JPH0550558B2 - - Google Patents
Info
- Publication number
- JPH0550558B2 JPH0550558B2 JP59118346A JP11834684A JPH0550558B2 JP H0550558 B2 JPH0550558 B2 JP H0550558B2 JP 59118346 A JP59118346 A JP 59118346A JP 11834684 A JP11834684 A JP 11834684A JP H0550558 B2 JPH0550558 B2 JP H0550558B2
- Authority
- JP
- Japan
- Prior art keywords
- detergent
- calcium carbonate
- granular detergent
- weight
- powder
- 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 - Lifetime
Links
- 239000003599 detergent Substances 0.000 claims description 42
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 22
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 10
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011164 primary particle Substances 0.000 claims description 5
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 description 20
- 229910000019 calcium carbonate Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- -1 alkylbenzene sulfonates Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 239000012190 activator Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940001468 citrate Drugs 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229940049920 malate Drugs 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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
Description
産業上の利用分野
本発明は粒状洗剤の粉体物性、特に無リン洗剤
の吸湿時の加圧固化性を改善する粒状洗剤の製造
方法に関する。
従来の技術
リン酸系ビルダーは優れた無機質ビルダーであ
り、従来は汎く粒状洗剤に配合されていた。しか
し、湖沼、内湾などの富栄養化への配慮から、無
リン化への努力が払われていた。しかし、湖沼、
内湾などの富栄養化への配慮から、無リン化への
努力が払われている。リン酸系ビルダーに代るも
のとしては、珪酸アルカリ塩、炭酸アルカリ塩、
重炭酸アルカリ塩などが用いられ、また、近年ゼ
オライトが注目されている。
しかしながら、これら代替ビルダーは洗浄力の
向上に対する効果は認められるものの、粉体特性
の改質効果は不十分であつた。
本出願人はこのような無リン粒状洗剤の吸湿に
基因する固化性を改善するため、粒状化した洗剤
の外面に非吸湿性のビルダー、金属石けんあるい
はアミノシリケートを層として被覆し、洗剤粒子
表面の性質を改質することを提案した（特開昭49
−38906号、特開昭50−51508号、特開昭50−
24305）。
また、水不溶性ないし水難溶性の粉体を粒状洗
剤に付着させることにより、粒状洗剤の粉体物性
を改善しうることを見出し、このような粉体とし
て平均粒径1.5μm以下の酸化マグネシウム、水酸
化アルミニウム、重質炭酸カルシウム、ホワイト
カーボン、酸化チタン（特開昭53−114807号公
報）あるいは平均粒径２〜5μmの炭酸カルシウム
（特開昭54−103406号公報）を提案した。
発明が解決しようとする問題点
しかし、特開昭50−24305号等に開示した洗剤
粒子を膜層で被覆する方法は、当初の吸湿による
固化の防止という点では効果があるものの、工程
の煩雑さ、均質品の取得の困難さ等の点で問題が
あるばかりでなく、洗剤の溶解性、長期保存時の
吸湿固化性等にも難があり、必ずしも満足すべき
ものではなかつた。
また、特開昭53−114807号公報等に記載された
ような粉体を付着させて被覆する方法は、製造操
作は簡便であるものの、十分に付着しにくいた
め、洗浄力を維持しつつ十分な粉体特性の改質効
果を得るという点でさらに改善がまたれていた。
問題を解決するための手段
本発明は、洗浄力を損なうことなく粉体物性を
改善することのできる粉状洗剤の製造方法を提供
することを目的とする。
すなわち、本発明の粒状洗剤の製造方法は、少
なくとも１種のアニオン界面活性剤と、アルカリ
金属珪酸塩と、アルカリ金属炭酸塩とを含有する
粒状洗剤の粒子表面に一次粒子径が0.1〜1.5μmで
あり、粒子の最小径／最大径比が0.3〜0.7のサイ
コロ状の微細沈降炭酸カルシウムを、該粒状洗剤
100重量部当り0.5〜３重量部付着せしめることを
特徴とする。
本発明の粒状洗剤で用いられるアニオン界面活
性剤としては、
アルキル基の炭素数が８〜15のアルキルベンゼ
ンスルホン酸塩、
アルキル基の炭素数が８〜18のアルキル硫酸
塩、
アルキル基の炭素数が８〜18のアルコールに酸
化エチレンを平均１〜８モル付加させたアルキル
エーテル硫酸塩、
炭素数12〜22のαーオレフインスルホン酸塩
（α−オレフインのスルホン化物でアルケンスル
