JPS6334902B2 - - Google Patents
Info
- Publication number
- JPS6334902B2 JPS6334902B2 JP11320280A JP11320280A JPS6334902B2 JP S6334902 B2 JPS6334902 B2 JP S6334902B2 JP 11320280 A JP11320280 A JP 11320280A JP 11320280 A JP11320280 A JP 11320280A JP S6334902 B2 JPS6334902 B2 JP S6334902B2
- Authority
- JP
- Japan
- Prior art keywords
- petroleum resin
- wax
- parts
- rosin
- modified
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003208 petroleum Substances 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 20
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 15
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 8
- 239000001993 wax Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004200 microcrystalline wax Substances 0.000 claims description 5
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000004203 carnauba wax Substances 0.000 claims description 4
- 235000013869 carnauba wax Nutrition 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 239000012170 montan wax Substances 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 229920001281 polyalkylene Polymers 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 125000004663 dialkyl amino group Chemical group 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000012190 activator Substances 0.000 description 16
- 125000002091 cationic group Chemical group 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000004078 waterproofing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FJEBWUFRAQKJMU-UHFFFAOYSA-N 2-n,2-n-dimethylpropane-1,2,3-triamine Chemical compound CN(C)C(CN)CN FJEBWUFRAQKJMU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
この発明は、防水剤として有用な炭化水素系エ
マルジヨン組成物に関し、特に紙および建材製品
例えばパルプ板、セメント板、石膏板、パーテイ
クルボード、インシユレーシヨンボード等の防水
剤用エマルジヨン組成物に関している。
これら製品は、一般に抄造法または成形法で作
られている。最近廃水の流出による環境汚染等の
公害防止の面から、抄造工程での白水を循環使用
されている。この結果、循環白水中に各種添加剤
が蓄積し、PHの低下、塩類濃度の上昇、消泡剤濃
度の増大等により、水質の悪化をもたらしてい
る。このため、従来の耐水剤はその性能を充分に
発揮することができなかつた。
従来用いられた防水剤は、パラフインワツク
ス、マイクロクリスタリンワツクス、α−オレフ
イン、モンタンロウ、カルナウバロウ、ポリエチ
レンワツクスのような炭化水素をアニオン活性
剤、ノニオン活性剤を用いて水中に分散させたエ
マルジヨンが一般に用いられていた。乳化剤とし
てカチオン活性剤を用いた製品も、一部用いられ
ていた。アニオン活性剤を用いた場合、用水の水
質が悪化しているとエマルジヨンの分散性が不良
で、所期の防水性を得ることが困難であり、また
ピツチトラブル等の原因ともなつた。ノニオン活
性剤は、劣悪な水に対しても安定性のあるエマル
ジヨンを製造できるが、循環水中に蓄積する傾向
があり、その親水性基のために製品の耐水性が低
下したり、またエマルジヨンを定着するために多
量のバンドを用いる必要がある。カチオン活性剤
としては、一般に高級脂肪酸アミン変性物が主と
して用いられる。しかし、この種のカチオン活性
剤水溶液は、極めて高粘度のためエマルジヨンの
粘度も高くなり、一般に20〜40％濃度の製品しか
得られなかつた。
本発明者は、上記のような欠点のない炭化水素
を水中に分散させるのに有用な界面活性剤につい
て鋭意研究を行つた。その結果、ロジンまたは石
油樹脂のカチオン変性物が、優れた界面活性を有
することを見出し、この発明が完成された。
この発明はパラフインワツクス、モンタンロ
ウ、カルナウバロウ、マイクロクリスタリンワツ
クス、α−オレフイン、ポリエチレンワツクスお
よび石油樹脂からなる群から選択される成分を、
カチオン変性ロジンおよびカチオン変性石油樹脂
からなる群から選択される界面活性剤10〜20重量
％（全固形分基準）の存在下に100〜500Kg／cm2の
圧力でピストン型高圧乳化機で水中に分散させた
