JPH02279519A - Production of titanium hydroxide fine powder - Google Patents
Production of titanium hydroxide fine powderInfo
- Publication number
- JPH02279519A JPH02279519A JP9774589A JP9774589A JPH02279519A JP H02279519 A JPH02279519 A JP H02279519A JP 9774589 A JP9774589 A JP 9774589A JP 9774589 A JP9774589 A JP 9774589A JP H02279519 A JPH02279519 A JP H02279519A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- titanium
- powder
- hydrolysis
- added
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 50
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000010419 fine particle Substances 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- -1 titanium alkoxide Chemical class 0.000 claims abstract description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 29
- 230000007062 hydrolysis Effects 0.000 abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 230000002209 hydrophobic effect Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 10
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 9
- 239000002537 cosmetic Substances 0.000 abstract description 3
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 3
- 229910052710 silicon Inorganic materials 0.000 abstract 3
- 239000010703 silicon Substances 0.000 abstract 3
- 230000016615 flocculation Effects 0.000 abstract 1
- 238000005189 flocculation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 239000000725 suspension Substances 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- 238000007865 diluting Methods 0.000 description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 150000004703 alkoxides Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CRFYEYAWEXPLTQ-UHFFFAOYSA-N C1(=CC=CC=C1)[Si](O[SiH2]O[Si](O[Si](C)(C)C)(C1=CC=CC=C1)C1=CC=CC=C1)(O[Si](C)(C)C)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)[Si](O[SiH2]O[Si](O[Si](C)(C)C)(C1=CC=CC=C1)C1=CC=CC=C1)(O[Si](C)(C)C)C1=CC=CC=C1 CRFYEYAWEXPLTQ-UHFFFAOYSA-N 0.000 description 1
- RASBDVLERRNNLJ-UHFFFAOYSA-N CCCCO[Ti] Chemical compound CCCCO[Ti] RASBDVLERRNNLJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YFCGDEUVHLPRCZ-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C YFCGDEUVHLPRCZ-UHFFFAOYSA-N 0.000 description 1
- XUGLYDDHAAAAMN-UHFFFAOYSA-N [diphenyl(trimethylsilyloxy)silyl]oxy-diphenyl-trimethylsilyloxysilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O[Si](C)(C)C)O[Si](O[Si](C)(C)C)(C=1C=CC=CC=1)C1=CC=CC=C1 XUGLYDDHAAAAMN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MPCPCZLNXMVLNN-UHFFFAOYSA-N bis[[dimethyl(triphenylsilyloxy)silyl]oxy]-dimethylsilane Chemical compound C[Si](O[Si](O[Si](O[Si](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)(C)C)(C)C)(O[Si](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C MPCPCZLNXMVLNN-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- QBNMGMSLXRJOOX-UHFFFAOYSA-N diphenyl-bis(trimethylsilyloxy)silane Chemical compound C=1C=CC=CC=1[Si](O[Si](C)(C)C)(O[Si](C)(C)C)C1=CC=CC=C1 QBNMGMSLXRJOOX-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KQJBQMSCFSJABN-UHFFFAOYSA-N octadecan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-] KQJBQMSCFSJABN-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、紫外線散乱効果、特に２８０〜３２０ｎｍの
ＵＶ−８波長領域における散乱効果が大きく、疎水性で
透明性を有する安定な微粒子水酸化チタン粉末の製造法
に関する。Detailed Description of the Invention <Industrial Application Field> The present invention provides stable fine particle hydroxylation that has a large ultraviolet scattering effect, particularly in the UV-8 wavelength region of 280 to 320 nm, and is hydrophobic and transparent. This invention relates to a method for producing titanium powder.
