound CCCCCCCCOO BESWQAXCVAOXFV-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、低粘度で、不純物
の少ないポリ（メタ）アクリル酸アミン塩水溶液及びそ
の効率的な製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous solution of an amine salt of poly (meth) acrylic acid having a low viscosity and containing few impurities, and to an efficient method for producing the same.
【０００２】[0002]
【従来の技術】ポリ（メタ）アクリル酸アミン塩水溶液
は、製紙、塗料、水処理、半導体業界等において利用さ
れている。一般に、ポリ（メタ）アクリル酸塩水溶液
（以下代表的な化合物であるアクリル酸ソーダ重合体で
代表させて説明する）は、アクリル酸を水溶液重合する
ことによりアクリル酸重合体水溶液を得た後に、該水溶
液を苛性ソーダで中和するという方法や、アクリル酸エ
ステル類を有機溶媒中で重合し、その後、溶媒除去とケ
ン化という方法により製造されているが、前記方法では
アクリル酸低重合体水溶液を得ることが難しい。例え
ば、溶媒中で重合する方法は、高価な有機溶媒を必要と
する上、有機溶媒の完全な除去は殆ど不可能であるた
め、有機溶媒が重合体水溶液中に残存し臭気発生の原因
となるばかりでなく、分子量の調整も十分可能とはいえ
ない。そのため、ポリアクリル酸塩水溶液を得る方法と
しては各種の方法が提案されてきている。例えば、重合
時間を長くする、重合開始剤を増量する、連鎖移動剤を
使用する、重合温度を高くする、アクリル酸ソーダ水溶
液としてから重合する、アクリル酸ソーダ水溶液に空気
を吹き込みながら重合する、などの方法である。2. Description of the Related Art Aqueous solutions of poly (meth) acrylic acid amine salts are used in papermaking, coatings, water treatment, the semiconductor industry, and the like. Generally, an aqueous solution of a poly (meth) acrylate (which will be described below as a representative example of a sodium acrylate polymer) is obtained by polymerizing acrylic acid into an aqueous solution of an acrylic acid polymer. The aqueous solution is neutralized with caustic soda or an acrylic acid ester is polymerized in an organic solvent, and then the solvent is removed and the saponification is produced. Difficult to get. For example, the method of polymerizing in a solvent requires an expensive organic solvent, and since it is almost impossible to completely remove the organic solvent, the organic solvent remains in the aqueous polymer solution and causes odor. Not only that, the adjustment of the molecular weight is not sufficiently possible. Therefore, various methods have been proposed as methods for obtaining an aqueous solution of polyacrylate. For example, extend the polymerization time, increase the amount of the polymerization initiator, use a chain transfer agent, increase the polymerization temperature, polymerize from a sodium acrylate aqueous solution, polymerize while blowing air into the sodium acrylate aqueous solution, and the like. This is the method.
【０００３】しかしながら、前記の提案はいずれも解決
しなければならない以下の様な課題を有している。すな
わち、重合時間を長くすることは製造施設・装置の面か
ら制限を受けるだけでなく、当然に製造費の上昇を招
く。多量の重合開始剤の使用は重合開始剤の断片等、例
えば過硫酸塩の場合は製品純度の低下を招く。連鎖移動
剤の使用は製品に臭気を付加する、例えばメルカプト系
連鎖移動剤による臭気、或いはアルコール等の有機溶媒
を用いた場合には重合終了後に該アルコールを除去する
工程が必要になる。高温での重合の場合は、耐圧装置を
用い加圧下に行わなければならず、設備面での制限があ
る。アクリル酸ソーダ水溶液としてから重合する場合
は、アクリル酸ソーダの溶解度の関係から、重合体水溶
液の濃縮工程を採用しなければ樹脂固形分３６重量％以
上のものは得られない。アクリル酸ソーダ水溶液に空気
を吹き込みながら重合する場合は、アクリル酸や開始剤
等の飛散が伴い、製造操作の面で種々の問題を生ずる。
また、半導体分野で使用する場合には、苛性ソーダを使
用するとナトリウムイオンが不純物とされるため、アク
リル酸ソーダ水溶液の利用は好まれない。However, each of the above proposals has the following problems that must be solved. In other words, increasing the polymerization time is not only limited by the manufacturing facilities and equipment, but also naturally increases the manufacturing cost. The use of a large amount of the polymerization initiator causes a decrease in product purity in the case of a fragment of the polymerization initiator, for example, in the case of persulfate. The use of a chain transfer agent adds an odor to the product. For example, when a mercapto-based chain transfer agent is used, or when an organic solvent such as an alcohol is used, a step of removing the alcohol is required after the polymerization is completed. In the case of polymerization at a high temperature, the polymerization must be performed under pressure using a pressure-resistant device, and there is a limitation in terms of equipment. In the case of polymerizing from an aqueous sodium acrylate solution, a resin solid content of 36% by weight or more cannot be obtained unless a concentration step of the aqueous polymer solution is employed due to the solubility of sodium acrylate. When the polymerization is carried out while blowing air into the aqueous solution of sodium acrylate, acrylic acid and an initiator are scattered, causing various problems in the production operation.