粒子径3.0μｍ以下の水性エマルジヨン組成物を提
供する。
この発明で使用するワツクス類および石油樹脂
は耐水性、揆水性である点で同等のものである。
α−オレフインは二重結合を有するものであり、
ワツクス類は通常二重結合は有しない。
この発明で用いるカチオン活性剤は、ロジン、
変性ロジン、石油樹脂または変性石油樹脂とジア
ルキルポリアルキレンジアミンとを反応させ、得
られるアミン変性物を無機酸、有機酸または第４
級化剤で処理して製造される。
ロジンとしては、ガムロジン、ウツドロジン、
トールロジンが用いられる。これと１〜23wt％
のα，β−不飽和多塩基酸、例えばマレイン酸、
無水マレイン酸、フマル酸またはイタコン酸と
を、170〜230℃で２〜６時間、加熱、反応させれ
ば変性ロジン（附加物）が得られる。石油樹脂
は、ナフサ分解時に副生される沸点−20〜250℃
の留分をフリーデルクラフツ反応で重合させたも
のである。変性石油樹脂は、２〜15wt％のα、
β−不飽和多塩基酸附加物である。
ジアルキルポリアルキレンジアミンとしては、
１，１−ジアルキルポリアルキレンジアミン例え
ばジメチルアミノプロピレンジアミンまたはジエ
チルアミノプロピレンジアミンが用いられる。原
料に対し附加した多塩基酸と等モル量のジアミン
化合物を加え、170〜230℃で２〜６時間、加熱反
応させてアミン変性物を得る。
アミン変性物のカチオン化には、遊離アミノ基
に当モル割合で、例えば塩酸、硫酸、リン酸など
の無機酸、例えばギ酸、酢酸、シユウ酸などの有
機酸およびエチレンクロルヒドリン、ベンジルク
ロライドなどのような第４級化剤が用いられ、両
者を90〜160℃の温度で混合する。引き続き、温
水を加えて30〜50％水溶液として、この発明で用
いるカチオン活性剤を得る。
このカチオン活性剤は、原料としてロジン、変
性ロジン、石油樹脂および変性石油樹脂を用いて
いるので、疎水性部分の分子量が大きいため、親
水性部分も加熱したとき、一部分解する。したが
つて、このカチオン活性剤を用いたエマルジヨン
で処理すると、製品のサイズ性、耐水性の向上を
助長する。
以上のようにして得たカチオン活性剤水溶液を
有効成分として被乳化物の1.0〜20wt％、好まし
くは２〜10wt％の割合で、少なくとも１種のパ
ラフインワツクス、モンタンロウ、カルナウバロ
ウ、マイクロクリスタリンワツクス、平均炭素数
約30のα−オレフイン、ポリエチレンワツクスお
よび石油樹脂溶融物と混合、撹拌し必要に応じ温
水で稀釈して50〜60wt％濃度の水性分散物を得
る。次いで、分散物を100〜500Kg／cm2、好ましく
は150〜300Kg／cm2の圧力下でピストン型高圧乳化
機を１回またはそれ以上通過させて乳化し、粒子
径3μｍ以下の極めて安定性に富む乳白色の微粒
子エマルジヨンを得る。
この発明のエマルジヨン組成物は、表面サイズ
法により紙の耐水処理、および建材製品の耐水化
処理に用いられる。パルプ板、セメント板、イン
シユレーシヨンボードのように、原料をスラリー
状にして抄造する工程を含む場合は、スラリーに
エマルジヨン組成物を添加し、その後常法により
処理するのが便宜である。一方、石膏ボード、パ
ーテイクルボードでは、成形前に原料と混和する
のが普通である。
この発明を、次の実施例によりさらに詳細に説
明する。
実施例 １
(A) 撹拌機付反応釜に石油樹脂900部を装入し加
熱、溶融後、無水マレイン酸100部を添加し、
180〜210℃で５時間、撹拌下に加熱、反応させ
て変性石油樹脂を得た。引き続きジエチルアミ
ノプロピレンジアミン133部を加え180〜210℃
で３時間、撹拌しながら加熱、反応させてアミ
ン変性石油樹脂を得た。
(B) 上記(A)で得たアミン変性石油樹脂100部を乳
化釜に装入し加熱、溶融後、系内の温度を100
℃に調節し氷酢酸６部を加え、引き続き80℃の
温水144部を加え、撹拌して乳化分散させて固
形分40％のカチオン活性剤水溶液を得た。
実施例 ２
実施例１(A)で得たアミン変性石油樹脂100部を
撹拌機付反応釜で加熱、溶融し、系内の温度を
150℃に調節し、エチレンクロルヒドリン８部を
添加し、撹拌下に150℃で５時間加熱反応させた。
次いで、系内の温度を90〜100℃まで低下させて
から、70℃の温水142部を加え撹拌下に乳化、分
散させて固形分40％のカチオン活性剤の水溶液を
得た。
実施例 ３
融点51〜52℃の末精製パラフインワツクス85部
および融点87℃のマイクロクリスタリンワツクス
10部を、乳化釜中で90℃で溶融し、実施例１で得
たカチオン活性剤水溶液12.5部、次いで90℃の温
水92.5部を加え、撹拌して分散物を得た。分散物
を90℃で、250Kg／cm2の圧力下にピストン型高圧
乳化機を１回通過させ、冷却して固形分50％、粒
径3μｍ以下の乳白色エマルジヨンを得た。
実施例 ４
融点72℃のパラフインワツクス70部および軟化
点90℃の石油樹脂20部を、乳化釜中で加熱、溶融
し、系内の温度を95℃に保ち実施例２で得たカチ
オン活性剤水溶液25部および90℃の温水85部を加
え、撹拌下に分散物を得た。分散物を90℃で300
Kg／cm2の圧力下にピストン型高圧乳化機を２回通
過させ、冷却して固形分50％の安定な乳白色エマ
ルジヨンを得た。
実施例 ５
実施例１(A)の処理法に準じて、ロジン100部お
よび無水マレイン酸10部を180〜210℃で３時間反
応させ、引き続きジエチルアミノプロピレンジア
ミン13部を180〜210℃で３時間反応させた。得ら
れるアミン変性ロジン100部およびエチレンクロ
ルヒドリン10.5部から、実施例２の処理法に準じ
てカチオン活性剤水溶液を得た。融点80℃のポリ
エチレンワツクス20部および融点78℃のα−オレ
フイン（平均炭素数30）60部を、乳化釜で加熱、
溶融し90℃に保ち、カチオン活性剤水溶液50部お
よび90℃の温水70部を加え、撹拌して分散物を得
た。
分散物を、90℃で200Kg／cm2の圧力下にピスト
ン型高圧乳化機を２回通過させ、冷却して粒径
3μｍ以下の安定な乳白色エマルジヨンを得た。
上記実施例で得たエマルジヨンおよび市販のエ
マルジヨンを用いて、紙にサイズを施してその性
能を比較した。
