JPH04351613A - Production of fine polymer particle - Google Patents
Production of fine polymer particleInfo
- Publication number
- JPH04351613A JPH04351613A JP12416491A JP12416491A JPH04351613A JP H04351613 A JPH04351613 A JP H04351613A JP 12416491 A JP12416491 A JP 12416491A JP 12416491 A JP12416491 A JP 12416491A JP H04351613 A JPH04351613 A JP H04351613A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- group
- alkyl group
- carbon atoms
- ester
- 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.)
- Pending
Links
- 239000002245 particle Substances 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 7
- 239000007870 radical polymerization initiator Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 16
- -1 acrylic ester Chemical class 0.000 abstract description 8
- 125000005429 oxyalkyl group Chemical group 0.000 abstract 2
- 239000003999 initiator Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical class CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical class OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011797 cavity material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000003479 dental cement Substances 0.000 description 1
- 239000011350 dental composite resin Substances 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000012153 distilled water 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
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は粒径分布が単分散である
（メタ）アクリル酸エステル系共重合体の微粒子の製造
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing fine particles of a (meth)acrylic acid ester copolymer having a monodisperse particle size distribution.
【０００２】0002
【従来の技術】従来より球形重合体粒子を得る方法とし
ては乳化重合法、シード重合法、懸濁重合法があるが、
これらの方法では得られる重合体粒子の粒径単分散性に
劣るという問題があった。[Prior Art] Conventionally, methods for obtaining spherical polymer particles include emulsion polymerization, seed polymerization, and suspension polymerization.
These methods have a problem in that the resulting polymer particles have poor particle size monodispersity.
【０００３】粒径分布が単分散である（メタ）アクリル
酸エステル系球形重合体微粒子を得る方法としては、例
えばメタノール・水混合溶媒中でポリビニルアルコール
又はポリビニルピロリドンを分散安定剤として用いてメ
タクリル酸エステルを分散重合する方法、メタノール・
エチレングリコール混合溶媒中でポリビニルピロリドン
を分散安定剤として用いて分散重合する方法により１μ
ｍより大きく１５μｍ以下の均一粒径分布を有する球形
重合体を得ることが高分子学会予稿集１９９０年第３９
集第２号第１１５頁に報告されている。As a method for obtaining (meth)acrylic acid ester-based spherical polymer particles having a monodisperse particle size distribution, for example, methacrylic acid is mixed with polyvinyl alcohol or polyvinylpyrrolidone as a dispersion stabilizer in a mixed solvent of methanol and water. Method for dispersion polymerization of esters, methanol/
1μ by a method of dispersion polymerization using polyvinylpyrrolidone as a dispersion stabilizer in an ethylene glycol mixed solvent.
It is possible to obtain a spherical polymer having a uniform particle size distribution of greater than m and less than or equal to 15 μm.
Reported on page 115, No. 2, Vol.
【０００４】0004
【発明が解決しようとする課題】しかし、上記の高分子
学会予稿集に記載された方法では分散安定剤を使用する
ため、分散安定剤が不純物として残存し易いという問題
があり、更に、得られる重合体の粒径が１〜１５μｍと
やや大きく、サブミクロンオーダーのものが得られ難い
という問題があった。[Problem to be Solved by the Invention] However, since the method described in the Proceedings of the Society of Polymer Science and Technology mentioned above uses a dispersion stabilizer, there is a problem that the dispersion stabilizer tends to remain as an impurity. There was a problem in that the particle size of the polymer was rather large at 1 to 15 μm, making it difficult to obtain particles on the submicron order.
【０００５】[0005]
【課題を解決するための手段】本発明者らはこのような
状況に鑑み、鋭意検討した結果、反応溶媒として水、ア
ルコール又は水・アルコール混合溶媒を用い、（メタ）
アクリル酸エステルを重合するにあたって極性基を有す
る燐酸エステルをコモノマーとして用い、油溶性ラジカ
ル重合開始剤を用いて重合を行なうと、不純物の原因の
１つである乳化剤や分散剤を使用せずとも粒径分布の単
分散性に優れた（メタ）アクリル酸エステル系球形重合
体微粒子が得られることを見出し、本発明に到達した。[Means for Solving the Problems] In view of the above circumstances, the present inventors have made extensive studies and found that (meth)
When acrylic ester is polymerized using a phosphoric ester having a polar group as a comonomer and an oil-soluble radical polymerization initiator, it is possible to form particles without using emulsifiers or dispersants, which are one of the causes of impurities. It was discovered that (meth)acrylic acid ester-based spherical polymer fine particles having excellent monodispersity in diameter distribution can be obtained, and the present invention was achieved.