ホン酸塩、ヒドロキシアルカンスルホン酸塩など
の混合物）、
炭素数12〜22のパラフインから得られるアルカ
ンスルホン酸塩、
高級脂肪酸塩、
高級脂肪酸とタウリンとの縮合物の塩（Ｎ−ア
シルアミノエタンスルホン酸塩）、
スルホコハク酸ジアルキルエステルの塩などが
例示される。これらはアルカリ金属塩が適当で、
スルホン酸やサルフエート型アニオン活性剤の場
合はマグネシウム塩も適している。アニオン活性
剤は粒状洗剤中に10〜40重量％配合するのが適当
であり、このましくは15〜30重量％である。
本発明の粒状洗剤は、また、無機ビルダーとし
てアルカリ金属珪酸塩およびアルカリ金属炭酸塩
を含有し、ナトリウム塩、カリウム塩が好適であ
る。アルカリ金属珪酸塩としては、M2Ｏ・
nSiO2（Ｍ：アルカリ金属）でモル比ｎが2.0〜3.6
のものが好ましい。アルカリ金属珪酸塩は洗剤中
に４〜20wt％配合するのが適当であり、好まし
くは８〜15wt％である。
アルカリ金属炭酸塩は洗剤中に２〜40wt％配
合するのが適当であり、好ましくは５〜30wt％
である。
上記各成分を含む洗剤は、噴霧乾燥法などによ
り造粒されて、通常粒径300〜600μmの粒状洗剤
とされる。
この粒状洗剤の粒子表面に、一次粒子径が0.1
〜1.5μm、好ましくは0.3〜1μmの沈降炭酸カルシ
ウムが付着される。この粉体による被覆は回転混
合機、振動混合機などの混合機により行うことが
でき、また、回転造粒機、転動造粒機、振動造粒
機のような造粒機などによつても行うことができ
る。
炭酸カルシウムの一次粒子径が1.5μmよりも大
きくなると粉体物性の改質効果が劣化し、一方、
0.1μm未満では凝集が激しく、粉体物性改良効果
が小さいばかりか、ハンドリングが困難になる。
微細沈降炭酸カルシウム粉体の使用量は、粒状
洗剤100重量部に対して0.5〜３重量部、好ましく
は１〜２重量部である。0.5重量部未満では粉体
物性の改良効果が不十分であり、一方、３重量部
を越えると洗浄力が低下してしまう。
また、本発明では微細沈降炭酸カルシウムの形
状がサイコロ状であることが重要であり、粒子の
最小径／最大径比が0.3〜0.7のサイコロ状を用い
る。さらに好ましい上記比率は0.4〜0.7である。
このようなサイコロ状の粒子とすることにより効
率よく粒状洗剤を被覆することができる。上記比
率範囲を逸脱すると、粉体物性の改質効果が不十
分となる。このような一次粒子径が0.1〜1.5μmの
サイコロ状の微細沈降炭酸カルシウムは、例えば
特公昭59−12607号公報に記載の方法により得ら
れる。すなわち、結晶面（001）、（100）および
（102）に対するＸ線回析強度比（Ｉ／Ｉ。）がそ
れぞれ64〜75、26〜38および31〜32の範囲にある
水酸化カルシウム粉末を用いてミルク濃度５〜15
％の懸濁液を調整し、以下の３段階に分けて二酸
化炭素を拭き込んで炭酸化することにより、結晶
方向性を有しないサイコロ状の粒子として微細沈
降性炭酸カルシウムが得られる。
炭酸カルシウム粒子の粒径は、第１段階での炭
酸化率を制御することにより調整でき、第１段階
での炭酸化率を小さくすると粒径の大きい炭酸カ
ルシウムが、また、炭酸化率を大きくすれば小さ
な粒径の炭酸カルシウムが得られる。
(1) 第１段階：反応開始温度15〜20℃において、
水酸化カルシウム１Kg当たり７／min以上の
供給速度で、炭酸化率が３〜10％に達するまで
二酸化炭素を吹き込む。
(2) 第２段階：１〜３／minの供給速度で、炭
酸化率が30〜70％に達するまで二酸化炭素を吹
き込む。
(3) 第３段階：７／min以上の供給速度で、炭
酸化率が100％に達するまで二酸化炭素を吹き
込む。
また、上記のサイコロ状炭酸カルシウムは、市
販品として入手することもでき、例えば、奥多摩
工業（株）（商品名：タマパールTP＃200）、フア
イザー・クレグレー社から入手できる。
本発明で表面改質される粒状洗剤は、クエン酸
塩、リンゴ酸塩、酒石酸塩、マレイン酸塩ポリマ
ー、アルキル置換コハク酸塩、トキシジ酢酸塩な
どの有機ビルダー、水溶性硫酸塩、再汚染防止剤
（CMC、PEG、PVAなど）、泡コントロール剤、
蛍光増白剤、漂白剤、色素、香料などを任意成分
として含有することもできる。
作 用
粒状洗剤に微細沈降炭酸カルシウムを付着させ
ることにより、洗剤粒子の粉体物性が改善され
る。なお、一般に沈降炭酸カルシウム紡錘形か柱
状であるが、このような形状のものは洗剤粒子表
面との接触面積が少なくて付着しにくいため粉体
特性改良効果が劣る。
効 果
本発明の製造方法によれば、洗浄力を低下させ
ることなく、流動性、吸湿固化性、加圧固化性な
どの粉体特性、特に吸湿時の加圧固化性を改良す
ることができる。
実施例
以下の組成の平均粒径400〜500μmの粒状洗剤
を噴霧乾燥により製造した。
アルキンベンゼンスルホン酸ソーダ
（Ｃ：10〜14） 12wt％
α−オレフインスルホン酸ソーダ
（Ｃ：13〜18） 12wt％
珪酸ソーダ（SiO2／Na2Ｏ＝2.2） 12wt％
炭酸ソーダ 10wt％
水 5wt％
硫酸ソーダ バランス
この粒状洗剤100重量部に対して、それぞれ第
１表に示した性状の沈降炭酸カルシウムを第１表
に示した重量部添加し、Ｖ型ミキサーで５分間混
合し、炭酸カルシウムを粒状洗剤の表面に付着さ
せて被覆した。
これら各試料（No.２〜８）および炭酸カルシウ
ムを付着させなかつた試料（No.１）の吸湿固化性
および洗浄力を以下の手順で測定して第１表に示
した。なお、第１表中の最小径／最大径の比は電
子顕微鏡写真で各粒子の最大径、最小径を測定
し、ｎ＝50の平均をとつた。
吸湿固化性（ダマ量）
洗剤用カルトン（22×15.5×5.5cm、透湿度
300g／m324hr）に粒子を充填し、35℃−100％の
ヒユーミデイテイボツクス（Humidity Box）に
３日静置後、カルトンを切り開き、４メツシユの
フルイ上に注意深くうつし、フルイをゆるやかに
振動したのちのフルイ上の重量と原試料の重量比
によつて示した。
洗浄力
試布（綿）をワイシヤツの衿に装着し、２〜７
日間着用して汚染したのち取りはずし、左右対称