パルプ Ｌ／Ｎ（50／50）晒クラフトパルプ
叩解度 350c.c.（CSF）
坪量 60g／m2
添加量 0.2、0.4、0.6および0.8％（固形物）
乾燥条件 90℃のドラムドライヤーで２分間
抄紙温度 40℃
抄紙温度 パルプ離解５分間でサイズ剤添加、そ
の５分後に稀釈し、さらに１分後に抄紙。
サイズ JIS−Ｐ−8122で測定
The present invention relates to a hydrocarbon emulsion composition useful as a waterproofing agent, and particularly to an emulsion composition for waterproofing paper and building material products such as pulp board, cement board, gypsum board, particle board, insulation board, etc. There is. These products are generally made by papermaking or molding methods. Recently, white water from the papermaking process has been recycled for use in order to prevent pollution such as environmental pollution caused by wastewater runoff. As a result, various additives accumulate in the circulating white water, resulting in deterioration of water quality due to a decrease in pH, an increase in salt concentration, an increase in antifoaming agent concentration, etc. For this reason, conventional water-resistant agents have not been able to fully demonstrate their performance. Conventionally used waterproofing agents are emulsions in which hydrocarbons such as paraffin wax, microcrystalline wax, α-olefin, montan wax, carnauba wax, and polyethylene wax are dispersed in water using an anionic activator or a nonionic activator. was commonly used. Some products used cationic activators as emulsifiers. When an anionic activator is used, if the quality of the water used is poor, the dispersibility of the emulsion is poor, making it difficult to obtain the desired waterproof properties and also causing pitting troubles. Nonionic surfactants can produce emulsions that are stable even in poor water conditions, but they tend to accumulate in circulating water, and their hydrophilic groups can reduce the water resistance of the product or cause emulsions to deteriorate. It is necessary to use a large amount of band for fixation. Generally, higher fatty acid amine modified products are mainly used as the cationic activator. However, this type of cationic activator aqueous solution has an extremely high viscosity, resulting in a high emulsion viscosity, and generally only a product with a concentration of 20 to 40% can be obtained. The present inventor has conducted intensive research on surfactants useful for dispersing hydrocarbons in water without the above-mentioned drawbacks. As a result, it was discovered that a cationically modified product of rosin or petroleum resin has excellent surface activity, and the present invention was completed. This invention comprises a component selected from the group consisting of paraffin wax, montan wax, carnauba wax, microcrystalline wax, α-olefin, polyethylene wax, and petroleum resin.