In addition, when used in the semiconductor field, the use of sodium acrylate aqueous solution is not preferred because sodium ions are impurities when sodium hydroxide is used.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、これ
らの問題を解決し、低粘度且つ高純度のポリ（メタ）ア
クリル酸アミン塩水溶液を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to solve these problems and to provide an aqueous solution of poly (meth) acrylic acid amine salt having low viscosity and high purity.
【０００５】本発明の他の目的は、低粘度且つ高純度の
ポリ（メタ）アクリル酸アミン塩水溶液の効率的な製造
方法を提供することにある。Another object of the present invention is to provide an efficient method for producing an aqueous solution of a poly (meth) acrylic acid amine salt having a low viscosity and a high purity.
【０００６】[0006]
【課題を解決するための手段】本発明は、不揮発分が３
９〜４１重量％のときの粘度が２０〜４００ｍＰａ・ｓ
／２５℃であるポリ（メタ）アクリル酸アミン塩水溶液
であって、過酸化水素濃度が０〜５ｐｐｍ、ｐＨが５．
０〜７．０であるポリ（メタ）アクリル酸アミン塩水溶
液に関する。According to the present invention, there is provided a semiconductor device having a nonvolatile content of 3%.
When the viscosity is 9 to 41% by weight, the viscosity is 20 to 400 mPa · s.
/ 25 ° C., aqueous solution of poly (meth) acrylic acid amine salt having a hydrogen peroxide concentration of 0 to 5 ppm and a pH of 5.0.
The present invention relates to a poly (meth) acrylic acid amine salt aqueous solution having an aqueous solution of 0 to 7.0.
【０００７】本発明は、また、ポリ（メタ）アクリル酸
アミン塩濃度が０．５〜５０重量％である上記のポリ
（メタ）アクリル酸アミン塩水溶液に関する。[0007] The present invention also relates to the above aqueous solution of the poly (meth) acrylic acid amine salt, wherein the concentration of the poly (meth) acrylic acid amine salt is 0.5 to 50% by weight.
【０００８】本発明は、また、アクリル酸又はメタクリ
ル酸を主体とする単量体を過酸化物系重合開始剤ととも
に加熱アミン水溶液中に添加しながら重合させることを
特徴とすポリ（メタ）アクリル酸アミン塩水溶液の製造
方法に関する。The present invention is also characterized in that poly (meth) acrylic is characterized in that a monomer mainly composed of acrylic acid or methacrylic acid is polymerized while being added to a heated amine aqueous solution together with a peroxide-based polymerization initiator. The present invention relates to a method for producing an aqueous solution of an acid amine salt.
【０００９】本発明は、また、アクリル酸又はメタクリ
ル酸に対してアミンの配合量が５０〜１００ｍｏｌ％で
ある上記の（メタ）アクリル酸アミン塩水溶液の製造方
法に関する。The present invention also relates to the above-mentioned method for producing an aqueous solution of an amine salt of (meth) acrylic acid, wherein the amount of the amine is 50 to 100 mol% based on acrylic acid or methacrylic acid.