【０００６】即ち、本発明の要旨は水及び／又はアルコ
ールからなる溶媒中で（メタ）アクリル酸エステルと一
般式（１）又は（２）で示される重合性有機燐酸エステ
ルとをラジカル重合開始剤を用いて共重合することを特
徴とする重合体微粒子の製造法にある。That is, the gist of the present invention is to combine a (meth)acrylic acid ester and a polymerizable organic phosphoric acid ester represented by the general formula (1) or (2) with a radical polymerization initiator in a solvent consisting of water and/or alcohol. A method for producing fine polymer particles characterized by copolymerizing using.
【０００７】[0007]
【化３】[C3]
【０００８】[0008]
【化４】[C4]
【０００９】（式中、Ｒ１ はアルキル基の炭素数が１
〜１２である（メタ）アクリロイルオキシアルキル基又
は（メタ）アクリロイルオキシアルキルオキシアルキル
基を示し、Ｒ２ は炭素数１〜１２のアルキル基を示し
、ｌは０又は１、ｍは１又は２、ｎは１又は２であり、
かつｌ＋ｍ＋ｎ＝３であり、Ｒ３ はアルキル基の炭素
数が１〜５である（メタ）アクリロイルオキシアルキル
基又は（メタ）アクリロイルオキシアルキルオキシアル
キル基又は水素原子であって、但し２つのＲ３ が同時
に水素原子であるものを除くものであり、Ｒ４ は水素
原子の１つが水酸基で置換されていてもよい炭素数１〜
５のアルキル基、アルキル基の炭素数が１〜５である（
メタ）アクリロイルオキシアルキル基又は（メタ）アク
リロイルオキシアルキルオキシアルキル基又は水素原子
であって、３個のＲ４ が同時に水素原子であるもの及
び同時に不飽和基を有する基であるものを除くものであ
る。）(In the formula, R1 is an alkyl group with 1 carbon number
-12 (meth)acryloyloxyalkyl group or (meth)acryloyloxyalkyloxyalkyl group, R2 represents an alkyl group having 1 to 12 carbon atoms, l is 0 or 1, m is 1 or 2, n is 1 or 2,
and l+m+n=3, and R3 is a (meth)acryloyloxyalkyl group or (meth)acryloyloxyalkyloxyalkyl group in which the alkyl group has 1 to 5 carbon atoms, or a hydrogen atom, provided that two R3's are present at the same time. Excluding those that are hydrogen atoms, R4 has 1 to 1 carbon atoms in which one of the hydrogen atoms may be substituted with a hydroxyl group.
5 alkyl group, the alkyl group has 1 to 5 carbon atoms (
A meth)acryloyloxyalkyl group, a (meth)acryloyloxyalkyloxyalkyl group, or a hydrogen atom, excluding those in which three R4's are simultaneously hydrogen atoms and groups having an unsaturated group at the same time. . )
【００１０】本発明で用いられる（メタ）アクリ
ル酸エステルとしてはメチル（メタ）アクリレート、エ
チル（メタ）アクリレート、プロピル（メタ）アクリレ
ート、ｎ−ブチル（メタ）アクリレート、ｓｅｃ−ブチ
ル（メタ）アクリレート、ｔｅｒｔ− ブチル（メタ）
アクリレート、２−エチルヘキシル（メタ）アクリレー
ト、ラウリル（メタ）アクリレート、トリデシル（メタ
）アクリレート、ステアリル（メタ）アクリレート、シ
クロヘキシル（メタ）アクリレート、ベンジル（メタ）
アクリレート等を例示でき、これらの中ではメチルメタ
クリレート、エチルメタクリレート、ブチルメタクリレ
ートが好ましく用いられる。The (meth)acrylic esters used in the present invention include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)
Acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate
Examples include acrylates, among which methyl methacrylate, ethyl methacrylate, and butyl methacrylate are preferably used.
