JP2006199921A - Low odorous aqueous liquid of copolymer and method for producing the same - Google Patents
Low odorous aqueous liquid of copolymer and method for producing the same Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 138
- 239000007788 liquid Substances 0.000 title claims abstract description 101
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000000178 monomer Substances 0.000 claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000009835 boiling Methods 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 22
- -1 acrylic ester Chemical class 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000012736 aqueous medium Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 10
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000839 emulsion Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 14
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 239000012855 volatile organic compound Substances 0.000 abstract description 22
- 239000011230 binding agent Substances 0.000 abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 6
- 230000003472 neutralizing effect Effects 0.000 abstract description 4
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 229920003146 methacrylic ester copolymer Polymers 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 235000019645 odor Nutrition 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000004745 nonwoven fabric Substances 0.000 description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000002518 antifoaming agent Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 3
- 239000004808 2-ethylhexylester Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N octadec-9-enoic acid Chemical compound CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Abstract
Description
本発明は、共重合体中に沸点が１０５℃を超えるアクリル酸エステル及び／又はメタクリル酸エステル単量体を必須単位とする共重合体と水性媒体からなるアクリル系共重合体水性液に関するものであり、さらに詳しくは、該共重合体水性液中に不純物として含まれるアルコールの量を著しく低減させた共重合体水性液及びその製造方法に関するものである。
本発明の共重合体水性液は、該共重合体の微粒子が水媒体に乳化した水性エマルション又は該共重合体が水媒体に溶解もしくは半溶解した水溶液をいう。
本発明の共重合体水性液によれば、有機揮発性物質の臭気のない乾燥皮膜を形成でき、該共重合体水性液は粘着剤、コーティング剤、バインダー、接着剤、分散剤、造粘剤、凝集剤などとして好適である。
The present invention relates to an aqueous acrylic copolymer solution comprising a copolymer having an acrylic acid ester and / or methacrylic acid ester monomer having a boiling point exceeding 105 ° C. as an essential unit and an aqueous medium in the copolymer. More specifically, the present invention relates to an aqueous copolymer liquid in which the amount of alcohol contained as an impurity in the aqueous copolymer liquid is significantly reduced, and a method for producing the same.
The aqueous copolymer liquid of the present invention refers to an aqueous emulsion in which fine particles of the copolymer are emulsified in an aqueous medium or an aqueous solution in which the copolymer is dissolved or semi-dissolved in an aqueous medium.
According to the aqueous copolymer liquid of the present invention, a dry film free from the odor of organic volatile substances can be formed, and the aqueous copolymer liquid is an adhesive, a coating agent, a binder, an adhesive, a dispersant, a thickener. It is suitable as a flocculant.
繊維質材料等のバインダー、コーティング剤や粘着剤に用いられる重合体には、皮膜形成性、皮膜の強度、基材との接着性、柔軟性及び耐候性の如き様々な物性が求められる。
従来より、かかる用途にはスチレン、アクリロニトリル、アクリル酸アルキルエステル（以下、アクリル酸エステルという）、メタクリル酸アルキルエステル（以下、メタクリル酸エステルという）及びアクリル酸、メタクリル酸等からなる単量体混合物を水媒体中で乳化重合したり水溶液重合して得られる共重合体が用いられてきた。
お絞りや汗拭きのように柔軟性の求められる不織布の製造に用いられるバインダーとしては、沸点が１０５℃を超えるアクリル酸エステルやメタクリル酸エステル単量体（以下、アクリル酸エステルとメタクリル酸エステルを総称して（メタ）アクリル酸エステルということがある）が、単量体の皮膚刺激性が少なく低毒性である点、引火点が高く安全性に優れる点、得られる共重合体の物性が優れる点等から使用されている。具体的には、アルキル基の炭素数が４〜１８の（メタ）アクリル酸エステルが使用されている。
かかるバインダーには、（メタ）アクリル酸エステルと、スチレンやメタクリル酸メチルエステル等の単量体を水性媒体中で乳化重合することによって得られるガラス転移温度が−３０℃ないし室温の共重合体の水性エマルションが使用されている。
また、ラベル、テープ等の粘着剤や各種のコーティング剤には、ガラス転移温度が−８０℃ないし８０℃の共重合体の水性エマルションや水溶液が一般に使用されている。
Polymers used for binders such as fibrous materials, coating agents and pressure-sensitive adhesives are required to have various physical properties such as film-forming properties, film strength, adhesion to substrates, flexibility and weather resistance.
Conventionally, for such applications, a monomer mixture comprising styrene, acrylonitrile, acrylic acid alkyl ester (hereinafter referred to as acrylic acid ester), methacrylic acid alkyl ester (hereinafter referred to as methacrylic acid ester), acrylic acid, methacrylic acid and the like is used. Copolymers obtained by emulsion polymerization or aqueous solution polymerization in an aqueous medium have been used.
Binders used in the manufacture of nonwoven fabrics that require flexibility, such as drawing and sweat wiping, are acrylic acid esters and methacrylic acid ester monomers with boiling points exceeding 105 ° C (hereinafter collectively referred to as acrylic acid esters and methacrylic acid esters). (It may be called (meth) acrylic acid ester), but it has low skin irritation and low toxicity of the monomer, high flash point and excellent safety, and excellent physical properties of the resulting copolymer Etc. are used. Specifically, a (meth) acrylic acid ester having 4 to 18 carbon atoms in the alkyl group is used.
Such a binder is a copolymer having a glass transition temperature of −30 ° C. to room temperature obtained by emulsion polymerization of a monomer such as (meth) acrylic acid ester and styrene or methyl methacrylate in an aqueous medium. An aqueous emulsion is used.
For adhesives such as labels and tapes and various coating agents, aqueous emulsions and aqueous solutions of copolymers having a glass transition temperature of −80 ° C. to 80 ° C. are generally used.
（メタ）アクリル酸エステル／スチレン系共重合体のうちでも、柔軟性単位として（メタ）アクリル酸ｎ−ブチルエステル単量体単位を有する共重合体を使用した場合には、スチレン単量体単位の使用割合を少なくできる点で耐候性に優れる不織布が得られる。
一方、（メタ）アクリル酸２−エチルへキシルエステル単量体単位を有する共重合体を使用した場合には、柔軟で風合いの良い不織布が得られる。
しかしながら、かかる（メタ）アクリル酸エステル／スチレン系共重合体の水性エマルションから形成される不織布には臭気が残り易く、それを除去することが容易でなかった。
不織布の臭気は、バインダーとして用いる共重合体水性液に残存する揮発性有機化合物に起因することが知られており、共重合体水性液からの揮発性有機化合物の低減化が求められていた。
Among the (meth) acrylic acid ester / styrene copolymers, when a copolymer having a (meth) acrylic acid n-butyl ester monomer unit is used as a flexible unit, a styrene monomer unit is used. The nonwoven fabric which is excellent in a weather resistance at the point which can reduce the use ratio of is obtained.
On the other hand, when a copolymer having a (meth) acrylic acid 2-ethylhexyl ester monomer unit is used, a non-woven fabric having a soft and good texture can be obtained.
However, an odor tends to remain on the nonwoven fabric formed from the aqueous emulsion of the (meth) acrylic acid ester / styrene copolymer, and it was not easy to remove it.
The odor of the nonwoven fabric is known to be caused by a volatile organic compound remaining in the aqueous copolymer liquid used as a binder, and reduction of the volatile organic compound from the aqueous copolymer liquid has been demanded.
