JPS6220212B2 - - Google Patents
Info
- Publication number
- JPS6220212B2 JPS6220212B2 JP58207994A JP20799483A JPS6220212B2 JP S6220212 B2 JPS6220212 B2 JP S6220212B2 JP 58207994 A JP58207994 A JP 58207994A JP 20799483 A JP20799483 A JP 20799483A JP S6220212 B2 JPS6220212 B2 JP S6220212B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- precondensate
- amino
- resin particles
- aqueous solution
- 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.)
- Expired
Links
- 229920005989 resin Polymers 0.000 claims description 43
- 239000011347 resin Substances 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 41
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 229920003180 amino resin Polymers 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- -1 amino compound Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 229940057995 liquid paraffin Drugs 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- RAPZEAPATHNIPO-UHFFFAOYSA-N risperidone Chemical compound FC1=CC=C2C(C3CCN(CC3)CCC=3C(=O)N4CCCCC4=NC=3C)=NOC2=C1 RAPZEAPATHNIPO-UHFFFAOYSA-N 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- SJJISKLXUJVZOA-UHFFFAOYSA-N Solvent yellow 56 Chemical compound C1=CC(N(CC)CC)=CC=C1N=NC1=CC=CC=C1 SJJISKLXUJVZOA-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- YSKUZVBSHIWEFK-UHFFFAOYSA-N ammelide Chemical compound NC1=NC(O)=NC(O)=N1 YSKUZVBSHIWEFK-UHFFFAOYSA-N 0.000 description 1
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
【発明の詳細な説明】
本発明は粒径が30ミクロンから3mmの小球状の
アミノ系樹粒子を製造する方法に関する。本発明
の実施により得られた粒子はポリアミド、エポキ
シ樹脂の充填材として、あるいは着色剤、濾過助
剤、塗料用の濃化剤として有用である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing small spherical amino-based tree particles having a particle size of 30 microns to 3 mm. The particles obtained by the practice of this invention are useful as fillers in polyamides and epoxy resins, and as colorants, filter aids, and thickening agents for paints.
ポリアミドやエポキシ樹脂の有機充填材として
メラミン樹脂粒子を用いることは知られている。
通常、かかる樹脂はメラミン樹脂硬化物の機械的
粉砕物であり、形状が不揃いであるとともに表明
も粗であり、不透明なものである。かかる粉砕品
は球状の充填材と比較して充填率が低くなる傾向
がある。また、透明の樹脂成形品を目的とする場
合はかかる不透明の充填材を用いることができな
い欠点がある。 It is known to use melamine resin particles as an organic filler for polyamide and epoxy resins.
Usually, such resin is a mechanically crushed product of a cured melamine resin, and is irregular in shape, coarse in texture, and opaque. Such pulverized products tend to have a lower filling rate than spherical fillers. Furthermore, when the objective is to produce a transparent resin molded product, there is a drawback that such an opaque filler cannot be used.
一方、ポリイソシアネート化合物とアルコール
のアルキレンオキサンド付加物とを反応させて得
られる水溶性化合物に、尿素とホルマリンを配合
して混合し、ついでリン酸水溶液よりなる硬化剤
を加え、60〜63℃で縮合反応を行つて白色の分散
液を得、この分散液に増白剤、尿素、水を加えて
から58〜60℃で反応させ、更に苛性ソーダ水溶液
を加えてPHを8.4に調製し、紙用の塗工剤として
有用な貯蔵安定性良好な尿素樹脂の分散液を製造
することは知られている(特開昭57−170916
号)。 On the other hand, a water-soluble compound obtained by reacting a polyisocyanate compound and an alkylene oxande adduct of alcohol is mixed with urea and formalin, and then a curing agent consisting of an aqueous phosphoric acid solution is added to the mixture at 60 to 63°C. A white dispersion was obtained by carrying out a condensation reaction, and a whitening agent, urea, and water were added to this dispersion, and the reaction was carried out at 58 to 60°C. Furthermore, an aqueous solution of caustic soda was added to adjust the pH to 8.4. It is known to produce a urea resin dispersion with good storage stability that is useful as a coating agent for
issue).