【００１１】一般式（１）で示される重合性有機燐酸エ
ステルの具体例として燐酸モノ２−（メタ）アクリロイ
ルオキキシエチルエステル、燐酸モノ３−（メタ）アク
リロイルオキシプロピルエステル、燐酸モノω−（メタ
）アクリロイルオキシペンチルエステル、燐酸モノω−
（メタ）アクリロイルオキシノニルエステル、燐酸モノ
ω−（メタ）アクリロイルオキシドデシルエステル、燐
酸ジ［（メタ）アクリロイルオキシエチル］ エステル
、燐酸ジ［（メタ）アクリロイルオキシプロピル］ エ
ステル、燐酸ジ［（メタ）アクリロイルオキシペンチル
］ エステル等を挙げることができ、これらの中では燐
酸モノ２−（メタ）アクリロイルオキキシエチルエステ
ル及び燐酸ジ［（メタ）アクリロイルオキシエチル］
エステルを好ましいものとしてあげることができる。Specific examples of the polymerizable organic phosphoric acid ester represented by the general formula (1) include phosphoric acid mono-2-(meth)acryloyloxyethyl ester, phosphoric acid mono-3-(meth)acryloyloxypropyl ester, and phosphoric acid monoω-( meth)acryloyloxypentyl ester, phosphoric acid monoω-
(meth)acryloyloxynonyl ester, mono-ω-(meth)acryloyloxydodecyl phosphate, di[(meth)acryloyloxyethyl] phosphate, di[(meth)acryloyloxypropyl] phosphate, di[(meth)phosphate] acryloyloxypentyl] esters, among which mono-2-(meth)acryloyloxyethyl phosphate and di[(meth)acryloyloxyethyl] phosphate
Esters can be mentioned as preferred.
【００１２】又、一般式（２）で示される重合性有機燐
酸エステルの具体例としては燐酸モノ２−（メタ）アク
リロイルオキキシエチルエステル、燐酸モノ３−（メタ
）アクリロイルオキシプロピルエステル、燐酸ジ［（メ
タ）アクリロイルオキシエチル］ エステル等のモノエ
タノールアミン塩、ジメチルアミノエチルメタクリレー
ト塩、次エチルアミノエチルメタクリレート塩等を例示
でき、これらの中では燐酸モノアクリロイルオキシエチ
ルエステルのジメチルアミノエチルメタクリレート塩を
好ましいものとして示すことができる。Further, specific examples of the polymerizable organic phosphoric acid ester represented by the general formula (2) include phosphoric acid mono-2-(meth)acryloyloxyethyl ester, phosphoric acid mono-3-(meth)acryloyloxypropyl ester, and phosphoric acid mono-2-(meth)acryloyloxypropyl ester. [(meth)acryloyloxyethyl] Examples include monoethanolamine salts, dimethylaminoethyl methacrylate salts, subethylaminoethyl methacrylate salts, etc. of esters, and among these, dimethylaminoethyl methacrylate salts of phosphoric acid monoacryloyloxyethyl esters are exemplified. It can be indicated as preferred.
【００１３】（メタ）アクリル酸エステルと上記の燐酸
エステルとの比率は（メタ）アクリル酸エステル１００
重量部に対して上記燐酸エステルが０．１〜５０重量部
であることが好ましく、１〜１０重量部であることがよ
り好ましい。この比率が上記比率をはずれると重合体が
沈殿、ゲル化、あるいは溶媒に溶解するようになる傾向
にあり、粒径単分散の球形重合体粒子が得られ難くなる
。[0013] The ratio of (meth)acrylic acid ester to the above-mentioned phosphoric acid ester is (meth)acrylic acid ester 100
The amount of the phosphoric acid ester is preferably 0.1 to 50 parts by weight, more preferably 1 to 10 parts by weight. If this ratio deviates from the above ratio, the polymer tends to precipitate, gel, or dissolve in the solvent, making it difficult to obtain spherical polymer particles with monodisperse particle size.