【００１０】[0010]
【発明の実施の形態】本発明におけるポリ（メタ）アク
リル酸アミン塩水溶液は、不揮発分が３９〜４１重量％
のときに、粘度が２０〜４００ｍＰａ・ｓ／２５℃であ
り、好ましくは５０〜３００ｍＰａ・ｓ／２５℃であ
る。粘度が２０ｍＰａ・ｓ／２５℃未満では、重合反応
時の重合開始剤量を多量に必要とするため、得られるポ
リ（メタ）アクリル酸アミン塩水溶液の製造費上昇を招
く。また、粘度が４００ｍＰａ・ｓ／２５℃を超える
と、４１重量％以上の不揮発分にしたとき粘度が上昇
し、取り扱いが不便となる。粘度の測定は例えばＢＬ型
回転粘度計（ＴＯＫＩＭＥＣ社製）を用いて行われる。
また、不揮発分は例えば熱風循環式箱形乾燥器（旭科学
（株）製）を用いて測定される。DETAILED DESCRIPTION OF THE INVENTION The aqueous solution of an amine salt of poly (meth) acrylic acid according to the present invention has a nonvolatile content of 39 to 41% by weight.
In this case, the viscosity is 20 to 400 mPa · s / 25 ° C., preferably 50 to 300 mPa · s / 25 ° C. When the viscosity is less than 20 mPa · s / 25 ° C., a large amount of a polymerization initiator is required at the time of the polymerization reaction, which causes an increase in the production cost of the resulting aqueous solution of poly (meth) acrylic acid amine salt. On the other hand, when the viscosity exceeds 400 mPa · s / 25 ° C., the viscosity increases when the nonvolatile content is 41% by weight or more, and handling becomes inconvenient. The viscosity is measured using, for example, a BL rotational viscometer (manufactured by TOKIMEC).
The nonvolatile content is measured using, for example, a hot air circulation type box dryer (manufactured by Asahi Science Co., Ltd.).
【００１１】また、本発明におけるポリ（メタ）アクリ
ル酸アミン塩水溶液は、不揮発分が３９〜４１重量％の
ときに、過酸化水素濃度が０〜５ｐｐｍであり、好まし
くは０ｐｐｍである。５ｐｐｍを超えるとポリ（メタ）
アクリル酸アミン塩水溶液は貯蔵中に発泡が見られる。The aqueous solution of the amine salt of poly (meth) acrylic acid in the present invention has a hydrogen peroxide concentration of 0 to 5 ppm, preferably 0 ppm, when the nonvolatile content is 39 to 41% by weight. If more than 5ppm, poly (meth)
The aqueous solution of the amine acrylate salt foams during storage.
【００１２】また、本発明におけるポリ（メタ）アクリ
ル酸アミン塩水溶液は、不揮発分が３９〜４１重量％の
ときに、ｐＨが５．０〜７．０であり、好ましくは、
５．３〜６．８である。ｐＨが５未満では、過酸化物系
重合開始剤が不純物として残存しやすい傾向にある。ま
た、ｐＨが７を超えると得られるポリ（メタ）アクリル
酸アミン塩水溶液の着色が激しくなる。In the present invention, the aqueous solution of the poly (meth) acrylic acid amine salt has a pH of 5.0 to 7.0 when the non-volatile content is 39 to 41% by weight.
5.3 to 6.8. If the pH is less than 5, the peroxide-based polymerization initiator tends to remain as an impurity. If the pH exceeds 7, the resulting aqueous solution of the amine salt of poly (meth) acrylic acid will become intensely colored.
【００１３】また、本発明におけるポリ（メタ）アクリ
ル酸アミン塩水溶液中のポリ（メタ）アクリル酸アミン
塩の濃度は、０．５〜５０重量％であることが好まし
い。５０重量％を超えると、過酸化物系重合開始剤が不
純物として残存しやすい傾向にある。また、０．５重量
％未満では、貯蔵中にポリ（メタ）アクリル酸アミン塩
水溶液中にカビが生えやすくなる傾向にある。In the present invention, the concentration of the amine salt of poly (meth) acrylate in the aqueous solution of amine salt of poly (meth) acrylate is preferably 0.5 to 50% by weight. If it exceeds 50% by weight, the peroxide-based polymerization initiator tends to remain as an impurity. If the amount is less than 0.5% by weight, mold tends to grow easily in the aqueous solution of the amine salt of poly (meth) acrylate during storage.
【００１４】また、本発明におけるポリ（メタ）アクリ
ル酸アミン塩水溶液の製造方法は、アクリル酸又はメタ
アクリル酸を原料として、有機溶媒の連鎖移動剤を使用
せずに、任意の粘度のポリアクリル酸塩、例えば不揮発
分が４１重量％以上の水溶液を、加水分解工程、脱溶工
程、脱臭工程或いは還元工程を別途設けずに、生産性よ
く製造することができる。The method for producing an aqueous solution of an amine salt of poly (meth) acrylic acid according to the present invention is a method for preparing an aqueous solution of polyacrylic acid having an arbitrary viscosity from acrylic acid or methacrylic acid without using a chain transfer agent of an organic solvent. An acid salt, for example, an aqueous solution having a non-volatile content of 41% by weight or more can be manufactured with high productivity without separately providing a hydrolysis step, a desolvation step, a deodorization step, or a reduction step.