かかる分散液の樹脂粒子は1〜3ミクロン前後
の微細なものであり、水より分離が困難である。 The resin particles in such a dispersion are fine, about 1 to 3 microns, and are more difficult to separate than water.
本発明者は溶媒中でアミノ系化合物とホルムア
ルデヒドを反応させて樹脂粒子を析出させる方法
において、粒径が30ミクロン〜3mmと大きな粒子
を得るべく種々検討を行つたところ、アミノ系化
合物とホルムアルデヒドの予備縮合を水溶媒中で
行ない、この予備縮合物の硬化を、水と、該縮合
物の非溶媒との混合液中で行うことによりかかる
目的とする粒径の樹脂粒子が得られることを見い
出し、本発明に到つた。しかも本発明の実施によ
り得られる樹脂粒子は透明であつた。 The present inventor conducted various studies in order to obtain large particles with a particle size of 30 microns to 3 mm in a method in which resin particles are precipitated by reacting an amino compound and formaldehyde in a solvent. It has been found that resin particles having the desired particle size can be obtained by performing precondensation in an aqueous solvent and curing the precondensate in a mixed solution of water and a non-solvent of the condensate. , arrived at the present invention. Furthermore, the resin particles obtained by carrying out the present invention were transparent.
即ち、本発明は、白濁点が40℃以上のアミノ系
化合物とホルマリンとの予備縮合物の水溶液に酸
性硬化剤を配合した樹脂溶液を、前記予備縮合物
の非溶媒と混合し、撹拌下に40〜90℃に前記樹脂
溶液と非溶媒の混合液を30分〜1時間加熱するこ
とにより予備縮合物の硬化を行つて透明で小球状
のアミノ樹脂を析出させることを特徴とするアミ
ノ系樹脂粒子の製造方法を提供するものである。 That is, in the present invention, a resin solution prepared by blending an acidic curing agent into an aqueous solution of a precondensate of formalin and an amino compound having a white turbidity point of 40° C. or higher is mixed with a nonsolvent of the precondensate, and the mixture is stirred. An amino resin characterized in that a precondensate is cured by heating a mixture of the resin solution and a nonsolvent at 40 to 90°C for 30 minutes to 1 hour to precipitate a transparent, small spherical amino resin. A method for producing particles is provided.
本発明の実施において、アミノ系化合物として
はメラシン、尿素、アンメリン、アンメリド等ア
ミノ基(−NH2)を有する化合物があげられる。 In the practice of the present invention, examples of amino compounds include compounds having an amino group ( -NH2 ) such as melasin, urea, ammeline, and ammelide.
酸性硬化剤としてはリン酸、硫酸、塩酸塩の鉱
酸、パラトルエンスルホン酸、蟻酸、キシレンス
ルホン酸等の有機酸があげられる。 Examples of the acidic curing agent include mineral acids such as phosphoric acid, sulfuric acid, and hydrochloride, and organic acids such as para-toluenesulfonic acid, formic acid, and xylenesulfonic acid.
アミノ系樹脂予備縮合物に非溶媒としてはシリ
コンオイル、流動パラフイン、ヘキサン、オクタ
ン等の直鎖パラフイン類、ベンゼン、トルエン、
キシレン等の芳香族パラフイン類、四塩化炭素等
があげられる。 Nonsolvents for the amino resin precondensate include silicone oil, liquid paraffin, hexane, linear paraffins such as octane, benzene, toluene,
Examples include aromatic paraffins such as xylene, carbon tetrachloride, and the like.
然して、アミノ系樹脂予備縮合物の製造は、ア
ミノ系化合物とホルムアルデヒドの水溶液(ホル
マリン)とを苛性ソーダ、苛性カリ等のアルカリ
触媒の存在下に60〜90℃の温度で白濁点が40℃以
上、好ましくは60〜70℃となるまで予備縮合す
る。アルカリ触媒を配合した液のPHは8〜12であ
る。 Therefore, in order to produce an amino resin precondensate, an amino compound and an aqueous solution of formaldehyde (formalin) are mixed in the presence of an alkali catalyst such as caustic soda or caustic potash at a temperature of 60 to 90°C, preferably with a cloudiness point of 40°C or higher. is precondensed until the temperature reaches 60-70°C. The pH of the liquid containing the alkaline catalyst is 8-12.