に切断したものを20枚づつ用意する。別に２〜３
日間着用した肌シヤツ（綿メリヤス）を用意し、
左右対称に分割する。このようにして汚染された
試布及び肌シヤツの各一方を標準洗剤（炭酸カル
シウム付着なし、第１表のNo.１）により、他方を
被検試料（炭酸カルシウム付着、第１表のNo.２以
降）により洗剤濃度0.15％、液温25℃、欲比30倍
で10分間洗濯した後、３分間づつ２回すすぐ。洗
浄後の各試布は各１対づつ左右を肉眼で比較判定
し、標準洗剤の洗浄力の評点で各試料洗剤の評点
を除して100倍した数値を洗浄力指数とした。
比較例
後記第２表に示した性状の炭酸カルシウムを用
いる以外は前述の実施例と同様にして試料No.９，
10の試料洗剤を調整し、その評価結果を第２表に
示した。
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing a granular detergent that improves the powder properties of a granular detergent, particularly the pressure solidification properties of a phosphorus-free detergent upon moisture absorption. Prior Art Phosphoric acid builders are excellent inorganic builders and have conventionally been widely incorporated into granular detergents. However, due to concerns about eutrophication of lakes, marshes, and inner bays, efforts were being made to eliminate phosphorus. However, lakes,
Efforts are being made to eliminate phosphorus from consideration of eutrophication in inner bays. Substitutes for phosphate builders include alkali silicate salts, alkali carbonate salts,
Alkaline bicarbonate salts and the like are used, and zeolites have been attracting attention in recent years. However, although these alternative builders were recognized to be effective in improving detergency, their effect on modifying powder properties was insufficient. In order to improve the solidifying properties of such phosphorus-free granular detergents due to moisture absorption, the applicant coated the outer surface of the granulated detergent with a layer of non-hygroscopic builder, metal soap, or aminosilicate, thereby improving the detergent particle surface. proposed to modify the properties of
−38906, JP-A No. 50-51508, JP-A-50-
24305). We also discovered that the powder properties of granular detergents can be improved by attaching water-insoluble or poorly water-soluble powders to granular detergents. Aluminum oxide, heavy calcium carbonate, white carbon, titanium oxide (Japanese Unexamined Patent Publication No. 114807/1982), or calcium carbonate with an average particle size of 2 to 5 μm (Japanese Unexamined Patent Publication No. 103406/1983) were proposed. Problems to be Solved by the Invention However, although the method of coating detergent particles with a membrane layer disclosed in JP-A No. 50-24305 is effective in preventing solidification due to initial moisture absorption, the process is complicated. In addition to problems such as the difficulty in obtaining a homogeneous product, there were also problems with detergent solubility and moisture absorption and solidification during long-term storage, and the results were not necessarily satisfactory. In