【００１５】本発明において用いられるアクリル酸又は
メタクリル酸を主体とする重合性単量体とは、アクリル
酸又はメタクリル酸の単独で又はそれらの混合物或いは
それらにイタコン酸、マレイン酸、無水マレイン酸等の
重合性単量体で、水溶性を損なわない範囲のその他の重
合性単量体との混合物であってよく、最終の製品に求め
られる特性に応じて選択される。好ましくは、アクリル
酸又はメタクリル酸の割合は単量体全体に対して、好ま
しくは９０〜１００重量％である。The polymerizable monomer mainly composed of acrylic acid or methacrylic acid used in the present invention refers to acrylic acid or methacrylic acid alone or in a mixture thereof, or in combination with itaconic acid, maleic acid, maleic anhydride and the like. And may be a mixture with other polymerizable monomers in a range that does not impair the water solubility, and is selected according to the properties required for the final product. Preferably, the proportion of acrylic acid or methacrylic acid is preferably from 90 to 100% by weight, based on the total monomers.
【００１６】また、本発明における重合方法は、過酸化
物系重合開始剤を用いたラジカル重合であり、アクリル
酸又はメタクリル酸を主体とする重合性単量体を加熱ア
ミン水溶液中に滴下しながら行われる。加熱アミン水溶
液の温度としては、好ましくは８０〜１００℃、より好
ましくは９０〜１００℃である。８０℃未満の温度であ
ると重合が円滑に行われないおそれがあり、また、分子
量を十分調整することが困難になる傾向がある。１００
℃を超えると粘度が低下する傾向にある。加熱アミン水
溶液は、一部は、単量体を加熱アミン水溶液に滴下して
反応させた後に反応系に滴下してもよいが、アミン使用
量の１０重量％以上は反応開始時に使用することが好ま
しい。The polymerization method of the present invention is a radical polymerization using a peroxide-based polymerization initiator, wherein a polymerizable monomer mainly composed of acrylic acid or methacrylic acid is dropped into a heated amine aqueous solution. Done. The temperature of the heated amine aqueous solution is preferably from 80 to 100 ° C, more preferably from 90 to 100 ° C. If the temperature is lower than 80 ° C., polymerization may not be carried out smoothly, and it may be difficult to sufficiently adjust the molecular weight. 100
If the temperature exceeds ℃, the viscosity tends to decrease. A part of the heated amine aqueous solution may be dropped into the reaction system after the monomer is dropped into the heated amine aqueous solution and reacted, but 10% by weight or more of the amine used amount may be used at the start of the reaction. preferable.
【００１７】また、本発明におけるアミンの配合量は、
ポリ（メタ）アクリル酸に対して５０〜１００ｍｏｌ％
配合することが好ましく、７０〜９０ｍｏｌ％配合する
ことが好ましい。アミンの配合量が５０ｍｏｌ％未満で
は過酸化物系重合開始剤が不純物として残存しやすい傾
向にあり、１００ｍｏｌ％を超えると得られるポリ（メ
タ）アクリル酸塩水溶液に臭気が付加される。In the present invention, the amount of the amine is as follows:
50 to 100 mol% based on poly (meth) acrylic acid
It is preferable to mix, and it is preferable to mix 70 to 90 mol%. If the amount of the amine is less than 50 mol%, the peroxide-based polymerization initiator tends to remain as an impurity. If the amount exceeds 100 mol%, an odor is added to the resulting aqueous solution of poly (meth) acrylate.