ここで白濁点とは、アミノ系樹脂予備縮合物の
3%水溶液を90℃より漸次冷却していつたとき、
液に白濁が見受けられる温度をいう〔工業化学雑
誌、60巻、1号567頁(1957年)〕。 Here, the cloudiness point refers to the point when a 3% aqueous solution of the amino resin precondensate is gradually cooled from 90°C.
The temperature at which cloudiness is observed in the liquid [Industrial Chemistry Magazine, Vol. 60 , No. 1, p. 567 (1957)].
予備縮合物の白濁点が40℃未満であると粒子製
造時の硬化反応時間が長くなり好ましくない。 If the cloudiness point of the precondensate is less than 40°C, the curing reaction time during particle production becomes undesirable.
アミノ化合物のアミノ基1当量に対するホルム
アルデヒドの仕込量は1/2〜1当量が好ましい。
必要に応じ、樹脂液は減圧脱水により樹脂固型分
を調製してもよい。 The amount of formaldehyde charged per equivalent of the amino group of the amino compound is preferably 1/2 to 1 equivalent.
If necessary, a resin solid content may be prepared from the resin liquid by dehydration under reduced pressure.
このようにして製造された予備縮合物の水溶液
に前記酸性硬化剤を配合し、系のPHを1〜6に調
整する。 The acidic curing agent is added to the aqueous solution of the precondensate thus produced, and the pH of the system is adjusted to 1-6.
この樹脂溶液を、前記予備縮合物の非溶媒と混
合し、撹拌下に40〜90℃の温度で30分〜60分反応
させてアミノ系樹脂粒子の析出を行わせる。この
際、混合液中にポリビニルアルコール、ポリビニ
ルピロリドン、CMC等の保護コロイド剤を配合
しておくことも可能である。 This resin solution is mixed with the non-solvent of the precondensate, and reacted with stirring at a temperature of 40 to 90°C for 30 to 60 minutes to precipitate amino resin particles. At this time, it is also possible to incorporate a protective colloid agent such as polyvinyl alcohol, polyvinylpyrrolidone, or CMC into the mixed solution.
また、混合液に染料、例えばスピロンレツド
2W(保谷土化学製商品名)、ソルベントイエロ−
56(商品名 オイルイエローGG−S、オリエン
ト化学製)、ソルベントオレンジ72(商品名 ダ
イヤレジン ブラウンA、三菱化成工業製)、ソ
ルベントブルー35(商品名 オイルブルーN、
オリエント化学製)等を配合しておけば染料は硬
化する樹脂粒子に吸収され、染色した透明のアミ
ノ系樹脂球状粒子が得られる。染料は予備縮合物
100重量部に対し、0.001〜1重量部の割合で用い
られる。 Also, add a dye to the mixture, such as Spiron Red.
2W (Hoyado Chemical product name), Solvent Yellow
56 (product name Oil Yellow GG-S, manufactured by Orient Chemical), Solvent Orange 72 (product name Diamond Resin Brown A, manufactured by Mitsubishi Chemical Industries), Solvent Blue 35 (product name Oil Blue N,
(manufactured by Orient Chemical Co., Ltd.), etc., the dye will be absorbed by the hardening resin particles, and transparent colored amino-based resin spherical particles will be obtained. Dye is a precondensate
It is used in a proportion of 0.001 to 1 part by weight per 100 parts by weight.
シリコンオイル等の非溶媒は水とも非相溶性で
あり、これは予備縮合物100重量部に対し100〜
900重量部の割合で用いる。 Non-solvents such as silicone oil are also incompatible with water, and this amount is 100 to 100 parts by weight per 100 parts by weight of the precondensate.
Used in a proportion of 900 parts by weight.