addition, the method of coating by adhering powder as described in JP-A No. 53-114807, etc., although the manufacturing operation is simple, does not adhere sufficiently, so it is difficult to adhere to the powder, so it is difficult to adhere to the powder. Further improvements were made in terms of obtaining the effect of modifying powder properties. Means for Solving the Problems An object of the present invention is to provide a method for producing a powder detergent that can improve powder physical properties without impairing detergency. That is, in the method for producing a granular detergent of the present invention, the particle surface of a granular detergent containing at least one kind of anionic surfactant, an alkali metal silicate, and an alkali metal carbonate has a primary particle size of 0.1 to 1.5 μm. The fine precipitated calcium carbonate in the form of dice with a particle minimum diameter/maximum diameter ratio of 0.3 to 0.7 is added to the granular detergent.
It is characterized in that it is deposited in an amount of 0.5 to 3 parts by weight per 100 parts by weight. The anionic surfactants used in the granular detergent of the present invention include alkylbenzene sulfonates whose alkyl group has 8 to 15 carbon atoms, alkyl sulfates whose alkyl group has 8 to 18 carbon atoms, and alkyl sulfates whose alkyl group has 8 to 18 carbon atoms. Alkyl ether sulfates made by adding an average of 1 to 8 moles of ethylene oxide to 8 to 18 alcohols, α-olefin sulfonates with 12 to 22 carbon atoms (sulfonated α-olefins, alkenesulfonates, hydroxyalkanesulfones) (mixtures of acid salts, etc.), alkanesulfonates obtained from paraffin having 12 to 22 carbon atoms, higher fatty acid salts, salts of condensates of higher fatty acids and taurine (N-acylaminoethanesulfonates), dialkyl sulfosuccinates Examples include ester salts. Alkali metal salts are suitable for these.
Magnesium salts are also suitable for sulfonic acid and sulfate type anionic activators. The anionic activator is suitably blended in the granular detergent in an amount of 10 to 40% by weight, preferably 15 to 30% by weight. The granular detergent of the present invention also contains alkali metal silicates and alkali metal carbonates as inorganic builders, with sodium salts and potassium salts being preferred. As the alkali metal silicate, M 2 O.
nSiO 2 (M: alkali metal) with a molar ratio n of 2.0 to 3.6
Preferably. It is appropriate to incorporate the alkali metal silicate into the detergent in an amount of 4 to 20 wt%, preferably 8 to 15 wt%. It is appropriate for the alkali metal carbonate to be blended in the detergent at 2 to 40 wt%, preferably 5 to 30 wt%.