【００１８】また、本発明に用いられるアミンとして
は、例えば、モノエタノールアミン、ジエタノールアミ
ン、トリエタノールアミン、Ｎ，Ｎ−ジメチルエタノー
ルアミン、Ｎ，Ｎ−ジエチルエタノールアミン、Ｎ−
（２−アミノエチル）エタノールアミン、Ｎ−メチルジ
エタノールアミン、Ｎ，Ｎ−ジブチルエタノールアミ
ン、Ｎ−メチルエタノールアミン、１２−アミノドデカ
ン酸、３−アミノ−１−プロパノール、ジイソプロピル
アミン、トリエチルアミン、２−エチルヘキシルアミ
ン、３−エトキシプロピルアミン、３−（ジエチルアミ
ノ）プロピルアミン、テトラエチレンジアミン、ｓｅｃ
−ブチルアミン、３−（メチルアミノ）プロピルアミ
ン、３−（ジメチルアミノ）プロピルアミン、３−メト
キシプロピルアミン等のアミンが挙げられる。これらの
アミンは単独で又は２種類以上組み合わせて使用され
る。The amine used in the present invention includes, for example, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-
(2-aminoethyl) ethanolamine, N-methyldiethanolamine, N, N-dibutylethanolamine, N-methylethanolamine, 12-aminododecanoic acid, 3-amino-1-propanol, diisopropylamine, triethylamine, 2-ethylhexyl Amine, 3-ethoxypropylamine, 3- (diethylamino) propylamine, tetraethylenediamine, sec
Amines such as -butylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine and 3-methoxypropylamine. These amines are used alone or in combination of two or more.
【００１９】また、半導体のＣＭＰ分野（Ｃｈｅｍｉｃ
ａｌ ａｎｄ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉ
ｎｇ）には、アミンとしてＮ，Ｎ−ジメチルエタノール
アミン等のアルカノールアミンを用いることが好まし
い。In the field of semiconductor CMP (Chemic),
al and Mechanical Polish
In ng), it is preferable to use an alkanolamine such as N, N-dimethylethanolamine as the amine.
【００２０】加熱アミン水溶液としての濃度は、得られ
る重合体水溶液の粘度に大きく作用するので、好ましく
は１重量％以上、より好ましくは５重量％以上であり、
上限としては飽和水溶液であっても良いが、余り高濃度
であると製品の着色が強まるため、その点からは５０重
量％以下が好ましい。Since the concentration of the heated amine aqueous solution greatly affects the viscosity of the obtained polymer aqueous solution, it is preferably 1% by weight or more, more preferably 5% by weight or more.
The upper limit may be a saturated aqueous solution, but if the concentration is too high, the coloring of the product will be intensified. From that point, 50% by weight or less is preferable.
【００２１】溶媒としての水は、重合性単量体と同量
（重量比）程度になるようにして重合するのが好まし
い。It is preferable that water as a solvent is polymerized so that the amount thereof is about the same as that of the polymerizable monomer (weight ratio).
【００２２】アクリル酸又はメタクリル酸を主体とする
単量体と過酸化物系重合開始剤は、反応の進行具合を見
ながら、連続的又は断続的に、且つ同時に又は別々に上
記の様な温度に加熱されたアミン水溶液中に滴下し重合
させる。The monomer mainly composed of acrylic acid or methacrylic acid and the peroxide-based polymerization initiator are continuously or intermittently and simultaneously or separately, while observing the progress of the reaction. And polymerized by dropping into an aqueous amine solution heated to a temperature.
【００２３】また、過酸化物系重合開始剤としては、例
えば、アクリル酸又はメタクリル酸の重合で用いられて
いる公知のものが同様に適用されるが、本発明におい
て、好ましいものは、クミルハイドロパーオキサイド、
ヘキサンハイドロパーオキサイド、オクタンハイドロパ
ーオキサイド、過酸化水素等のハイドロパーオキサイド
であり、特に過酸化水素が好ましい。これらの重合開始
剤は単独で又は２種類以上を組み合わせて使用すること
ができる。As the peroxide-based polymerization initiator, for example, known ones used in the polymerization of acrylic acid or methacrylic acid are similarly applied. In the present invention, preferred is cumyl. Hydroperoxide,
Hydroperoxides such as hexane hydroperoxide, octane hydroperoxide, and hydrogen peroxide, with hydrogen peroxide being particularly preferred. These polymerization initiators can be used alone or in combination of two or more.
【００２４】過酸化物系重合開始剤の使用量としては、
単量体１００重量部あたり１〜３５重量部が好ましく、
重合時間や目的とする分子量を考慮して決定される。重
合時間としては４〜１２時間とすることが好ましい。The amount of the peroxide-based polymerization initiator used is
1 to 35 parts by weight per 100 parts by weight of the monomer is preferable,
It is determined in consideration of the polymerization time and the target molecular weight. The polymerization time is preferably 4 to 12 hours.