加熱、硬化により製造された球状の樹脂粒子
は、過、水による洗浄、乾燥され、商品とな
る。この樹脂粒子の粒径は30μ〜3mmであり、透
明である。粒径は樹脂液の非溶媒中での分散強度
により所望の球径を有する樹脂粒子を得ることが
できる。 The spherical resin particles produced by heating and curing are washed with filtrate and water and dried to become commercial products. The resin particles have a particle size of 30 μm to 3 mm and are transparent. Resin particles having a desired spherical diameter can be determined depending on the dispersion strength of the resin liquid in a non-solvent.
この樹脂粒子はポリアミド、エポキシ樹脂、フ
エノール樹脂、不飽和ポリエステル樹脂等の充填
材として、また、染色した樹脂粒子は着色材とし
て有用である。 These resin particles are useful as fillers for polyamides, epoxy resins, phenolic resins, unsaturated polyester resins, etc., and the dyed resin particles are useful as colorants.
以下、実施例によつて本発明を更に詳細に説明
する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 1
冷却器を備えたステンレス製反応器内に、メラ
ミン630gおよび37%ホルマリン1215gを投入
し、更に苛性ソーダを投入して液のPHを8.5に調
整した。ついで80℃で白濁点が62℃(水混和度
110)となるまで縮合反応させた。Example 1 Into a stainless steel reactor equipped with a cooler, 630 g of melamine and 1215 g of 37% formalin were charged, and caustic soda was further added to adjust the pH of the liquid to 8.5. Then, at 80℃, the cloudy point is 62℃ (water miscibility
The condensation reaction was carried out until 110).
この予備縮合樹脂水溶液400gを、別の反応器
内にとり35%塩酸26gを添加し、よく混合後、シ
リコンオイル(東芝シリコン製YF−33)を1200
g添加し、樹脂液がシリコンオイル中で微粒子に
分散するような撹拌条件下、60℃で1時間硬化反
応を続けて樹脂粒子を製造し、過、洗浄後、樹
脂粒子を乾燥し、平均粒径が約100ミクロンの透
明な球状微粒子を380g得た。 400 g of this precondensation resin aqueous solution was placed in another reactor, and 26 g of 35% hydrochloric acid was added thereto. After mixing well, 1200 g of silicone oil (YF-33 manufactured by Toshiba Silicon Co., Ltd.) was added.
The curing reaction was continued at 60°C for 1 hour under stirring conditions such that the resin liquid was dispersed into fine particles in silicone oil to produce resin particles. After filtering and washing, the resin particles were dried to obtain an average particle size. 380 g of transparent spherical fine particles with a diameter of about 100 microns were obtained.
実施例 2
冷却器を備えた反応容器内に、メラミン518
g、尿素124g、37%ホルマリン1000gおよび日
本合成化学製ポリビニルアルコール“ゴーセノー
ル T−330”(商品名)16gを投入し、ついで48
%苛性ソーダ水溶液を加えて液のPHを11.5とし、
80℃に加熱して予備縮合反応を行い、白濁点60℃
の水溶液を得た。Example 2 Melamine 518 was placed in a reaction vessel equipped with a condenser.
g, 124 g of urea, 1000 g of 37% formalin, and 16 g of polyvinyl alcohol “Gosenol T-330” (trade name) made by Nippon Gosei, and then 48 g of
% caustic soda aqueous solution to adjust the pH of the liquid to 11.5.
Heating to 80℃ to perform precondensation reaction, cloudy point 60℃
An aqueous solution of was obtained.
この予備縮合樹脂水溶液400gを別の反応容器
内にとり、35%塩酸26gを添加し、よく混合後、
流動パラフインを1200g添加し、撹拌しつつ60℃
で1時間反応させて樹脂粒子を析出させた。 400 g of this precondensed resin aqueous solution was placed in another reaction vessel, 26 g of 35% hydrochloric acid was added, and after mixing thoroughly,
Add 1200g of liquid paraffin and heat to 60℃ while stirring.
The mixture was reacted for 1 hour to precipitate resin particles.