一方、（メタ）アクリル酸ｎ−ブチルエステルや（メタ）アクリル酸２−エチルへキシルエステル単量体単位を有する共重合体を粘着剤に使用した場合は、優れた粘着性や接着性を発現するが、食品包装分野のラベル等の粘着剤として使用する場合は、臭気が残り易く、バインダーと同様に共重合体水性液からの揮発性有機化合物の低減化が求められていた。 On the other hand, when a copolymer having (meth) acrylic acid n-butyl ester or (meth) acrylic acid 2-ethylhexyl ester monomer unit is used for the pressure-sensitive adhesive, it exhibits excellent tackiness and adhesiveness. However, when used as an adhesive such as a label in the food packaging field, odor tends to remain, and reduction of volatile organic compounds from the aqueous copolymer liquid has been demanded in the same manner as the binder.
かかる共重合体水性液中の揮発性有機化合物の低減に関しては、多数の提案があり、例えば特許文献１には、水性媒体の存在下でラジカル開始剤により単量体混合物を重合させた後に、有機過酸化物を含んだレドックス開始剤を添加してさらに重合を７日間以上行うことにより、（メタ）アクリル酸エステル単量体の残存量を０．０２〜０．１質量％にまで減少させることが開示されている。
また、酢酸ビニル系エマルション又は合成ゴムラテツクスにおける揮発性物質の除去のためには、加圧水蒸気の吹き込みが行われている。特許文献２には、９０〜９５℃に維持された酢酸ビニル系エマルションに加圧水蒸気を４８時間吹き込むことにより、酢酸ビニルモノマー、メチルアルコール等の含有量が極めて少ないエマルションを得たという記載があり、また特許文献３では、ブタジエン−スチレン共重合体ラテックス中の残存単量体等の除去のために、加圧水蒸気を吹き込むという発明が提案されている。
しかしながら、不織布バインダーとして好適な（メタ）アクリル酸エステル／スチレン系共重合体の水性エマルションや、粘着剤等として好適な（メタ）アクリル酸エステル系共重合体の水性液に含まれる臭気原因物質を極微量に低減させることに関する文献は知られていない。
Regarding the reduction of volatile organic compounds in the aqueous copolymer liquid, there have been many proposals, for example, in Patent Document 1, after polymerizing a monomer mixture with a radical initiator in the presence of an aqueous medium, The residual amount of (meth) acrylic acid ester monomer is reduced to 0.02 to 0.1% by mass by adding a redox initiator containing an organic peroxide and further conducting polymerization for 7 days or more. It is disclosed.
Further, in order to remove volatile substances in the vinyl acetate emulsion or the synthetic rubber latex, pressurized steam is blown. Patent Document 2 has a description that an emulsion having extremely low contents of vinyl acetate monomer, methyl alcohol, and the like was obtained by blowing pressurized steam into a vinyl acetate emulsion maintained at 90 to 95 ° C. for 48 hours, Patent Document 3 proposes an invention in which pressurized steam is blown in order to remove residual monomers and the like in the butadiene-styrene copolymer latex.
However, an odor-causing substance contained in an aqueous emulsion of a (meth) acrylate ester / styrene copolymer suitable as a nonwoven fabric binder or an aqueous solution of a (meth) acrylate copolymer suitable as an adhesive, etc. There is no known literature on reducing the amount to a very small amount.
前記のとおり、（メタ）アクリル酸エステル／スチレン系共重合体の水性液を用いた不織布バインダーや、（メタ）アクリル酸エステル系共重合体の水性液を用いた粘着剤やコーティング剤には臭気が残り易いという問題があった。本発明においては、臭気成分の残らない（メタ）アクリル酸エステル系共重合体の水性液を安定性良く製造して提供することを課題とした。 As described above, there are odors in non-woven fabric binders using aqueous (meth) acrylate / styrene copolymer liquids, and adhesives and coating agents using aqueous (meth) acrylate copolymer aqueous liquids. There was a problem that it was easy to remain. In this invention, it made it the subject to manufacture and provide the aqueous liquid of the (meth) acrylic acid ester-type copolymer with no odor component remaining stably.
本発明者らは、上記課題を解決するために鋭意検討した結果、沸点が１０５℃を超える（メタ）アクリル酸エステル単量体単位を必須成分とする共重合体をバインダーや粘着剤等に使用した場合おいて、臭気として感知される物質は、主に（メタ）アクリル酸エステル単量体と該エステル鎖を構成するアルコールであるとの知見を得た。
例えば（メタ）アクリル酸ｎ−ブチルエステル／スチレン系共重合体をバインダーとする不織布において臭気として感知される物質は、未反応の（メタ）アクリル酸ｎ−ブチルエステル単量体とｎ−ブチルアルコールである。
不織布の臭気低減のためには、前記共重合体水性液中の（メタ）アクリル酸エステル単量体とアルコールの両方を減少させる必要があることを見出し、本発明を完成するに至った。
従来、（メタ）アクリル酸エステル単量体単位を必須成分とする共重合体水性液、例えば、（メタ）アクリル酸ｎ−ブチルエステル／スチレン系共重合体からなる水性エマルションに対して適用されていた揮発性有機化合物の除去方法では、重合終了後に残存した（メタ）アクリル酸ｎ−ブチルエステル単量体の低減にだけ注意が払われていた結果、単量体を除去する際の処理温度が高すぎて共重合体中のエステル結合の加水分解が起こり、それによって生成するｎ−ブタノールに起因する臭気を取り除くことが困難であった。同様のことは、他の（メタ）アクリル酸エステル単量体にも当てはまり、エステル結合の加水分解によって生成したアルコールに起因する臭気が問題となっている。
本発明においては、エステルの加水分解を抑制した条件を採用することにより、上記の問題を解決することを可能にした。
As a result of intensive studies to solve the above problems, the present inventors have used a copolymer having a (meth) acrylate monomer unit having a boiling point exceeding 105 ° C. as an essential component for a binder, an adhesive, and the like. In this case, it was found that the substance perceived as odor was mainly (meth) acrylate monomer and alcohol constituting the ester chain.
For example, the non-reacted (meth) acrylic acid n-butyl ester monomer and n-butyl alcohol are substances that are detected as odors in the nonwoven fabric containing a (meth) acrylic acid n-butyl ester / styrene copolymer as a binder. It is.
In order to reduce the odor of the nonwoven fabric, it has been found that it is necessary to reduce both the (meth) acrylic acid ester monomer and the alcohol in the aqueous copolymer liquid, and the present invention has been completed.
Conventionally, it has been applied to an aqueous copolymer liquid containing a (meth) acrylic acid ester monomer unit as an essential component, for example, an aqueous emulsion composed of a (meth) acrylic acid n-butyl ester / styrene copolymer. In the method of removing volatile organic compounds, attention was paid only to the reduction of the (meth) acrylic acid n-butyl ester monomer remaining after the completion of the polymerization. It was too high to cause ester bond hydrolysis in the copolymer, and it was difficult to remove the odor caused by n-butanol produced thereby. The same applies to other (meth) acrylic acid ester monomers, and the odor caused by alcohol produced by hydrolysis of the ester bond is a problem.
In the present invention, the above-mentioned problem can be solved by adopting the conditions in which the hydrolysis of the ester is suppressed.
本発明は、沸点が１０５℃を超える（メタ）アクリル酸エステル単量体からなる単位を有する共重合体であって、アルコールの含有量が３００ｐｐｍ以下である共重合体水性液、該共重合体水性液の製造方法に関するものである。
すなわち、本発明は、
The present invention is a copolymer having a unit composed of a (meth) acrylic acid ester monomer having a boiling point exceeding 105 ° C., and an aqueous copolymer solution having an alcohol content of 300 ppm or less, the copolymer The present invention relates to a method for producing an aqueous liquid.