in water in a piston-type high-pressure emulsifier at a pressure of 100-500 Kg/ cm2 in the presence of 10-20% by weight (based on total solids) of a surfactant selected from the group consisting of cationically modified rosins and cationically modified petroleum resins. An aqueous emulsion composition having a dispersed particle size of 3.0 μm or less is provided. The waxes and petroleum resins used in this invention are equivalent in terms of water resistance and water repellency.
α-olefin has a double bond,
Waxes usually do not have double bonds. The cationic activator used in this invention is rosin,
A modified rosin, a petroleum resin, or a modified petroleum resin is reacted with a dialkyl polyalkylene diamine, and the resulting amine-modified product is treated with an inorganic acid, an organic acid, or a quaternary acid.
Manufactured by treatment with a grading agent. Examples of rosin include gum rosin, uds rosin,
Tall rosin is used. This and 1-23wt%
α,β-unsaturated polybasic acids such as maleic acid,
A modified rosin (adjunct) is obtained by heating and reacting maleic anhydride, fumaric acid or itaconic acid at 170 to 230°C for 2 to 6 hours. Petroleum resin is a by-product during naphtha decomposition and has a boiling point of -20 to 250℃.
This fraction is polymerized by Friedel-Crafts reaction. The modified petroleum resin contains 2 to 15 wt% α,
It is a β-unsaturated polybasic acid adduct. As dialkyl polyalkylene diamine,
1,1-dialkylpolyalkylene diamines such as dimethylaminopropylene diamine or diethylaminopropylene diamine are used. A diamine compound in an amount equimolar to the added polybasic acid is added to the raw material, and the mixture is heated and reacted at 170 to 230°C for 2 to 6 hours to obtain an amine-modified product. For cationization of the amine-modified product, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as formic acid, acetic acid, and oxalic acid, and ethylene chlorohydrin, benzyl chloride, etc. are used in equimolar proportions to free amino groups. A quaternizing agent such as is used and both are mixed at a temperature of 90 to 160°C. Subsequently, warm water is added to obtain a 30 to 50% aqueous solution to obtain the cationic activator used in the present invention. Since this cationic activator uses rosin, modified rosin, petroleum resin, and modified petroleum resin as raw materials, the hydrophilic part also partially decomposes when heated because the molecular weight of the hydrophobic part is large. Therefore, treatment with an emulsion using this cationic activator helps improve the sizing properties and water resistance of the product. The cationic activator aqueous solution obtained as described above is used as an active ingredient in an amount of 1.0 to 20 wt%, preferably 2 to 10 wt% of the emulsified material, to at least one type of paraffin wax, montan wax, carnauba wax, or microcrystalline wax. , an α-olefin having an average carbon number of about 30, a polyethylene wax, and a petroleum resin melt, mixed, stirred, and diluted with warm water as necessary to obtain an aqueous dispersion having a concentration of 50 to 60 wt%. The dispersion is then passed through a piston-type high-pressure emulsifier one or more times under a pressure of 100 to 500 Kg/cm 2 , preferably 150 to 300 Kg/cm 2 to emulsify it to a very stable particle size of 3 μm or less. A rich, opalescent, fine-particle emulsion is obtained. The emulsion composition of the present invention is used for water-resistant treatment of paper and building materials by the surface sizing method. In cases where the material includes a step of turning raw materials into a slurry and making paper, such as pulp boards, cement boards, and insulation boards, it is convenient to add an emulsion composition to the slurry and then process it by a conventional method. On the other hand, for gypsum board and particle board, it is common to mix it with raw materials before forming. This invention will be explained in more detail by the following examples. Example 1 (A) 900 parts of petroleum resin was charged into a reaction vessel equipped with a stirrer, and after heating and melting, 100 parts of maleic anhydride was added,
The mixture was heated and reacted with stirring at 180 to 210°C for 5 hours to obtain a modified petroleum resin. Subsequently, 133 parts of diethylaminopropylene diamine was added to the mixture at 180-210°C.