過、水洗して樹脂粒子を分離し、これを乾燥
した。得られた樹脂粒子は、平均粒径が約90ミク
ロンの球状体であり、透明であつた。 The resin particles were separated by filtering and washing with water, and then dried. The obtained resin particles were spherical with an average particle size of about 90 microns and were transparent.
実施例 3
尿素300gと37%ホルマリン810gの混合溶液に
48%苛性ソーダ水溶液を添加し、PHを9に調整し
た。ついで撹拌下、80℃で30分予備縮合反応を行
つた。Example 3 A mixed solution of 300 g of urea and 810 g of 37% formalin
A 48% caustic soda aqueous solution was added to adjust the pH to 9. Then, a precondensation reaction was carried out at 80° C. for 30 minutes while stirring.
ついで、蟻酸を水溶液のPHが4.2となるように
添加し、白濁点60℃の樹脂水溶液を得た。 Then, formic acid was added so that the pH of the aqueous solution was 4.2, to obtain an aqueous resin solution with a cloudy point of 60°C.
この水溶液400gをとり、これに35%塩酸26g
を添加し、よく混合液、流動パラフインを1200g
添加し、撹拌しつつ60℃で1時間反応させて樹脂
粒子を析出させた。 Take 400g of this aqueous solution and add 26g of 35% hydrochloric acid to it.
Add, mix well, and 1200g of liquid paraffin.
The mixture was added and reacted at 60° C. for 1 hour with stirring to precipitate resin particles.
過、水洗して樹脂粒子を分離し、これを乾燥
した。得られた樹脂粒子は、平均粒径が約60ミク
ロンの球状体であり、透明であつた。 The resin particles were separated by filtering and washing with water, and then dried. The obtained resin particles were spherical with an average particle size of about 60 microns and were transparent.
実施例 4
冷却器を備えた反応容器内に、メラミン518
g、尿素124g、37%ホルマリン1000gおよび日
本合成化学製ポリビニルアルコール“ゴーセノー
ルT−330”(商品名)16gを投入し、ついで48%
苛性ソーダ水溶液を加えて液のPHを11.5とし、80
℃に加熱して予備縮合反応を行い、白濁点60℃の
水溶液を得た。Example 4 Melamine 518 was placed in a reaction vessel equipped with a condenser.
g, 124 g of urea, 1000 g of 37% formalin, and 16 g of polyvinyl alcohol "Gohsenol T-330" (trade name) manufactured by Nippon Gosei, and then 48%
Add caustic soda aqueous solution to adjust the pH of the solution to 11.5, and reduce to 80.
A precondensation reaction was carried out by heating to .degree. C. to obtain an aqueous solution with a cloudy point of 60.degree.
この予備縮合樹脂水溶液400gを別の反応容器
内にとり、35%塩酸26gを添加し、よく混合後、
シリコンオイルと四塩化炭素の2:1混合液を
1200g添加し、ゆるく撹拌しつつ60℃で1時間反
応させて樹脂粒子を製造した。 400 g of this precondensed resin aqueous solution was placed in another reaction vessel, 26 g of 35% hydrochloric acid was added, and after mixing thoroughly,
A 2:1 mixture of silicone oil and carbon tetrachloride
1200g was added and reacted at 60°C for 1 hour with gentle stirring to produce resin particles.
過、水洗して樹脂粒子を分離し、これを乾燥
した。得られた樹脂粒子は、平均粒径が約2.5mm
の球状体であり、透明であつた。 The resin particles were separated by filtering and washing with water, and then dried. The obtained resin particles have an average particle size of approximately 2.5 mm.
It was spherical and transparent.
実施例 5
冷却器を備えた反応容器内に、メラミン518
g、尿素124g、37%ホルマリン1000gおよび日
本合成化学製ポリビニルアルコール“ゴーセノー
ル T−330”(商品名)16gを投入し、ついで48
%苛性ソーダ水溶液を加えて液のPHを11.5とし、
80℃に加熱して予備縮合反応を行い、白濁点60℃
の水溶液を得た。Example 5 Melamine 518 was placed in a reaction vessel equipped with a condenser.
g, 124 g of urea, 1000 g of 37% formalin, and 16 g of polyvinyl alcohol “Gosenol T-330” (trade name) made by Nippon Gosei, and then 48 g of
% caustic soda aqueous solution to adjust the pH of the liquid to 11.5.