That is, the present invention
〔１〕沸点が１０５℃を超える（メタ）アクリル酸エステル及び／又はメタクリル酸エステル単量体からなる単位を有し、かつ酸価が０．０５ｍｅｑ／ｇ以上である共重合体中の酸性基の一部又は全部を塩基で中和して得られる重合体塩及び水性媒体からなり、該アクリル酸エステル及び／又はメタクリル酸エステルに由来するアルコールの含有量が３００ｐｐｍ以下である共重合体水性液。
〔２〕沸点が１０５℃を超えるアクリル酸エステル及び／又はメタクリル酸エステル単量体からなる単位を有し、かつ酸価が０．０５ｍｅｑ／ｇ以上である共重合体中の酸性基の一部又は全部を塩基で中和して得られる重合体塩及び水性媒体からなる共重合体水性液を、減圧蒸留の可能な容器に仕込み、撹拌下に、共重合体水性液の温度を５５〜８５℃としかつ該容器内を水が沸騰する圧力に維持した状態で、該容器内の共重合体水性液中に加圧水蒸気を吹き込むとともに、該容器内の気相部の水蒸気及び該共重合体水性液から気化した揮発性有機化合物を排気ポンプにより系外に除去することを特徴とする〔１〕の共重合体水性液の製造方法。
〔３〕共重合体水性液と水蒸気の割合が、共重合体水性液１００質量部当たり、水蒸気５〜１５０質量部である〔２〕に記載の共重合体水性液の製造方法。
〔４〕沸点が１０５℃を超えるアクリル酸エステル及び／又はメタクリル酸エステル単量体からなる単位の割合が、共重合体を構成する全単量体単位の合計量を基準にして２０〜９０質量％であり、かつ酸価が０．１〜３．０ｍｅｑ／ｇである〔１〕に記載の共重合体水性液。
〔５〕沸点が１０５℃を超えるアクリル酸エステル及び／又はメタクリル酸エステル単量体からなる単位の割合が、共重合体を構成する全単量体単位の合計量を基準にして２０〜９０質量％であり、かつ酸価が０．１〜３．０ｍｅｑ／ｇである〔２〕又は〔３〕のいずれかに記載の共重合体水性液の製造方法。
〔６〕沸点が１０５℃を超えるアクリル酸エステル及び／又はメタクリル酸エステル単量体からなる単位が、アクリル酸ｎ−ブチルエステル及び／又はメタクリル酸ｎ−ブチルエステルである〔１〕又は〔４〕のいずれかに記載の共重合体水性液。
〔７〕沸点が１０５℃を超えるアクリル酸エステル及び／又はメタクリル酸エステル単量体からなる単位が、アクリル酸２−エチルヘキシルエステル及び／又はメタクリル酸２−エチルヘキシルエステルである〔１〕又は〔４〕のいずれかに記載の共重合体水性液。
〔８〕沸点が１０５℃を超えるアクリル酸エステル及び／又はメタクリル酸エステル単量体からなる単位が、アクリル酸ｎ−ブチルエステル及び／又はメタクリル酸ｎ−ブチルエステルである〔２〕、〔３〕又は〔５〕のいずれかに記載の共重合体水性液の製造方法。
〔９〕沸点が１０５℃を超えるアクリル酸エステル及び／又はメタクリル酸エステル単量体からなる単位が、アクリル酸２−エチルヘキシルエステル及び／又はメタクリル酸２−エチルヘキシルである〔２〕、〔３〕又は〔５〕のいずれかに記載の共重合体水性液の製造方法。
〔１０〕共重合体の酸価が０．１〜２．５ｍｅｑ／ｇであって、アルコールの含有量が２５０ｐｐｍ以下である〔６〕又は〔７〕のいずれかに記載の重合体水性エマルション。
〔１１〕共重合体の酸価が０．１〜２．５ｍｅｑ／ｇであって、アルコールの含有量が２５０ｐｐｍ以下である〔８〕又は〔９〕のいずれかに記載の水性エマルションの製造方法。
[1] An acidic group in a copolymer having a unit composed of a (meth) acrylic acid ester and / or a methacrylic acid ester monomer having a boiling point exceeding 105 ° C. and having an acid value of 0.05 meq / g or more Copolymer aqueous liquid comprising a polymer salt obtained by neutralizing a part or all of the base with a base and an aqueous medium, and an alcohol content derived from the acrylate ester and / or methacrylic acid ester is 300 ppm or less .
[2] A part of acidic groups in the copolymer having a unit consisting of an acrylic ester and / or methacrylic ester monomer having a boiling point exceeding 105 ° C. and having an acid value of 0.05 meq / g or more Alternatively, a copolymer aqueous solution comprising a polymer salt obtained by neutralizing the whole with a base and an aqueous medium is charged into a container capable of distillation under reduced pressure, and the temperature of the copolymer aqueous solution is set to 55 to 85 under stirring. In a state in which the temperature in the vessel is maintained at a pressure at which water is boiled, pressurized water vapor is blown into the aqueous copolymer liquid in the vessel, and water vapor in the gas phase portion in the vessel and the aqueous copolymer are supplied. The method for producing an aqueous copolymer liquid according to [1], wherein a volatile organic compound vaporized from the liquid is removed from the system by an exhaust pump.
[3] The method for producing an aqueous copolymer liquid according to [2], wherein the ratio of the aqueous copolymer liquid to water vapor is 5 to 150 parts by mass of water vapor per 100 parts by mass of the aqueous copolymer liquid.
[4] The proportion of units composed of acrylic acid ester and / or methacrylic acid ester monomer having a boiling point exceeding 105 ° C. is 20 to 90 mass based on the total amount of all monomer units constituting the copolymer. %, And the copolymer has an acid value of 0.1 to 3.0 meq / g.
[5] The proportion of units consisting of acrylic acid ester and / or methacrylic acid ester monomer having a boiling point exceeding 105 ° C. is 20 to 90 mass based on the total amount of all monomer units constituting the copolymer. %, And the acid value is 0.1 to 3.0 meq / g. The method for producing an aqueous copolymer liquid according to any one of [2] and [3].
[6] The unit consisting of an acrylic ester and / or methacrylic ester monomer having a boiling point exceeding 105 ° C. is an acrylic acid n-butyl ester and / or a methacrylic acid n-butyl ester [1] or [4] The aqueous copolymer liquid according to any one of the above.
[7] The unit consisting of an acrylic ester and / or methacrylic ester monomer having a boiling point exceeding 105 ° C. is 2-ethylhexyl acrylate and / or 2-ethylhexyl methacrylate [1] or [4] The aqueous copolymer liquid according to any one of the above.
[8] The unit consisting of an acrylate ester and / or a methacrylic acid ester monomer having a boiling point exceeding 105 ° C. is an acrylic acid n-butyl ester and / or a methacrylic acid n-butyl ester [2], [3] Or the manufacturing method of the copolymer aqueous liquid in any one of [5].
[9] The unit consisting of an acrylate ester and / or a methacrylic acid ester monomer having a boiling point exceeding 105 ° C. is 2-ethylhexyl acrylate and / or 2-ethylhexyl methacrylate [2], [3] or [5] The method for producing an aqueous copolymer liquid according to any one of [5].
[10] The polymer aqueous emulsion according to any one of [6] or [7], wherein the copolymer has an acid value of 0.1 to 2.5 meq / g and an alcohol content of 250 ppm or less.