It is. A detergent containing each of the above components is granulated by a spray drying method or the like to form a granular detergent with a particle size of usually 300 to 600 μm. The particle surface of this granular detergent has a primary particle size of 0.1
~1.5 μm, preferably 0.3-1 μm of precipitated calcium carbonate is deposited. This powder coating can be performed using a mixer such as a rotary mixer or a vibration mixer, or a granulator such as a rotary granulator, a rolling granulator, or a vibration granulator. can also be done. When the primary particle size of calcium carbonate is larger than 1.5 μm, the effect of modifying powder physical properties deteriorates;
If the particle size is less than 0.1 μm, agglomeration will be severe, and not only will the effect of improving powder physical properties be small, but it will also be difficult to handle. The amount of fine precipitated calcium carbonate powder used is 0.5 to 3 parts by weight, preferably 1 to 2 parts by weight, per 100 parts by weight of granular detergent. If it is less than 0.5 parts by weight, the effect of improving powder physical properties will be insufficient, while if it exceeds 3 parts by weight, the detergency will decrease. Furthermore, in the present invention, it is important that the fine precipitated calcium carbonate has a dice-like shape, and a dice-like shape with a particle minimum diameter/maximum diameter ratio of 0.3 to 0.7 is used. A more preferable ratio is 0.4 to 0.7.
By forming such dice-shaped particles, the granular detergent can be efficiently coated. If the ratio is outside the above range, the effect of modifying the powder physical properties will be insufficient. Such dice-shaped fine precipitated calcium carbonate having a primary particle size of 0.1 to 1.5 μm can be obtained, for example, by the method described in Japanese Patent Publication No. 12607/1983. That is, calcium hydroxide powder having X-ray diffraction intensity ratios (I/I.) for crystal planes (001), (100), and (102) in the ranges of 64 to 75, 26 to 38, and 31 to 32, respectively, was used. Use milk concentration 5-15
% suspension and carbonate it by wiping in carbon dioxide in the following three stages to obtain fine precipitated calcium carbonate as dice-shaped particles with no crystal orientation. The particle size of calcium carbonate particles can be adjusted by controlling the carbonation rate in the first stage, and if the carbonation rate in the first stage is decreased, calcium carbonate with a larger particle size will be produced, and the carbonation rate will be increased. This will yield calcium carbonate with a small particle size. (1) First stage: At a reaction initiation temperature of 15 to 20°C,
Carbon dioxide is blown in at a feed rate of 7/min or more per 1 kg of calcium hydroxide until the carbonation rate reaches 3 to 10%. (2) Second stage: Blow in carbon dioxide at a feed rate of 1 to 3/min until the carbonation rate reaches 30 to 70%. (3) Third stage: Blow in carbon dioxide at a supply rate of 7/min or more until the carbonation rate reaches 100%. Moreover, the above-mentioned diced calcium carbonate can also be obtained as a commercial product, for example, from Okutama Kogyo Co., Ltd. (trade name: Tama Pearl TP #200) and Pfizer-Clegley. The granular detergent surface-modified in the present invention includes organic builders such as citrate, malate, tartrate, maleate polymers, alkyl-substituted succinates, toxidiacetates, water-soluble sulfates, anti-refouling agents, etc. agents (CMC, PEG, PVA, etc.), foam control agents,
Optional ingredients such as optical brighteners, bleaching agents, dyes, and fragrances may also be included. Effect By attaching fine precipitated calcium carbonate to granular detergent, the powder physical properties of detergent particles are improved. Incidentally, precipitated calcium carbonate is generally spindle-shaped or columnar, but such shapes have a small contact area with the surface of detergent particles and are difficult to adhere to, resulting in poor powder property improvement effects. Effects According to the production method of the present invention, powder properties such as fluidity, moisture absorption solidification properties, and pressure solidification properties, particularly pressure solidification properties upon moisture absorption, can be improved without reducing detergency. . Example A granular detergent having the following composition and an average particle size of 400 to 500 μm was produced by spray drying. Sodium alkynebenzenesulfonate (C: 10-14) 12wt% Sodium α-olefin sulfonate (C: 13-18) 12wt% Sodium silicate (SiO 2 /Na 2 O = 2.2) 12wt% Sodium carbonate 10wt% Water 5wt% Sodium sulfate Balance To 100 parts by weight of this granular detergent, add the parts by weight shown in Table 1 of precipitated calcium carbonate having the properties shown in Table 1, mix for 5 minutes with a V-type mixer, and add calcium carbonate to 100 parts by weight of this granular detergent. It was attached and coated on the surface of the detergent. The hygroscopic hardening properties and detergency of each of these samples (Nos. 2 to 8) and the sample to which calcium carbonate was not attached (No. 1) were measured according to the following procedure and are shown in Table 1. The minimum diameter/maximum diameter ratio in Table 1 was determined by measuring the maximum diameter and minimum diameter of each particle using an electron microscope photograph, and taking the average of n=50. Moisture absorption solidification (lump amount) Detergent carton (22 x 15.5 x 5.5 cm, moisture permeability
300g/m 3 24hr) was filled with particles and left to stand in a Humidity Box at 35°C - 100% for 3 days, then the carton was cut open and carefully placed on a 4-mesh sieve. It is shown by the weight ratio of the original sample to the weight on the sieve after being vibrated. Cleaning power Attach the sample cloth (cotton) to the collar of the dress shirt and wash it for 2 to 7 minutes.