【００１４】本発明において用いられる溶媒は水、アル
コール又は水／アルコール混合溶媒が用いられ、アルコ
ールとしては単一成分のアルコールでもよく、複数種の
アルコールの混合物でもよい。アルコールとしては低級
アルコールが好ましく用いられ、メタノール、エタノー
ル、イソプロパノールがより好ましく用いられる。The solvent used in the present invention is water, alcohol, or a water/alcohol mixed solvent, and the alcohol may be a single component alcohol or a mixture of multiple types of alcohols. As the alcohol, lower alcohols are preferably used, and methanol, ethanol, and isopropanol are more preferably used.
【００１５】本発明においては、粒径単分散性に優れた
重合体粒子を得る観点から（メタ）アクリル酸エステル
と重合性燐酸エステルの合計量が溶媒１００重量部に対
して１〜１００重量部であることが好ましく、３〜５０
重量部であることがより好ましい。In the present invention, from the viewpoint of obtaining polymer particles with excellent particle size monodispersity, the total amount of (meth)acrylic ester and polymerizable phosphoric ester is 1 to 100 parts by weight based on 100 parts by weight of the solvent. is preferably 3 to 50
Parts by weight are more preferred.
【００１６】本発明で用いられるラジカル重合開始剤と
しては水溶性、油溶性のいずれのものでも用いうるが、
両者の中では油溶性のラジカル重合開始剤が好ましく用
いられる。The radical polymerization initiator used in the present invention may be either water-soluble or oil-soluble, but
Among the two, oil-soluble radical polymerization initiators are preferably used.
【００１７】油溶性のラジカル重合開始剤としては２，
２−アゾビスイソブチロニトリル、２，２’− アゾビ
ス−２，４− ジメチルバレロニトリル等のアゾ化合物
、ケトンパーオキサイド、ジアシルパーオキサイド、ジ
アルキルパーオキサイド、ハイドロパーオキサイド、パ
ーエステル等を例示でき、これらの中では２，２−アゾ
ビスイソブチロニトリル、２，２’− アゾビス−２，
４− ジメチルバレロニトリル、ベンゾイルパーオキサ
イドを好ましいものとして示すことができる。As the oil-soluble radical polymerization initiator, 2,
Examples include azo compounds such as 2-azobisisobutyronitrile and 2,2'-azobis-2,4-dimethylvaleronitrile, ketone peroxide, diacyl peroxide, dialkyl peroxide, hydroperoxide, and perester. , among these are 2,2-azobisisobutyronitrile, 2,2'-azobis-2,
4-dimethylvaleronitrile and benzoyl peroxide are preferred.
【００１８】該ラジカル重合開始剤は（メタ）アクリル
酸エステルと重合性燐酸エステルの合計量１００重量部
に対して０．０１〜５重量％程度用いられる。The radical polymerization initiator is used in an amount of about 0.01 to 5% by weight based on 100 parts by weight of the total amount of (meth)acrylic ester and polymerizable phosphoric ester.
【００１９】本発明の方法においては重合条件は特に限
定されるものではなく、例えば重合時間は重合温度や重
合開始剤の濃度、量等によって異なるが、一般には重合
温度５０〜９０℃、重合時間３０分〜５時間が適当であ
る。In the method of the present invention, the polymerization conditions are not particularly limited; for example, the polymerization time varies depending on the polymerization temperature, the concentration and amount of the polymerization initiator, etc., but in general, the polymerization temperature is 50 to 90°C, and the polymerization time is 50 to 90°C. 30 minutes to 5 hours is appropriate.
【００２０】本発明において規定した特定のモノマーの
組み合わせを特定の条件下で重合することにより初めて
０．１〜１μｍサブミクロンオーダーでかつ単分散性を
有する球形重合体粒子が得られるという優れた特徴を有
する。[0020] An excellent feature is that spherical polymer particles having a submicron order of 0.1 to 1 μm and monodispersity can be obtained for the first time by polymerizing the specific combination of monomers specified in the present invention under specific conditions. has.
【００２１】こうして得られる単分散性球形重合体粒子
は溶媒への分散や溶解が容易であり、歯科床用材料を初
めとした歯科用高分子材料、塗料用材料、フィルムスペ
ーサー、トナー用樹脂、カラム充填剤等広い用途分野に
応用可能であり、例えば義歯床用材料等の高分子粉末成
分として用いる場合、短時間でモノマーと混練し易いこ
とから操作性に優れるという特徴を有する。The monodisperse spherical polymer particles thus obtained are easily dispersed and dissolved in solvents, and can be used as dental polymer materials including dental floor materials, paint materials, film spacers, toner resins, It can be applied to a wide range of fields such as column fillers, and when used as a polymer powder component for denture base materials, for example, it is easy to knead with monomers in a short time, so it has excellent operability.