[11] The method for producing an aqueous emulsion according to any one of [8] and [9], wherein the copolymer has an acid value of 0.1 to 2.5 meq / g and an alcohol content of 250 ppm or less. .
本発明によれば、（メタ）アクリル酸エステル単量体とアルコールの両方を極めて微量にまで低減させた共重合体水性液が得られる。
該共重合体水性液において、例えば（メタ）アクリル酸ｎ−ブチルエステルとｎ−ブチルアルコールの両方を極めて微量にまで低減させた水性液は、不織布製造用のバインダーとして好適に使用でき、得られる不織布は臭気を有しない。
According to the present invention, an aqueous copolymer liquid in which both the (meth) acrylic acid ester monomer and the alcohol are reduced to a very small amount can be obtained.
In the aqueous copolymer liquid, for example, an aqueous liquid in which both (meth) acrylic acid n-butyl ester and n-butyl alcohol are reduced to a very small amount can be suitably used and obtained as a binder for producing a nonwoven fabric. Nonwoven fabric has no odor.
本発明において揮発性有機化合物を除去する対象の共重合体水性液は、前記のとおり、沸点が１０５℃を超える（メタ）アクリル酸エステル単量体からなる単位を一構成単位とし、かつ酸価が０．０５ｍｅｑ／ｇ以上である共重合体中の酸性基の一部又は全部を塩基で中和して得られる重合体塩及び水性媒体からなり、該（メタ）アクリル酸エステルに由来するアルコールの含有量が３００ｐｐｍ以下である共重合体水性液、すなわち水性エマルション又は水溶液である。
該共重合体の中和は、１００％未満の中和でも良いが、好ましくは１００％中和である。中和用塩基としては、水酸化アンモニウム又は炭酸ナトリウム等が好ましい。
共重合体の酸価が０．０５ｍｅｑ／ｇ未満であると、エマルション粒子の分散安定性が劣り、揮発性有機化合物の除去のために共重合体水性液中に加圧水蒸気を供給したとき、凝集が起こる。酸価の上限は特に制約されないが、耐水性が必要な場合は、５．０ｍｅｑ／ｇ以下であることが好ましい。水性液の安定性が良く且つ耐水性に加え耐湿性も必要な場合は０．１〜３．０ｍｅｑ／ｇであることがより好ましい。共重合体に酸価を与えるための単量体としては、アクリル酸及び／又はメタクリル酸（以下、（メタ）アクリル酸という）が好ましい。
In the present invention, the aqueous copolymer liquid from which volatile organic compounds are removed has, as described above, a unit composed of a (meth) acrylic acid ester monomer having a boiling point exceeding 105 ° C. as a constituent unit, and an acid value. An alcohol derived from the (meth) acrylic acid ester, comprising a polymer salt obtained by neutralizing a part or all of the acidic groups in the copolymer having a ≧ 0.05 meq / g with a base and an aqueous medium Is an aqueous copolymer liquid having a content of 300 ppm or less, that is, an aqueous emulsion or aqueous solution.
The neutralization of the copolymer may be neutralization of less than 100%, but is preferably 100% neutralization. As the base for neutralization, ammonium hydroxide or sodium carbonate is preferable.
When the acid value of the copolymer is less than 0.05 meq / g, the dispersion stability of the emulsion particles is inferior, and when pressurized steam is supplied into the aqueous copolymer liquid for the removal of volatile organic compounds, aggregation occurs. Happens. The upper limit of the acid value is not particularly limited, but when water resistance is required, it is preferably 5.0 meq / g or less. When the stability of the aqueous liquid is good and moisture resistance is required in addition to water resistance, it is more preferably 0.1 to 3.0 meq / g. As a monomer for giving an acid value to the copolymer, acrylic acid and / or methacrylic acid (hereinafter referred to as (meth) acrylic acid) is preferable.
本発明において、（メタ）アクリル酸エステル単量体の沸点が水の沸点（常圧で１００℃）を超える単量体を使用した場合に、本発明の条件下で、加圧水蒸気によって共重合体水性液からアルコールを効率よく除去することができる。この際に、（メタ）アクリル酸エステルの沸点が１１０℃を超える単量体を使用するのが好ましい。
沸点が１０５℃を超える（メタ）アクリル酸エステル単量体の具体例は、アルキル基の炭素数が４〜１８の（メタ）アクリル酸エステルであり、（メタ）アクリル酸ｎ−ブチルエステル、（メタ）アクリル酸イソブチルエステル、（メタ）アクリル酸ｔｅｒｔ−ブチルエステル、（メタ）アクリル酸ｎ−へキシルエステル、（メタ）アクリル酸シクロヘキシルエステル、（メタ）アクリル酸２−エチルへキシルエステル、（メタ）アクリル酸ｎ−オクチルエステル、（メタ）アクリル酸イソボルニルエステル、（メタ）アクリル酸ラウリルエステル、（メタ）アクリル酸ステアリルエステルが例示される。
また、アルキルエステル鎖に酸素を有する単量体も使用することができる。かかる単量体としては、（メタ）アクリル酸２−メトキシエチルエステル、（メタ）アクリル酸３−メトキシブチルエチルが例示される。
In the present invention, when a monomer having a boiling point of (meth) acrylic acid ester monomer exceeding the boiling point of water (at 100 ° C. at normal pressure) is used, a copolymer is formed by pressurized steam under the conditions of the present invention. Alcohol can be efficiently removed from the aqueous liquid. In this case, it is preferable to use a monomer having a boiling point of (meth) acrylic acid ester exceeding 110 ° C.
Specific examples of the (meth) acrylic acid ester monomer having a boiling point exceeding 105 ° C. are (meth) acrylic acid esters having 4 to 18 carbon atoms in the alkyl group, and (meth) acrylic acid n-butyl ester, ( (Meth) acrylic acid isobutyl ester, (meth) acrylic acid tert-butyl ester, (meth) acrylic acid n-hexyl ester, (meth) acrylic acid cyclohexyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth Examples thereof include n-octyl acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, and stearyl ester (meth) acrylate.
A monomer having oxygen in the alkyl ester chain can also be used. Examples of such monomers include (meth) acrylic acid 2-methoxyethyl ester and (meth) acrylic acid 3-methoxybutylethyl.
共重合体中の、沸点が１０５℃を超える（メタ）アクリル酸エステル単量体単位の好ましい割合は１０〜９５質量％であり、より好ましくは、２０〜９０質量％である。（メタ）アクリル酸ｎ−ブチルエステル／スチレン系共重合体の場合は、２５〜６０質量％が更に好ましい。 The preferable ratio of the (meth) acrylic acid ester monomer unit whose boiling point exceeds 105 ° C. in the copolymer is 10 to 95% by mass, and more preferably 20 to 90% by mass. In the case of (meth) acrylic acid n-butyl ester / styrene copolymer, 25 to 60% by mass is more preferable.
上記共重合体を構成する他の単量体としては、沸点が１０５℃を超える（メタ）アクリル酸エステル単量体とラジカル共重合可能な単量体であれば適宜使用することができ、具体的には沸点が１０５℃以下の（メタ）アクリル酸エステル単量体、（メタ）アクリル酸、スチレン、（メタ）アクリロニトリル、（メタ）アクリル酸２−ヒドロキシエチル、Ｎ−メチロール（メタ）アクリルアミド、酢酸ビニル等が挙げられる。 As the other monomer constituting the copolymer, any monomer that can be radically copolymerized with a (meth) acrylic acid ester monomer having a boiling point exceeding 105 ° C. can be used. Specifically, a (meth) acrylic acid ester monomer having a boiling point of 105 ° C. or lower, (meth) acrylic acid, styrene, (meth) acrylonitrile, 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide, Examples include vinyl acetate.