The mixture was heated and reacted with stirring for 3 hours to obtain an amine-modified petroleum resin. (B) Charge 100 parts of the amine-modified petroleum resin obtained in (A) above into an emulsification pot, heat and melt, and then reduce the temperature in the system to 100 parts.
℃ and added 6 parts of glacial acetic acid, followed by adding 144 parts of 80°C warm water and stirring to emulsify and disperse to obtain an aqueous cationic activator solution with a solid content of 40%. Example 2 100 parts of the amine-modified petroleum resin obtained in Example 1 (A) was heated and melted in a reaction vessel equipped with a stirrer, and the temperature in the system was lowered.
The temperature was adjusted to 150°C, 8 parts of ethylene chlorohydrin was added, and the mixture was heated and reacted at 150°C for 5 hours with stirring.
Next, the temperature in the system was lowered to 90 to 100°C, and then 142 parts of 70°C warm water was added and emulsified and dispersed with stirring to obtain an aqueous solution of a cationic activator with a solid content of 40%. Example 3 85 parts of refined paraffin wax with a melting point of 51-52°C and microcrystalline wax with a melting point of 87°C
10 parts were melted at 90°C in an emulsification pot, 12.5 parts of the aqueous cation activator solution obtained in Example 1, and then 92.5 parts of 90°C warm water were added and stirred to obtain a dispersion. The dispersion was passed through a piston-type high-pressure emulsifier once at 90° C. under a pressure of 250 kg/cm 2 and cooled to obtain a milky white emulsion with a solid content of 50% and a particle size of 3 μm or less. Example 4 70 parts of paraffin wax with a melting point of 72°C and 20 parts of petroleum resin with a softening point of 90°C were heated and melted in an emulsifying pot, and the temperature in the system was maintained at 95°C to obtain the cation activity obtained in Example 2. 25 parts of an aqueous solution of the agent and 85 parts of 90°C warm water were added to obtain a dispersion with stirring. Dispersion at 90℃ for 300
The mixture was passed twice through a piston-type high-pressure emulsifier under a pressure of Kg/cm 2 and cooled to obtain a stable milky white emulsion with a solid content of 50%. Example 5 According to the treatment method of Example 1(A), 100 parts of rosin and 10 parts of maleic anhydride were reacted at 180 to 210°C for 3 hours, and then 13 parts of diethylaminopropylene diamine were reacted at 180 to 210°C for 3 hours. Made it react. A cationic activator aqueous solution was obtained from 100 parts of the obtained amine-modified rosin and 10.5 parts of ethylene chlorohydrin according to the treatment method of Example 2. 20 parts of polyethylene wax with a melting point of 80°C and 60 parts of α-olefin (average carbon number 30) with a melting point of 78°C were heated in an emulsifying pot.
The mixture was melted and maintained at 90°C, and 50 parts of a cation activator aqueous solution and 70 parts of 90°C warm water were added and stirred to obtain a dispersion. The dispersion was passed through a piston-type high-pressure emulsifier twice at 90℃ under a pressure of 200Kg/ cm2 , cooled, and the particle size was determined.