【００２２】更に、本発明の方法では重合時に乳化剤や
分散剤等の助剤を用いないため不純物の混入のない重合
物を得易く、歯科用接着剤、歯科用コンポジットレジン
、歯科用コーティング材料等の歯科用高分子材料のよう
な口腔内用材料、医用材料あるいは化粧品材料等用の為
害性のない重合体を得る方法として有用である。Furthermore, since the method of the present invention does not use auxiliary agents such as emulsifiers and dispersants during polymerization, it is easy to obtain polymers free of impurities, which can be used for dental adhesives, dental composite resins, dental coating materials, etc. This method is useful as a method for obtaining harmless polymers for use in oral cavity materials such as dental polymer materials, medical materials, cosmetic materials, and the like.
【００２３】[0023]
【実施例】以下に実施例により本発明を更に詳しく説明
するが、本発明はこれらの実施例に限定されるものでは
ない。なお、以下の記載中、「部」は他に規定のない限
り「重量部」を示す。EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In the following description, "parts" indicate "parts by weight" unless otherwise specified.
【００２４】又、生成物の平均粒径は得られた高分子化
合物粉末の電子顕微鏡写真から粒子１００個の粒径を測
定し、その重量平均粒径を求めた。The average particle size of the product was determined by measuring the particle size of 100 particles from an electron micrograph of the obtained polymer compound powder, and determining the weight average particle size.
【００２５】又、単分散性は動的光散乱測定装置（大塚
電子社製、ＤＬＳ−７００）を用いて重量平均粒径（ｄ
ｗ ）と数平均粒径（ｄｎ ）を求め、その比（ｄｗ
／ｄｎ ）を単分散性の指標とした。この指標は１に近
いほど単分散性であることを示す。[0025] Monodispersity can also be determined by measuring the weight average particle diameter (d
w ) and number average particle diameter (dn), and their ratio (dw
/dn) was used as an index of monodispersity. The closer this index is to 1, the more monodisperse it is.
【００２６】実施例１
５００ｍｌのガラス製セパラブルフラスコにエタノール
５０部とアゾビスイソブチロニトリル（以下ＡＩＢＮと
略記する）０．１部とを仕込み、次いでメチルメタクリ
レート（以下ＭＭＡと略記する）９．８部と燐酸モノ２
−（メタ）アクリロイルオキキシエチルエステル（以下
ＰＭＭＡＥと略記する）０．２部とを仕込み充分撹拌し
、更に蒸留水２５０部を仕込んで撹拌混合後、撹拌下、
フラスコ内を窒素置換後、引き続き窒素を流しながら７
０℃で３時間重合を行なった。Example 1 A 500 ml glass separable flask was charged with 50 parts of ethanol and 0.1 part of azobisisobutyronitrile (hereinafter abbreviated as AIBN), and then methyl methacrylate (hereinafter abbreviated as MMA) 9 .8 parts and 2 parts of monophosphoric acid
- 0.2 parts of (meth)acryloyl oxyethyl ester (hereinafter abbreviated as PMMAE) and stirred thoroughly, further charged with 250 parts of distilled water, mixed with stirring, and with stirring,
After purging the inside of the flask with nitrogen, continue to flow nitrogen until 7
Polymerization was carried out at 0°C for 3 hours.
【００２７】重合終了後、生成物を遠心分離して乾燥し
、重合体粉末７．１ｇを得た。得られた重合体は電子顕
微鏡観察によれば単分散性指標１．０１で平均粒径０．
５μｍの球形微粒子であった。After the polymerization was completed, the product was centrifuged and dried to obtain 7.1 g of polymer powder. According to electron microscopy, the obtained polymer had a monodispersity index of 1.01 and an average particle size of 0.
They were spherical fine particles with a diameter of 5 μm.