本発明の共重合体水性液を不織布製造用のバインダーとして用いる場合には、共重合単量体としてスチレン単位を含み、かつガラス転移温度が−３０℃ないし室温の共重合体からなる水性エマルションが好適である。バインダー用にさらに好ましい水性エマルションは、共重合体中に（メタ）アクリル酸ｎ−ブチルエステル単量体単位を含み、該単量体が共重合体を構成する全単量体単位の合計量を基準にして２５〜６０質量％であり、かつ酸価が０．１〜１．０ｍｅｑ／ｇである水性エマルションである。 When the aqueous copolymer liquid of the present invention is used as a binder for producing a nonwoven fabric, an aqueous emulsion comprising a copolymer having a styrene unit as a copolymerizable monomer and having a glass transition temperature of −30 ° C. to room temperature. Is preferred. A more preferable aqueous emulsion for the binder contains a (meth) acrylic acid n-butyl ester monomer unit in the copolymer, and the total amount of all monomer units constituting the copolymer by the monomer. It is an aqueous emulsion having 25 to 60% by mass and an acid value of 0.1 to 1.0 meq / g on the basis.
本発明の共重合体水性液をラベル用粘着剤として用いる場合には、（メタ）アクリル酸エステルと共重合可能な単量体としてメタクリル酸メチルエステルを含み、かつガラス転移温度が−８０℃ないし８０℃の共重合体からなる水性エマルション又は水溶液が好適である。粘着剤にさらに好ましい共重体水性液は、共重合体中にアクリル酸２−エチルへキシルエステル単量体単位を含み、該単量体が共重合体を構成する全単量体単位の合計量を基準にして２０〜９０質量％であり、かつ酸価が０．１〜３．０ｍｅｑ／ｇである。 When the copolymer aqueous liquid of the present invention is used as a pressure-sensitive adhesive for labels, it contains methacrylic acid methyl ester as a monomer copolymerizable with (meth) acrylic acid ester and has a glass transition temperature of −80 ° C. to An aqueous emulsion or aqueous solution made of a copolymer at 80 ° C. is preferred. A more preferable copolymer aqueous liquid for the pressure-sensitive adhesive contains the 2-ethylhexyl acrylate ester monomer unit in the copolymer, and the total amount of all monomer units constituting the copolymer by the monomer. And the acid value is 0.1 to 3.0 meq / g.
本発明の水性液における好ましい固形分濃度は、１５〜７０質量％である。
通常上記水性液は、水性媒体中で乳化重合法又は水溶液重合により製造することができ、重合後の水性液中には、通常１０００〜３０００ｐｐｍ程度の残存単量体を主体とする揮発性有機化合物が含まれている。本発明の一つは、かかる濃度の揮発性有機化合物を含む水性液からそれを除去し、得られる水性液から形成される皮膜より臭気が感じられなくなることである。
The preferable solid content concentration in the aqueous liquid of the present invention is 15 to 70% by mass.
Usually, the aqueous liquid can be produced by an emulsion polymerization method or an aqueous solution polymerization in an aqueous medium. In the aqueous liquid after polymerization, a volatile organic compound mainly composed of about 1000 to 3000 ppm of a residual monomer. It is included. One aspect of the present invention is that it removes it from an aqueous liquid containing such a concentration of volatile organic compounds and makes the odor less perceivable than a film formed from the resulting aqueous liquid.
本発明においては、共重合体水性液から揮発性有機化合物を除去するために、該水性液を仕込んだ容器内を水が沸騰する温度と圧力に維持した状態で、該水性液中に加圧水蒸気を吹き込むとともに、該容器内の気相部の水蒸気及び該水性液から気化した揮発性有機化合物を排気ポンプにより系外に除去する。
加圧水蒸気を吹き込む際、共重合体水性液温度を５５〜８５℃にする。水蒸気の吹き込む時の共重合体水性液温度が、５５℃未満であると揮発性物質の除去速度が劣り、一方８５℃を越えると、共重合体や残存する単量体のエステル結合が加水分解してアルコールが新たに生成するため、アルコールの含有量が減少し難い。加圧水蒸気を吹き込む時の容器内圧力は、容器内の水を沸騰させるために、９０〜３６０ｍｍＨｇ（０．０４〜０．０８５ＭＰａ）程度となる。
In the present invention, in order to remove volatile organic compounds from the aqueous copolymer liquid, pressurized water vapor is added to the aqueous liquid while maintaining the temperature and pressure at which the water is boiled in the container charged with the aqueous liquid. And the volatile organic compound vaporized from the water vapor and the aqueous liquid are removed out of the system by an exhaust pump.
When the pressurized steam is blown, the aqueous copolymer liquid temperature is set to 55 to 85 ° C. When the temperature of the aqueous copolymer solution when steam is blown is less than 55 ° C, the removal rate of volatile substances is poor. On the other hand, when the temperature exceeds 85 ° C, the ester bonds of the copolymer and the remaining monomer are hydrolyzed. Since alcohol is newly generated, the alcohol content is unlikely to decrease. The pressure in the container when the pressurized steam is blown is about 90 to 360 mmHg (0.04 to 0.085 MPa) in order to boil the water in the container.
本発明においては、加圧水蒸気の供給と等量の水蒸気を排気ポンプにより系外に除去する。かかる水蒸気とともに共重合体水性液中の揮発性有機化合物が除去される。処理槽と排気ポンプの間にコンデンサーを置き、そこで揮発性有機化合物及び水蒸気を凝縮させることが好ましい。
加圧水蒸気としては、ゲージ圧０．１０〜０．２５ＭＰａ（温度１１０〜１３０℃）程度の水蒸気が好ましい。共重合体水性液と加圧水蒸気の好ましい割合は、共重合体水性液１００質量部当たり、加圧水蒸気５〜１５０質量部であり、さらに好ましい水蒸気量は１０〜１２０質量部である。加圧水蒸気の量が１５０質量部を越えると共重合体水性液粒子の損傷が起こり易くなり、一方加圧水蒸気の量が５質量部未満では該アルコールを３００ｐｐｍ以下に低減させるのに時間がかかり過ぎる。
In the present invention, an amount of water vapor equivalent to the supply of pressurized water vapor is removed from the system by an exhaust pump. The volatile organic compound in the copolymer aqueous liquid is removed together with the water vapor. It is preferable to place a condenser between the treatment tank and the exhaust pump, where volatile organic compounds and water vapor are condensed.
The pressurized water vapor is preferably water vapor having a gauge pressure of about 0.10 to 0.25 MPa (temperature of 110 to 130 ° C.). A preferred ratio of the aqueous copolymer liquid and the pressurized water vapor is 5 to 150 parts by mass of pressurized water vapor per 100 parts by mass of the aqueous copolymer liquid, and a more preferable amount of water vapor is 10 to 120 parts by mass. When the amount of pressurized steam exceeds 150 parts by mass, the aqueous copolymer liquid particles are easily damaged. On the other hand, when the amount of pressurized steam is less than 5 parts by mass, it takes too much time to reduce the alcohol to 300 ppm or less.