A stable milky white emulsion with a diameter of 3 μm or less was obtained. Using the emulsion obtained in the above example and a commercially available emulsion, paper was sized and their performances were compared. Pulp L/N (50/50) bleached kraft pulp Beating degree 350c.c. (CSF) Basis weight 60g/ m2 Addition amount 0.2, 0.4, 0.6 and 0.8% (solids) Drying conditions 2 in a drum dryer at 90℃ Minute paper making temperature 40℃ Paper making temperature Add sizing agent after 5 minutes of pulp disintegration, dilute after 5 minutes, and make paper after another 1 minute. Size Measured according to JIS-P-8122
【表】
ジヨン
[Front] Jiyoung
Claims (1)
ウバロウ、マイクロクリスタリンワツクス、α−
オレフイン、ポリエチレンワツクスおよび石油樹
脂からなる群から選択される成分を、カチオン変
性ロジンおよびカチオン変性石油樹脂からなる群
から選択される界面活性剤1.0〜20重量％（全固
形分基準）の存在下に100〜500Kg／cm2の圧力でピ
ストン型高圧乳化機で水中に分散させた粒子径
3.0μｍ以下の水性エマルジヨン組成物。 ２ 前記界面活性剤がロジン、変性ロジン、石油
樹脂または変性石油樹脂とジアルキルアミノポリ
アルキレンジアミンとの反応生成物を無機酸、有
機酸または第４級化剤で処理して得たものである
特許請求の範囲第１項記載の水性エマルジヨン組
成物。 ３ 前記界面活性剤を全固形分の２〜10重量％の
割合で用いる特許請求の範囲第１項記載の水性エ
マルジヨン組成物。[Claims] 1 Parafine wax, montan wax, carnauba wax, microcrystalline wax, α-
A component selected from the group consisting of olefin, polyethylene wax, and petroleum resin in the presence of 1.0 to 20% by weight (based on total solids) of a surfactant selected from the group consisting of cationically modified rosin and cationically modified petroleum resin. The particle size was dispersed in water using a piston-type high-pressure emulsifier at a pressure of 100 to 500 kg/ cm2 .
Aqueous emulsion composition with a diameter of 3.0 μm or less. 2. A patent in which the surfactant is obtained by treating a rosin, a modified rosin, a petroleum resin, or a reaction product of a modified petroleum resin and a dialkylamino polyalkylene diamine with an inorganic acid, an organic acid, or a quaternizing agent. The aqueous emulsion composition according to claim 1. 3. The aqueous emulsion composition according to claim 1, wherein the surfactant is used in an amount of 2 to 10% by weight of the total solid content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11320280A JPS5738838A (en) | 1980-08-18 | 1980-08-18 | Aqueous emulsion composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11320280A JPS5738838A (en) | 1980-08-18 | 1980-08-18 | Aqueous emulsion composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5738838A JPS5738838A (en) | 1982-03-03 |
| JPS6334902B2 true JPS6334902B2 (en) | 1988-07-12 |
Family
ID=14606132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11320280A Granted JPS5738838A (en) | 1980-08-18 | 1980-08-18 | Aqueous emulsion composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5738838A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0622808U (en) * | 1992-06-30 | 1994-03-25 | 和嘉治 近藤 | Tea stove |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2116483C (en) * | 1994-02-25 | 1997-07-22 | Lionel Borenstein | Water-resistant gypsum compositions and emulsion for making same |
| JP4615927B2 (en) * | 2004-08-03 | 2011-01-19 | ユニチカ株式会社 | Aqueous dispersion and aqueous heat sealant |
| EP2062943A1 (en) * | 2007-11-14 | 2009-05-27 | Akzo Nobel N.V. | Asphalt modifiers for "warm mix" applications including adhesion promoter |
-
1980
- 1980-08-18 JP JP11320280A patent/JPS5738838A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0622808U (en) * | 1992-06-30 | 1994-03-25 | 和嘉治 近藤 | Tea stove |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5738838A (en) | 1982-03-03 |
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