【００２８】実施例２〜５
ＭＭＡとＰＭＭＡＥの使用量をＭＭＡ９部とＰＭＭＡＥ
１部とし、重合開始剤の種類、使用量を表１に示したよ
うにした以外は実施例１と同様にして単分散性球形重合
体微粒子粉末を得た。得られた重合体粉末の収量、平均
粒径及び単分散性指標を表１に示す。Examples 2 to 5 The amounts of MMA and PMMAE used were 9 parts of MMA and 9 parts of PMMAE.
A monodisperse spherical polymer fine particle powder was obtained in the same manner as in Example 1, except that the type and amount of the polymerization initiator were as shown in Table 1. Table 1 shows the yield, average particle size, and monodispersity index of the obtained polymer powder.
【００２９】[0029]
【表１】[Table 1]
【００３０】実施例６〜１５
モノマー組成を表２に示したものとした以外は実施例１
と同様にして単分散性重合体球形粉末を得た。得られた
重合体粉末の収量、平均粒径及び単分散性指標を表２に
示す。Examples 6 to 15 Example 1 except that the monomer composition was as shown in Table 2.
A monodisperse polymer spherical powder was obtained in the same manner as above. Table 2 shows the yield, average particle size, and monodispersity index of the obtained polymer powder.
【００３１】[0031]
【表２】[Table 2]
【００３２】実施例１６〜２４
溶媒を表３に示すものとした以外は実施例２と同様（実
施例１６〜２３）あるいは実施例１０と同様（実施例２
４）にして単分散性球形重合体粉末を得た。得られた重
合体粉末の収量、平均粒径及び単分散性指標を表３に示
す。Examples 16-24 Same as Example 2 (Examples 16-23) or Same as Example 10 (Example 2) except that the solvent was used as shown in Table 3.
4) A monodisperse spherical polymer powder was obtained. Table 3 shows the yield, average particle size, and monodispersity index of the obtained polymer powder.
【００３３】[0033]
【表３】[Table 3]
【００３４】比較例１
ＭＭＡ９．８部とＰＭＭＡＥ０．２部の代わりにＭＭＡ
１０部のみを用いた以外は実施例１と同様にして重合体
粉末を得た。得られた重合体粉末は電子顕微鏡観察によ
れば無定形粒子であった。Comparative Example 1 MMA in place of 9.8 parts of MMA and 0.2 parts of PMMAE
A polymer powder was obtained in the same manner as in Example 1 except that only 10 parts were used. The obtained polymer powder was found to be amorphous particles when observed with an electron microscope.
【００３５】比較例２
５００ｍｌのガラス製セパラブルフラスコにエタノール
３００部とＡＩＢＮ０．１部とを仕込み、次いで９部の
ＭＭＡと１部のＰＭＭＡＥとを仕込み充分撹拌した後、
撹拌下、フラスコ内を窒素置換後、引き続き窒素を流し
ながら７０℃で５時間重合を行なった。Comparative Example 2 300 parts of ethanol and 0.1 part of AIBN were charged into a 500 ml separable glass flask, and then 9 parts of MMA and 1 part of PMMAE were charged and stirred thoroughly.
While stirring, the inside of the flask was replaced with nitrogen, and then polymerization was carried out at 70° C. for 5 hours while nitrogen was continuously flowing.
【００３６】重合終了後、生成物を大量のメタノール中
に投入して未反応物を除去して重合物を回収した。得ら
れた重合体は粉体ではなく一塊の塊状物であった。これ
を２日間減圧乾燥後、ボールミルで粉砕して重合体粉末
を得た。粉砕後の粒子は無定形の粒子であった。After the polymerization was completed, the product was poured into a large amount of methanol to remove unreacted materials and recover the polymer. The obtained polymer was not a powder but a lump. This was dried under reduced pressure for 2 days and then ground in a ball mill to obtain a polymer powder. The particles after pulverization were amorphous particles.