本発明において、上記の水蒸気処理に要する時間は、加圧水蒸気の供給速度及びその他の条件によっても異なるが、生産性の点で１０時間以内が好ましい。本発明によれば、各種条件の選択により、３〜６時間の水蒸気処理で、該アルコール濃度が３００ｐｐｍ以下の共重合体水性液を製造することができる。好ましいアルコール濃度は２５０ｐｐｍ以下であり、後記した実施例によれば３〜４時間の水蒸気処理により、アルコールの濃度を１００ｐｐｍ以下にした共重合体水性液を得ることも可能である。さらに、アルコール以外の揮発性有機化合物、すなわち水性液に残存するスチレン単量体や（メタ）アクリル酸エステル単量体も同様な水準にまで低下させることができる。 In the present invention, the time required for the steam treatment described above is preferably within 10 hours from the viewpoint of productivity, although it varies depending on the supply rate of pressurized steam and other conditions. According to the present invention, an aqueous copolymer liquid having an alcohol concentration of 300 ppm or less can be produced by steam treatment for 3 to 6 hours by selecting various conditions. The preferred alcohol concentration is 250 ppm or less, and according to the examples described later, it is possible to obtain an aqueous copolymer liquid having an alcohol concentration of 100 ppm or less by steam treatment for 3 to 4 hours. Furthermore, volatile organic compounds other than alcohol, that is, styrene monomers and (meth) acrylic acid ester monomers remaining in the aqueous liquid can be reduced to a similar level.
本発明においては、共重合体水性液の突沸を回避するために、加圧水蒸気を吹き込む期間撹拌を行う。撹拌の所要動力は、用いる容器の形状によっても異なるが、通常化学プラントで使用される円筒形の容器を用いるなら、形状に若干の差異があったとしても０．５〜１．５ＫＷ／ｍ3が好ましい。
撹拌に伴い、泡が生成し易くなるので、これを抑えるために消泡剤を適量使用することができる。好ましい消泡剤としては、例えばサンノプコ（株）商品名ＳＮデフォーマーＰＣ等のポリエーテル系消泡剤及びシリコーン系消泡剤が挙げられる。
本発明における揮発性有機化合物の除去方法は、バッチ又は連続処理法として使用することができるが、アルコール濃度をできる限り低濃度にできる点で、バッチ処理方が好ましい。
In the present invention, in order to avoid bumping of the aqueous copolymer liquid, stirring is performed for a period during which pressurized steam is blown. The power required for stirring varies depending on the shape of the container to be used, but if a cylindrical container usually used in a chemical plant is used, even if there is a slight difference in shape, 0.5 to 1.5 KW / m 3 Is preferred.
Since foam is easily generated with stirring, an appropriate amount of antifoaming agent can be used to suppress this. Examples of preferable antifoaming agents include polyether antifoaming agents and silicone antifoaming agents such as San Nopco's trade name SN deformer PC.
The removal method of the volatile organic compound in the present invention can be used as a batch or continuous processing method, but the batch processing method is preferable in that the alcohol concentration can be made as low as possible.
以下、実施例及び比較例を挙げて、本発明をさらに具体的に説明する。なお、以下の各例において、（メタ）アクリル酸エステルやアルコールの測定は、ガスクロマトグラフィーによりおこなった。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In each of the following examples, (meth) acrylic acid ester and alcohol were measured by gas chromatography.
スチレン（以下、ＳＴという）５０ｋｇ、アクリル酸ｎ−ブチルエステル（以下、ＢＡとう）１５０ｋｇ、アクリル酸２−エチルヘキシルエステル（以下、２−ＥＨＡという）２５ｋｇ、メタクリル酸ｎ−ブチルエステル（以下、ＢＭＡという）２５ｋｇ、アクリル酸（以下、ＡＡという）５ｋｇ、メタクリル酸２−ヒドロキシエチルエステル（以下、ＨＥＭＡという）５ｋｇ及びＮ−メチロールアクリルアミド（以下、Ｎ−ＭＡＭという）５ｋｇを、水７５ｋｇ及びラウリル硫酸ナトリウム１．２５ｋｇと混合撹拌し、単量体エマルションを作成した。 50 kg of styrene (hereinafter referred to as ST), 150 kg of acrylic acid n-butyl ester (hereinafter referred to as BA), 25 kg of acrylic acid 2-ethylhexyl ester (hereinafter referred to as 2-EHA), methacrylic acid n-butyl ester (hereinafter referred to as BMA) ) 25 kg, acrylic acid (hereinafter referred to as AA) 5 kg, methacrylic acid 2-hydroxyethyl ester (hereinafter referred to as HEMA) 5 kg and N-methylolacrylamide (hereinafter referred to as N-MAM) 5 kg, water 75 kg and sodium lauryl sulfate 1 A monomer emulsion was prepared by mixing and stirring with 25 kg.
水１７５ｋｇを仕込み８５℃に昇温した槽型反応器に、４時間かけて単量体エマルションと過硫酸アンモニウム５％水溶液２０ｋｇを滴下しながら、乳化重合を行った。得られたエマルション状の共重合体水性液をアンモニアでｐＨを５に調整した後、消泡剤ＳＮデフォーマーＰＣ（サンノプコ（株）製）０．２６ｋｇを添加した。上記水性液における酸価は０．３ｍｅｑ／ｇである。上記重合によって得られた共重合体水性液の固形分濃度は５２質量％であり、これに含まれる主な揮発性有機化合物の量は以下のとおりであった。
ＢＡ；４４０ｐｐｍ、ＢＭＡ；３００ｐｐｍ、ｎ−ブチルアルコール；５２０ｐｐｍ、ＳＴ；５０ｐｐｍ
Emulsion polymerization was carried out while dropping 175 kg of water into a tank reactor heated to 85 ° C. while dropping a monomer emulsion and 20 kg of 5% aqueous solution of ammonium persulfate over 4 hours. After adjusting the pH of the resulting emulsion-like copolymer aqueous liquid to 5 with ammonia, 0.26 kg of antifoam SN deformer PC (manufactured by San Nopco Co., Ltd.) was added. The acid value in the aqueous liquid is 0.3 meq / g. The solid content concentration of the aqueous copolymer liquid obtained by the above polymerization was 52% by mass, and the amounts of main volatile organic compounds contained therein were as follows.
BA; 440 ppm, BMA; 300 ppm, n-butyl alcohol; 520 ppm, ST; 50 ppm
上記エマルション状の共重合体水性液５００ｋｇの入った槽型反応器に加圧水蒸気供給管及び排気管を取り付け、共重合体水性液温度を８０℃に昇温した後、撹拌下、圧力０．１５ＭＰａの加圧水蒸気を流量２５ｋｇ／Ｈｒで共重合体水性液液内に吹き込みながら、他方排気ポンプで系内水蒸気を排気することにより、系内を水の沸騰状態に維持した。その時の圧力は０．０６ＭＰａであった。撹拌は、所要動力Ｐｖ＝１．０ｋＷ／ｍ3でおこなった。 A pressurized steam supply pipe and an exhaust pipe were attached to the tank reactor containing 500 kg of the emulsion-like copolymer aqueous liquid, and the temperature of the copolymer aqueous liquid was raised to 80 ° C., and the pressure was 0.15 MPa with stirring. While the pressurized water vapor was blown into the aqueous copolymer liquid at a flow rate of 25 kg / Hr, the water vapor was exhausted by the exhaust pump on the other hand, thereby maintaining the water in a boiling state. The pressure at that time was 0.06 MPa. Stirring was performed at a required power Pv = 1.0 kW / m 3 .