【００２５】本発明の製造方法は、加熱アミン水溶液に
アクリル酸又はメタクリル酸を主体とする単量体と過酸
化物系重合開始剤を添加しながら重合させる方法であ
り、加熱アミン水溶液の温度が８０℃以上という高温及
びアルカリ性という条件下での重合反応であるにも関わ
らず重合開始剤の失活、分解が少なく、得られる重合体
は殆ど分解されず、有機溶媒或いは連鎖移動剤を使用し
なくても分子量の調整が可能で、又、精製という別工程
を設けずとも不純物の少ない水溶液として製品が得られ
る。The production method of the present invention is a method of polymerizing a heated amine aqueous solution while adding a monomer mainly composed of acrylic acid or methacrylic acid and a peroxide-based polymerization initiator. Despite the high temperature of 80 ° C. or higher and the polymerization reaction under alkaline conditions, the polymerization initiator is hardly deactivated or decomposed, the obtained polymer is hardly decomposed, and an organic solvent or a chain transfer agent is used. The molecular weight can be adjusted without the use of the compound, and the product can be obtained as an aqueous solution containing few impurities without providing a separate step of purification.
【００２６】[0026]
【実施例】以下、本発明を実施例により説明するが、本
発明はこれに制限されるものではない。なお、部及び％
は、それぞれ重量部及び重量％を示す。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, parts and%
Represents parts by weight and% by weight, respectively.
【００２７】実施例１〜５ 冷却器、温度計、滴下ロート、窒素ガス吹き込み管及び
攪拌機を備えた１リットルの四つ口フラスコにイオン交
換水とジメチルエタノールアミンを表１に示す（ａ）配
合で仕込み、１００℃まで加熱した。その後、表１に示
される９８％アクリル酸と３５％過酸化水素水の混合液
（ｂ）を連続的に４時間かけて滴下し重合させた。その
後、同温度で１時間熟成し、次いで、表１に示す滴下液
（ｃ）ジメチルエタノールアミンを１時間かけて滴下し
た。その後、２時間保温した。そして、前記四つ口フラ
スコを室温まで冷却し、不揮発分が４０重量％になるよ
うにイオン交換水を添加した。実施例１〜５の製造方法
で得られたポリアクリル酸塩は低粘度であり、また残存
過酸化水素がヨウ素滴定法で検出されなかった。Examples 1 to 5 A 1-liter four-necked flask equipped with a condenser, a thermometer, a dropping funnel, a nitrogen gas injection tube and a stirrer was mixed with ion-exchanged water and dimethylethanolamine as shown in Table 1 And heated to 100 ° C. Thereafter, a mixed solution (b) of 98% acrylic acid and 35% hydrogen peroxide solution shown in Table 1 was dropped continuously over 4 hours to polymerize. Thereafter, the mixture was aged at the same temperature for 1 hour, and then a dropping solution (c) dimethylethanolamine shown in Table 1 was added dropwise over 1 hour. Thereafter, the temperature was kept for 2 hours. Then, the four-necked flask was cooled to room temperature, and ion-exchanged water was added so that the nonvolatile content became 40% by weight. The polyacrylates obtained by the production methods of Examples 1 to 5 had low viscosity, and no residual hydrogen peroxide was detected by the iodine titration method.
【００２８】[0028]
【表１】 [Table 1]
【００２９】比較例１、２ 冷却器、温度計、滴下ロート、窒素ガス吹き込み管及び
攪拌機を備えた１リットルの四つ口フラスコにイオン交
換水を表２に示す（ａ）配合で仕込み、１００℃まで加
熱した。その後、表２に示される９８％アクリル酸と３
５％過酸化水素水の混合液（ｂ）を連続的に４時間かけ
て滴下し重合させた。その後、同温度で１時間熟成し、
次いで、表２に示す滴下液（ｃ）ジメチルエタノールア
ミンを１時間かけて滴下した。その後、２時間保温し
た。そして、前記四つ口フラスコを室温まで冷却し、不
揮発分が４０重量％になるようにイオン交換水を添加し
た。比較例１、２の製造方法で得られたポリアクリル酸
塩は比較的高粘度であり、また残存過酸化水素がヨウ素
滴定法で検出さた。Comparative Examples 1 and 2 Ion-exchanged water was charged into a 1-liter four-necked flask equipped with a condenser, a thermometer, a dropping funnel, a nitrogen gas injection tube and a stirrer according to the composition shown in Table 2 (a). Heated to ° C. Then, 98% acrylic acid and 3 shown in Table 2 were added.