Heating to 80℃ to perform precondensation reaction, cloudy point 60℃
An aqueous solution of was obtained.
この予備縮合樹脂水溶液400gを別の反応容器
内にとり、これに保土谷化学製染料“スピロンレ
ツド”0.2gおよび35%塩酸26gを添加し、よく
混合後、シリコンオイルを1200g添加し、撹拌し
つつ60℃で1時間反応させて樹脂粒子を析出させ
た。 400 g of this precondensed resin aqueous solution was placed in another reaction container, and 0.2 g of Hodogaya Chemical's dye "Spiron Red" and 26 g of 35% hydrochloric acid were added thereto. After mixing thoroughly, 1200 g of silicone oil was added, and the mixture was stirred for 60 min. The reaction was carried out at ℃ for 1 hour to precipitate resin particles.
過、水洗して樹脂粒子を分離し、これを乾燥
した。得られた樹脂粒子は、平均粒径が約85ミク
ロンの球状体であり、赤色透明であつた。 The resin particles were separated by filtering and washing with water, and then dried. The obtained resin particles were spherical with an average particle size of about 85 microns, and were transparent and red.
Claims (1)
リンとの予備縮合物の水溶液に酸性硬化剤を配合
した樹脂溶液を、前記予備縮合物の非溶媒と混合
し、撹拌下に40〜90℃に前記樹脂溶液と非溶媒の
混合液を30分〜1時間加熱することにより予備縮
合物の硬化を行つて透明で小球状のアミノ樹脂を
製造することを特徴とするアミノ系樹脂粒子の製
造方法。 2 アミノ系化合物がメラミンもしくは尿素、ま
たは両者の混合物であることを特徴とする特許請
求の範囲第1項記載の製造方法。 3 予備縮合物の硬化が染料の存在下に行われる
ことを特徴とする特許請求の範囲第1項記載の製
造方法。[Scope of Claims] 1. A resin solution prepared by blending an acidic curing agent into an aqueous solution of a precondensate of formalin and an amino compound with a cloudy point of 40°C or higher is mixed with a non-solvent of the precondensate, and the mixture is stirred. An amino-based amino resin characterized in that the precondensate is cured by heating the mixture of the resin solution and non-solvent at 40 to 90°C for 30 minutes to 1 hour to produce a transparent, small spherical amino resin. Method for producing resin particles. 2. The manufacturing method according to claim 1, wherein the amino compound is melamine, urea, or a mixture of both. 3. The manufacturing method according to claim 1, wherein the precondensate is cured in the presence of a dye.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20799483A JPS6099119A (en) | 1983-11-05 | 1983-11-05 | Preparation of particles of amino resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20799483A JPS6099119A (en) | 1983-11-05 | 1983-11-05 | Preparation of particles of amino resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6099119A JPS6099119A (en) | 1985-06-03 |
JPS6220212B2 true JPS6220212B2 (en) | 1987-05-06 |
Family
ID=16548914
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20799483A Granted JPS6099119A (en) | 1983-11-05 | 1983-11-05 | Preparation of particles of amino resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6099119A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6268810A (en) * | 1985-09-20 | 1987-03-28 | Dainichi Color & Chem Mfg Co Ltd | Ultraviolet light reflective resin particle and production thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5213987A (en) * | 1975-07-22 | 1977-02-02 | Kanebo Ltd | Casing line of plural kinds small lot products |
-
1983
- 1983-11-05 JP JP20799483A patent/JPS6099119A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5213987A (en) * | 1975-07-22 | 1977-02-02 | Kanebo Ltd | Casing line of plural kinds small lot products |
Also Published As
Publication number | Publication date |
---|---|
JPS6099119A (en) | 1985-06-03 |
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