〈従来の技術〉
微粒子粉末の製造法には、（１）物理的粉砕、例えば機
械的粉砕、超音波法、（２）液相法、例えば沈殿・析出
法、アルコキシド法、水熱合成法、凍結乾燥法、（３）
気相法、例えば蒸発凝縮法、気相合成法、熱分解法があ
る。これらの製造法のうち、アルコキシド法は、出発原
料として金属アルコキシドを用い、加水分解させ、酸化
物、水酸化物、あるいは水和物の沈殿を得、これを仮焼
して粉末を得る方法である。金属アルコキシドの加水分
解で生成する酸化物粒子は、反応溶媒にほとんど溶解し
ないので、合成された後の熟成による粒子の成長はない
ため、合成される粒子の太きざは、加水分解時により決
定されると考えられている。このため、この方法の特徴
は、１）出発原料の純度が高ければ高いほど、高純度の
粉末が得られる。２）比較的低温で加水分解するため、
温度の制御がしやすい。３）反応温度やｐＨ１水／アル
コキシド比、溶媒を変えることにより加水分解条件を制
御できる。４）加水分解法により直接１０〜１１００ｎ
程度の１次粒子の酸化物が得られることである。このた
め、近年、セラミックスの製造に関する研究が盛んに行
われ、その応用例も数多くある。<Prior art> Methods for producing fine powder particles include (1) physical pulverization, such as mechanical pulverization, ultrasonic method, (2) liquid phase method, such as precipitation/precipitation method, alkoxide method, hydrothermal synthesis method, Freeze-drying method, (3)
There are gas phase methods such as evaporation condensation method, gas phase synthesis method, and thermal decomposition method. Among these manufacturing methods, the alkoxide method uses a metal alkoxide as a starting material, hydrolyzes it to obtain a precipitate of oxide, hydroxide, or hydrate, and calcinates this to obtain a powder. be. Oxide particles produced by hydrolysis of metal alkoxides are hardly soluble in the reaction solvent, so there is no growth of the particles due to aging after synthesis, so the size of the synthesized particles is determined by the time of hydrolysis. It is believed that Therefore, the characteristics of this method are as follows: 1) The higher the purity of the starting material, the more pure powder can be obtained. 2) Because it hydrolyzes at relatively low temperatures,
Easy to control temperature. 3) Hydrolysis conditions can be controlled by changing the reaction temperature, pH 1 water/alkoxide ratio, and solvent. 4) 10-1100n directly by hydrolysis method
It is possible to obtain primary particle oxides of about 100%. For this reason, research on the production of ceramics has been actively conducted in recent years, and there are many examples of its applications.
〈発明が解決しようとする課題〉
従来技術の問題点
しかしながら、従来の金属アルコキシドを出発・原料と
した微粒子の製造法では、溶液内では微粒子が生成する
ものの、溶媒を除く段階で粒子が凝集し、ｌｏｏｎｍ以
下のような微粒子の粉末を得ることは難しいという欠点
を有している。このため、紫外線散乱効果を有した粉末
を製造する場合、希望する紫外線散乱効果が得られない
。特に、化粧品等に配合する場合、皮膚に有害とされる
２８０〜３２０ｎｍのＵＶ−Ｂ波長領域における紫外線
散乱効果が十分ではなくなる。<Problems to be Solved by the Invention> Problems with the Prior Art However, in the conventional method for producing fine particles using metal alkoxide as a starting material, fine particles are formed in a solution, but the particles aggregate when the solvent is removed. It has the disadvantage that it is difficult to obtain powder with fine particles smaller than . Therefore, when producing a powder having an ultraviolet scattering effect, the desired ultraviolet scattering effect cannot be obtained. In particular, when incorporated into cosmetics, etc., the ultraviolet scattering effect in the UV-B wavelength region of 280 to 320 nm, which is considered harmful to the skin, will not be sufficient.
発明の目的
本発明は、隠蔽力が弱い、すなわち透明性があり、疎水
性を有し、紫外線散乱効果、特にＵＶ−８波長領域にお
ける散乱効果の大きい凝集することのない安定な微粒子
水酸化チタン粉末を提供することを目的としている。Purpose of the Invention The present invention provides stable fine particle titanium hydroxide that does not agglomerate and has a weak hiding power, that is, is transparent, hydrophobic, and has a large ultraviolet scattering effect, particularly in the UV-8 wavelength region. The purpose is to provide powder.
本発明者らは、前記目的を達成すべく鋭意研究した結果
、チタンアルコキシドの加水分解前後においてシリコー
ンを加えることにより合成した水酸化チタンが、凝集す
ることなく安定で、透明性かあり、疎水性を有し、皮膚
に有害であるとされる２ ８０〜３２０ ｎ ｍのＵＶ
−Ｂ波長領域における紫外線散乱効果の大きいことを見
出し、本発明を完成した。As a result of intensive research to achieve the above object, the present inventors found that titanium hydroxide, which was synthesized by adding silicone before and after hydrolysis of titanium alkoxide, was stable without agglomeration, transparent, and hydrophobic. UV radiation between 280 and 320 nm, which is said to be harmful to the skin.