加圧水蒸気の吹き込みを４時間かけて行うことにより、合計で水蒸気１００ｋｇ供給した。この水蒸気量は、共重合体水性液１００質量部に対して２０質量部の割合である。
得られた重合体共重合体水性液について、外観及び揮発性有機化合物量を評価した。 外観は目視により評価し、ＳＴ単量体、ＢＡ単量体及びｎ−ブチルアルコールの含有量は、ガスクロマトグラフィーにより測定した。
ガスクロマトグラフィーの測定に際しては、共重合体水性液５ｇとエタノール１０ｇを混合して３０分静置し、１２０００ｒｐｍ×１０分で遠心分離して上澄みを２ｇとり、これに内部標準としてエチレングリコールモノメチルエーテルアセテートの１％水溶液０．０６ｇを加えた溶液をガスクロマトグラフィーの注入液とした。
By blowing pressurized steam over 4 hours, a total of 100 kg of steam was supplied. The amount of water vapor is 20 parts by mass with respect to 100 parts by mass of the aqueous copolymer liquid.
About the obtained polymer copolymer aqueous liquid, the external appearance and the amount of volatile organic compounds were evaluated. The appearance was visually evaluated, and the contents of ST monomer, BA monomer and n-butyl alcohol were measured by gas chromatography.
In the measurement of gas chromatography, 5 g of the copolymer aqueous solution and 10 g of ethanol were mixed and allowed to stand for 30 minutes, centrifuged at 12,000 rpm × 10 minutes, 2 g of the supernatant was taken, and ethylene glycol monomethyl ether was used as an internal standard. A solution obtained by adding 0.06 g of a 1% aqueous solution of acetate was used as an injection solution for gas chromatography.
上記実施例１の重合体共重合体水性液における重合体の単量体組成、水蒸気処理条件及び残存単量体等の測定結果については、実施例１〜４及び比較例１〜４と合わせて表１に記載した。 About measurement results, such as a monomer composition of a polymer in the polymer copolymer aqueous liquid of the above-mentioned Example 1, water vapor treatment conditions, and a residual monomer, it combines with Examples 1-4 and Comparative Examples 1-4. It described in Table 1.
実施例１において使用した単量体を表１に示した単量体に変更した以外は、すべて実施例１と同じ操作を行った。 The same operation as in Example 1 was performed except that the monomers used in Example 1 were changed to the monomers shown in Table 1.
単量体の種類及び水蒸気処理条件を表１に記載のものに変更した以外は、実施例１と同じ方法で実施した。なお、実施例３で使用した水蒸気量は、共重合体水性液１００質量部に対して１５質量部の割合である。 It implemented by the same method as Example 1 except having changed into the thing of Table 1 and the kind of monomer and water-vapor-treatment conditions. In addition, the amount of water vapor | steam used in Example 3 is a ratio of 15 mass parts with respect to 100 mass parts of copolymer aqueous liquids.
単量体の種類及び水蒸気処理条件を表１に記載のものに変更した以外は、実施例１と同じ方法で実施した。なお、実施例４で使用した水蒸気量は、共重合体水性液１００質量部に対して１０質量部の割合である。 It implemented by the same method as Example 1 except having changed into the thing of Table 1 and the kind of monomer and water-vapor-treatment conditions. In addition, the amount of water vapor | steam used in Example 4 is a ratio of 10 mass parts with respect to 100 mass parts of copolymer aqueous liquids.
＜比較例１＞
実施例１で使用した単量体において、アクリル酸を０．５ｋｇに減量した以外は、実施例１と同じ方法で実施した。
<Comparative Example 1>
The same procedure as in Example 1 was performed except that the amount of acrylic acid in the monomer used in Example 1 was reduced to 0.5 kg.
＜比較例２＞
実施例１で使用した単量体において、アクリル酸を６２．５ｋｇに増量し、水蒸気供給温度を８０℃から９０℃にする以外は、実施例１と同じ方法で実施した。
<Comparative example 2>
The same procedure as in Example 1 was performed except that the amount of acrylic acid in the monomer used in Example 1 was increased to 62.5 kg and the steam supply temperature was changed from 80 ° C. to 90 ° C.
＜比較例３＞
加圧水蒸気の供給時の共重合体水性液温度を８０℃から４５℃に下げた以外は、実施例１と同じ方法で実施した。
<Comparative Example 3>
The same procedure as in Example 1 was performed except that the temperature of the aqueous copolymer liquid at the time of supplying pressurized steam was lowered from 80 ° C to 45 ° C.
＜比較例４＞
加圧水蒸気の供給時の共重合体水性液温度を８０℃から９５℃に上げた以外は、実施例１と同じ方法で実施した。
<Comparative example 4>
The same procedure as in Example 1 was performed except that the copolymer aqueous liquid temperature at the time of supplying pressurized steam was increased from 80 ° C. to 95 ° C.
２−ＥＨＡ８０Ｋｇ、メタクリル酸メチルエステル（以下、ＭＭＡという）２０Ｋｇ、Ｎ−ＭＡＭ０．１Ｋｇ、及びＡＡ２Ｋｇを単量体単位として乳化重合をおこなった後中和してエマルション状の共重合体水性液を得た。
この共重合体水性液の固形分濃度は５０％、酸価は０．３ｍｅｑ／ｇ、ｐＨは７．０であった。また、これに含まれる主な揮発性有機化合物の量は以下のとおりであった。
２−ＥＨＡ；９１０ｐｐｍ、２−エチルヘキシルアルコール；４１０ｐｐｍ、ＭＭＡ；５０ｐｐｍ
Emulsion polymerization is performed using 2-EHA 80 kg, methacrylic acid methyl ester (hereinafter referred to as MMA) 20 kg, N-MAM 0.1 kg, and AA 2 kg as monomer units, and then neutralized to obtain an emulsion-like copolymer aqueous liquid. It was.
The aqueous copolymer solution had a solid content concentration of 50%, an acid value of 0.3 meq / g, and a pH of 7.0. Moreover, the quantity of the main volatile organic compound contained in this was as follows.
2-EHA; 910 ppm, 2-ethylhexyl alcohol; 410 ppm, MMA; 50 ppm
該共重合体水性液５００Ｋｇの入った槽型反応器に水蒸気供給管及び排気管を取り付けた。水性液の温度を６０℃に昇温した後、撹拌下、圧力０．１５ＭＰａの水蒸気を流量１００Ｋｇ／Ｈｒで液内に吹込みながら、他方排気ポンプで系内水蒸気を排気する事により、系内を水の沸騰状態に維持した。この時の圧力は０．０２ＭＰａであった。 A water vapor supply pipe and an exhaust pipe were attached to a tank reactor containing 500 kg of the aqueous copolymer liquid. After raising the temperature of the aqueous liquid to 60 ° C., the steam in the system was exhausted with the other exhaust pump while blowing water vapor with a pressure of 0.15 MPa into the liquid at a flow rate of 100 kg / hr with stirring. Was maintained in a boiling state of water. The pressure at this time was 0.02 MPa.
水蒸気の吹込みを５時間かけて行うことにより、合計で水蒸気５００Ｋｇ供給した。この水蒸気量は、該水性液１００質量部に対して１００質量部の割合である。
得られた水性重合体について、外観及び揮発有機化合物量を評価した。外観は目視により評価し、２−ＥＨＡ単量体、２−エチルヘキシルアルコール、及びＭＭＡ単量体の含有量は、ガスクロマトグラフィーにより測定した。
上記実施例５の水性重合体における単量体組成、水蒸気処理条件、及び、残存単量体等の測定結果については、実施例５〜７及び比較例５〜９と合わせて表２に記載した。
A total of 500 kg of water vapor was supplied by blowing water vapor over 5 hours. The amount of water vapor is 100 parts by mass with respect to 100 parts by mass of the aqueous liquid.