After being worn for a day and becoming contaminated, they are removed and cut into symmetrical pieces, making 20 pieces each. 2-3 separately
Prepare a skin shirt (cotton knitted) that has been worn for days,
Split symmetrically. One of the thus contaminated test cloths and skin shirts was treated with a standard detergent (no calcium carbonate, No. 1 in Table 1), and the other was treated with a test sample (calcium carbonate, No. 1 in Table 1). After washing for 10 minutes at a detergent concentration of 0.15%, a liquid temperature of 25℃, and a washing ratio of 30 times, rinse twice for 3 minutes each. After washing, the left and right sides of each pair of sample cloths after washing were compared and judged with the naked eye, and the value obtained by dividing the rating of each sample detergent by the rating of the cleaning power of the standard detergent and multiplying the result by 100 was used as the detergency index. Comparative Example Sample No. 9,
Ten sample detergents were prepared and the evaluation results are shown in Table 2.
【表】【table】
【表】【table】
Claims (1)
ルカリ金属珪酸塩と、アルカリ金属炭酸塩とを含
有する粒状洗剤の粒子表面に、一次粒子径が0.1
〜1.5μmであり、粒子の最小径／最大径比が0.3〜
0.7のサイコロ状の微細沈降炭酸カルシウムを、
該粒状洗剤100重量部当り0.5〜３重量部付着せし
めることを特徴とする粒状洗剤の製造方法。1 A particle surface of a granular detergent containing at least one anionic surfactant, an alkali metal silicate, and an alkali metal carbonate has a primary particle size of 0.1
~1.5μm, and the particle minimum diameter/maximum diameter ratio is ~0.3
0.7 dice-shaped fine precipitated calcium carbonate,
A method for producing a granular detergent, which comprises depositing 0.5 to 3 parts by weight per 100 parts by weight of the granular detergent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11834684A JPS60262895A (en) | 1984-06-11 | 1984-06-11 | Manufacture of granular detergent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11834684A JPS60262895A (en) | 1984-06-11 | 1984-06-11 | Manufacture of granular detergent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60262895A JPS60262895A (en) | 1985-12-26 |
| JPH0550558B2 true JPH0550558B2 (en) | 1993-07-29 |
Family
ID=14734416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11834684A Granted JPS60262895A (en) | 1984-06-11 | 1984-06-11 | Manufacture of granular detergent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60262895A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8904750D0 (en) * | 1989-03-02 | 1989-04-12 | Unilever Plc | Agglomerates for addition to detergent powders |
| JP6774798B2 (en) * | 2016-06-30 | 2020-10-28 | ライオン株式会社 | Coated α-sulfofatty acid alkyl ester salt particles |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5152404A (en) * | 1974-09-06 | 1976-05-10 | Unilever Nv | Senzaisoseibutsunoseizoho |
| JPS53114807A (en) * | 1977-03-18 | 1978-10-06 | Lion Corp | Modification of ranulated detergent |
-
1984
- 1984-06-11 JP JP11834684A patent/JPS60262895A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5152404A (en) * | 1974-09-06 | 1976-05-10 | Unilever Nv | Senzaisoseibutsunoseizoho |
| JPS53114807A (en) * | 1977-03-18 | 1978-10-06 | Lion Corp | Modification of ranulated detergent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60262895A (en) | 1985-12-26 |
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