【００３７】[0037]
【発明の効果】本発明の方法によれば乳化剤や分散安定
剤等の助剤を使用することなくサブミクロンオーダーの
均一粒径の球形重合体微粒子が得られ、助剤を用いてい
ないので不純物の混入のない粒子が得られるという特徴
を有し、得られる重合体粉末は溶媒、モノマー等との易
溶解性、易分散性に優れるため幅広い用途に適用可能で
あり、しかも為害性もないため歯科材料等の口腔内用、
医用材料、化粧品材料として特に適しているという優れ
た重合体を得るに有効な方法である。Effects of the Invention: According to the method of the present invention, spherical polymer fine particles with a uniform particle size on the submicron order can be obtained without using auxiliary agents such as emulsifiers and dispersion stabilizers, and since no auxiliary agents are used, impurities can be obtained. The resulting polymer powder has excellent solubility and dispersibility with solvents, monomers, etc., so it can be applied to a wide range of applications, and is not harmful. For intraoral use such as dental materials,
This is an effective method for obtaining excellent polymers that are particularly suitable as medical materials and cosmetic materials.
Claims (1)
（メタ）アクリル酸エステルと一般式（１）又は（２）
で示される重合性有機燐酸エステルとをラジカル重合開
始剤を用いて共重合することを特徴とする重合体微粒子
の製造法。 【化１】 【化２】 （式中、Ｒ１ はアルキル基の炭素数が１〜１２である
（メタ）アクリロイルオキシアルキル基又は（メタ）ア
クリロイルオキシアルキルオキシアルキル基を示し、Ｒ
２ は炭素数１〜１２のアルキル基を示し、ｌは０又は
１、ｍは１又は２、ｎは１又は２であり、かつｌ＋ｍ＋
ｎ＝３であり、Ｒ３ はアルキル基の炭素数が１〜５で
ある（メタ）アクリロイルオキシアルキル基又は（メタ
）アクリロイルオキシアルキルオキシアルキル基又は水
素原子であって、但し２つのＲ３ が同時に水素原子で
あるものを除くものであり、Ｒ４ は水素原子の１つが
水酸基で置換されていてもよい炭素数１〜５のアルキル
基、アルキル基の炭素数が１〜５である（メタ）アクリ
ロイルオキシアルキル基又は（メタ）アクリロイルオキ
シアルキルオキシアルキル基又は水素原子であって、３
個のＲ４ が同時に水素原子であるもの及び同時に不飽
和基を有する基であるものを除くものである。）Claim 1: (Meth)acrylic acid ester and general formula (1) or (2) in a solvent consisting of water and/or alcohol.
A method for producing fine polymer particles, which comprises copolymerizing a polymerizable organic phosphoric acid ester represented by the following using a radical polymerization initiator. [Formula 1] [Formula 2] (wherein, R1 represents a (meth)acryloyloxyalkyl group or a (meth)acryloyloxyalkyloxyalkyl group in which the alkyl group has 1 to 12 carbon atoms, and R
2 represents an alkyl group having 1 to 12 carbon atoms, l is 0 or 1, m is 1 or 2, n is 1 or 2, and l+m+
n=3, and R3 is a (meth)acryloyloxyalkyl group or (meth)acryloyloxyalkyloxyalkyl group in which the alkyl group has 1 to 5 carbon atoms, or a hydrogen atom, provided that two R3's are hydrogen at the same time. Atoms are excluded, and R4 is an alkyl group having 1 to 5 carbon atoms in which one of the hydrogen atoms may be substituted with a hydroxyl group, and (meth)acryloyloxy in which the alkyl group has 1 to 5 carbon atoms. an alkyl group or a (meth)acryloyloxyalkyloxyalkyl group or a hydrogen atom, and 3
This excludes those in which R4's are both a hydrogen atom and a group having an unsaturated group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12416491A JPH04351613A (en) | 1991-05-29 | 1991-05-29 | Production of fine polymer particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12416491A JPH04351613A (en) | 1991-05-29 | 1991-05-29 | Production of fine polymer particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04351613A true JPH04351613A (en) | 1992-12-07 |
Family
ID=14878534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12416491A Pending JPH04351613A (en) | 1991-05-29 | 1991-05-29 | Production of fine polymer particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04351613A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851319A (en) * | 2009-03-30 | 2010-10-06 | 罗门哈斯公司 | Improved polymerisable compound |
-
1991
- 1991-05-29 JP JP12416491A patent/JPH04351613A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851319A (en) * | 2009-03-30 | 2010-10-06 | 罗门哈斯公司 | Improved polymerisable compound |
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