A mixed solution (b) of 5% aqueous hydrogen peroxide was dropped continuously over 4 hours to polymerize. After that, aging at the same temperature for 1 hour,
Next, dimethylethanolamine, a dropping solution (c) shown in Table 2, was added dropwise over 1 hour. Thereafter, the temperature was kept for 2 hours. Then, the four-necked flask was cooled to room temperature, and ion-exchanged water was added so that the nonvolatile content became 40% by weight. The polyacrylates obtained by the production methods of Comparative Examples 1 and 2 had a relatively high viscosity, and the residual hydrogen peroxide was detected by an iodine titration method.
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【発明の効果】本発明によれば、低粘度で、且つ不純物
の少ないポリ（メタ）アクリル酸塩が水溶液として生産
性よく製造することができ、得られたポリ（メタ）アク
リル酸塩水溶液は、顔料分散剤、洗剤等に広く使用され
るものであるため、本発明はそれらを使用する業界にお
いて非常に有効なものである。According to the present invention, a poly (meth) acrylate having a low viscosity and few impurities can be produced as an aqueous solution with good productivity. Since the present invention is widely used in pigment dispersants, detergents, and the like, the present invention is very effective in the industry where they are used.
フロントページの続き (72)発明者 間宮 勉 茨城県鹿島郡波崎町大字砂山五番壱 日立 化成工業株式会社山崎事業所内 (72)発明者 新谷 健一 茨城県鹿島郡波崎町大字砂山五番壱 日立 化成工業株式会社山崎事業所内 Ｆターム(参考） 4J011 BB01 BB02 BB09 BB12 BB15 HA02 HB06 HB22 4J100 AK03P CA01 DA06 FA03 FA17 FA19 JA01 JA11 JA13 JA46 Continued on the front page (72) Inventor, Tsutomu Mamiya Oyama, Gozan, Hasaki-cho, Kashima-gun, Ibaraki Prefecture Hitachi Chemical Co., Ltd. F term (reference) in the Yamazaki Plant of Industrial Co., Ltd. 4J011 BB01 BB02 BB09 BB12 BB15 HA02 HB06 HB22 4J100 AK03P CA01 DA06 FA03 FA17 FA19 JA01 JA11 JA13 JA46
Claims (4)
度が２０〜４００ｍＰａ・ｓ／２５℃、過酸化水素濃度
が０〜５ｐｐｍ、ｐＨが５．０〜７．０であるポリ（メ
タ）アクリル酸アミン塩水溶液。1. A poly (meta) having a viscosity of 20 to 400 mPa · s / 25 ° C., a hydrogen peroxide concentration of 0 to 5 ppm, and a pH of 5.0 to 7.0 when the nonvolatile content is 39 to 41% by weight. ) Amine acrylate aqueous solution.
０．５〜５０重量％である請求項１記載のポリ（メタ）
アクリル酸アミン塩水溶液。2. The poly (meth) acrylate according to claim 1, wherein the concentration of the poly (meth) acrylate amine salt is 0.5 to 50% by weight.
Amine acrylate aqueous solution.
る単量体を過酸化物系重合開始剤とともに加熱アミン水
溶液中に添加しながら重合させることを特徴とするポリ
（メタ）アクリル酸アミン塩水溶液の製造方法。3. A poly (meth) acrylic acid amine salt aqueous solution, wherein a monomer mainly composed of acrylic acid or methacrylic acid is polymerized while being added to a heated amine aqueous solution together with a peroxide-based polymerization initiator. Manufacturing method.
ミンの配合量が５０〜１００ｍｏｌ％である請求項３記
載のポリ（メタ）アクリル酸アミン塩水溶液の製造方
法。4. The method for producing an aqueous solution of an amine salt of poly (meth) acrylic acid according to claim 3, wherein the amount of the amine is 50 to 100 mol% with respect to acrylic acid or methacrylic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000039843A1 (en) * | 1998-12-25 | 2000-07-06 | Hitachi Chemical Company, Ltd. | Cmp abrasive, liquid additive for cmp abrasive and method for polishing substrate |
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| CN108892746A (en) * | 2018-06-06 | 2018-11-27 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of novel polypropylene acid salt aqueous solution |
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