About the obtained aqueous polymer, the external appearance and the amount of volatile organic compounds were evaluated. The appearance was visually evaluated, and the contents of 2-EHA monomer, 2-ethylhexyl alcohol, and MMA monomer were measured by gas chromatography.
The measurement results of the monomer composition, the steam treatment conditions, the residual monomer, etc. in the aqueous polymer of Example 5 are listed in Table 2 together with Examples 5-7 and Comparative Examples 5-9. .
２−ＥＨＡ２５Ｋｇ、ＭＭＡ６０メチルメタクリレート６０Ｋｇ、及びメタクリル酸（以下、ＭＡＡという）１５Ｋｇを単量体として共重合をおこない、アンモニア水で中和して水溶液状の共重合体水性液を得た。
この共重合体水性液の固形分濃度は３０％、酸価は１．７ｍｅｑ／ｇ、ｐＨ８．０であった。また、これに含まれる主な揮発性有機化合物の量は以下のとおりであった。
２−ＥＨＡ；１４００ｐｐｍ、２−エチルヘキシルアルコール；４７０ｐｐｍ、ＭＭＡ；１１０ｐｐｍ
上記共重合体水性液５００Ｋｇの入った槽型反応器に水蒸気供給管及び排気管を取り付けた。
単量体の種類及び水蒸気処理条件を表２に記載のものに変更した以外は、実施例５と同じ方法で操作をおこなった。なお、実施例６で使用した水蒸気量は、水性液１００質量部に対して１００質量部の割合である。
Copolymerization was carried out using 2-EHA (25 kg), MMA60 methyl methacrylate (60 kg) and methacrylic acid (hereinafter referred to as MAA) (15 kg) as monomers, and neutralized with ammonia water to obtain an aqueous copolymer aqueous solution.
The aqueous copolymer solution had a solid content concentration of 30%, an acid value of 1.7 meq / g, and a pH of 8.0. Moreover, the quantity of the main volatile organic compound contained in this was as follows.
2-EHA; 1400 ppm, 2-ethylhexyl alcohol; 470 ppm, MMA; 110 ppm
A steam supply pipe and an exhaust pipe were attached to a tank reactor containing 500 kg of the aqueous copolymer liquid.
The operation was performed in the same manner as in Example 5 except that the monomer type and steam treatment conditions were changed to those shown in Table 2. In addition, the amount of water vapor used in Example 6 is a ratio of 100 parts by mass with respect to 100 parts by mass of the aqueous liquid.
単量体の種類及び水蒸気処理条件を表２に記載のものに変更した以外は、実施例６と同じ方法で実施した。なお、実施例７で使用した水蒸気量は、水性液１００質量部に対して８０質量部の割合である。 It implemented by the same method as Example 6 except having changed into the thing of Table 2 the kind of monomer, and water vapor | steam processing conditions. In addition, the amount of water vapor used in Example 7 is a ratio of 80 parts by mass with respect to 100 parts by mass of the aqueous liquid.
実施例５で使用した単量体において、アクリル酸を３５Ｋｇに増量した以外は、実施例５と同じ方法で実施した。 The same procedure as in Example 5 was performed except that the amount of acrylic acid in the monomer used in Example 5 was increased to 35 kg.
＜比較例５＞
実施例５で使用した単量体において、アクリル酸を０．２Ｋｇに減量した以外は、実施例５と同じ方法で実施した。
<Comparative Example 5>
The same procedure as in Example 5 was performed, except that the amount of acrylic acid in the monomer used in Example 5 was reduced to 0.2 kg.
＜比較例６＞
水蒸気の供給時の水性液温度を６０℃から４５℃に下げた以外は、実施例５と同じ方法で実施した。
<Comparative Example 6>
The same procedure as in Example 5 was performed, except that the temperature of the aqueous liquid at the time of supplying steam was lowered from 60 ° C to 45 ° C.
＜比較例７＞
水蒸気の供給時の水性液温度を６０℃から９５℃に上げた以外は、実施例５と同じ方法で実施した。
<Comparative Example 7>
The same procedure as in Example 5 was performed, except that the temperature of the aqueous liquid at the time of supplying steam was increased from 60 ° C to 95 ° C.
＜比較例８＞
水蒸気の供給量を５００Ｋｇから１５Ｋｇに減量した以外は、実施例５と同じ方法で実施した。なお、比較例９で使用した水蒸気量は、水性液１００質量部に対して３質量部の割合である。
<Comparative Example 8>
It implemented by the same method as Example 5 except having reduced the supply_amount | feed_rate of water vapor | steam from 500 kg to 15 kg. The amount of water vapor used in Comparative Example 9 is a ratio of 3 parts by mass with respect to 100 parts by mass of the aqueous liquid.
本発明によれば、人体に有害な揮発性物質の含有量の少ない共重合体水性液が容易に得られ、かかる共重合体水性液は臭気が少なく、衛生面での要求が厳しい用途、例えば紙お絞り用のバインダーや食品ラベル用の粘着剤、コーティング剤又は感圧接着剤等として使用できる。
According to the present invention, an aqueous copolymer liquid having a low content of volatile substances harmful to the human body can be easily obtained, such an aqueous copolymer liquid has less odor, and has severe demands on hygiene, for example, It can be used as a binder for paper drawing, an adhesive for food labels, a coating agent or a pressure sensitive adhesive.
Claims (11)
The method for producing an aqueous emulsion according to any one of claims 8 and 9, wherein the copolymer has an acid value of 0.1 to 2.5 meq / g and an alcohol content of 250 ppm or less.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013133413A (en) * | 2011-12-27 | 2013-07-08 | Toagosei Co Ltd | Method for producing aqueous copolymer emulsion |
| JP2015117315A (en) * | 2013-12-18 | 2015-06-25 | 花王株式会社 | Method for producing polymer dispersion |
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| JPH1060368A (en) * | 1996-05-29 | 1998-03-03 | Basf Ag | Binder for low-release coating composition |
| JP2002060415A (en) * | 2000-08-21 | 2002-02-26 | Yayoi Chemical Industry Co Ltd | Method for producing emulsion resin |
| JP2002265520A (en) * | 2001-03-14 | 2002-09-18 | Sumitomo Chem Co Ltd | Method of removing volatile component from copolymer latex |
| JP2003073427A (en) * | 2001-08-31 | 2003-03-12 | Nippon A & L Kk | Copolymer latex and paper coating composition containing the same |
| JP2004176227A (en) * | 2002-11-28 | 2004-06-24 | Nippon A & L Kk | Fiber-bundling aqueous composition and carbon fiber strand |
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| JPH06172453A (en) * | 1992-12-10 | 1994-06-21 | Lion Corp | Production of self-dispersible and salt-sensitive polymer |
| JPH1060368A (en) * | 1996-05-29 | 1998-03-03 | Basf Ag | Binder for low-release coating composition |
| JP2002060415A (en) * | 2000-08-21 | 2002-02-26 | Yayoi Chemical Industry Co Ltd | Method for producing emulsion resin |
| JP2002265520A (en) * | 2001-03-14 | 2002-09-18 | Sumitomo Chem Co Ltd | Method of removing volatile component from copolymer latex |
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| JP2013133413A (en) * | 2011-12-27 | 2013-07-08 | Toagosei Co Ltd | Method for producing aqueous copolymer emulsion |
| JP2015117315A (en) * | 2013-12-18 | 2015-06-25 | 花王株式会社 | Method for producing polymer dispersion |
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