They discovered that the ultraviolet scattering effect is large in the -B wavelength region, and completed the present invention.
く課題を解決するための手段〉
すなわち、本発明は、チタンアルコキシドを加水分解し
て水酸化チタンを製造する際に、下記−般式（Ｉ）及び
（１１）
［（ＣＲ３）２Ｓ ｉ Ｏ］ ｎ
（式中、ｎは３〜７の整数である）・ （１）ＣＨ
３［Ｒ２５ｉＯ］ｎ５ｉ（ＣＨ３）３（式中、ｎは１〜
４の整数、Ｒはメチル基、フェニル基を表わす）
・ （１１）で表わされるシリコーン
から選ばれる１種または２種以上を加えることを特徴と
する微粒子水酸化チタン粉末の製造法に関するものであ
る。Means for Solving the Problems> That is, the present invention provides the following - general formulas (I) and (11) [(CR3)2S i O] when producing titanium hydroxide by hydrolyzing titanium alkoxide. n (in the formula, n is an integer from 3 to 7) (1) CH
3[R25iO]n5i(CH3)3 (where n is 1-
An integer of 4, R represents a methyl group or a phenyl group)
- This relates to a method for producing fine particle titanium hydroxide powder, characterized in that one or more silicones selected from the silicones represented by (11) are added.
以下、本発明について詳述する。The present invention will be explained in detail below.
本発明に使用するチタンアルコキシドは、水酸化チタン
の製造に一般に用いられるものでよく、たとえば、テト
ラメトキシチタン、テトラエトキシチタン、テトラ−１
−プロポキシチタン、テトラ−ｎ−プロポキシチタン、
テトラ−ｎ−ブトキシチタン、テトラ−１−ブトキシチ
タン、テトラ−５ｅｅ−ブトキシチタン、テトラ−ｔ−
ブトキシチタン、テトラ−オクタデシロキシチタンなど
があげられる。The titanium alkoxide used in the present invention may be one commonly used in the production of titanium hydroxide, such as tetramethoxytitanium, tetraethoxytitanium, tetra-1
-propoxytitanium, tetra-n-propoxytitanium,
Tetra-n-butoxytitanium, tetra-1-butoxytitanium, tetra-5ee-butoxytitanium, tetra-t-
Examples include butoxytitanium, tetra-octadecyloxytitanium, and the like.
本発明に使用するシリコーンは、下記一般式％式％）
（式中、ｎは３〜７の整数である） ・ （Ｉ）Ｃ
Ｈ３［Ｒ２５ｉＯ］ｎ５ｉ（ＣＨ３）３（式中、ｎは１
〜４の整数、Ｒはメチル基、フェニル基を表わす）
・ （ＩＩ ）であり、例えば、ヘキ
サメチルシクロトリシロキサン、オクタメチルシクロテ
トラシロキサン、デカメチルシクロペンタシロキサン、
ヘキサメチルジシロキサン、オクタメチルトリシロキサ
ン、デカメチルテトラシロキサン、トチ゛カメチルペン
タシロキサン、ヘキサメチルジフェニルトリシロキサン
、ヘキサメチルテトラフェニルテトラシロキサン、ヘキ
サメチルへキサフェニルペンタシロキサンなどがあげら
れる。これらのシリコーンは、１種または２種以上が用
いられる。The silicone used in the present invention has the following general formula % (in the formula, n is an integer from 3 to 7) (I)C
H3[R25iO]n5i(CH3)3 (where n is 1
An integer of ~4, R represents a methyl group or a phenyl group)
- (II), such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
Examples include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, acamethylpentasiloxane, hexamethyldiphenyltrisiloxane, hexamethyltetraphenyltetrasiloxane, and hexamethylhexaphenylpentasiloxane. One or more types of these silicones may be used.
チタンアルコキシドとシリコーンの量的関係については
、チタンアルコキシド１００重量部（以下部と略す）に
対してシリコーン５〜５００部であり、好ましくは、１
０〜３００部である。Regarding the quantitative relationship between titanium alkoxide and silicone, it is 5 to 500 parts of silicone per 100 parts by weight of titanium alkoxide (hereinafter referred to as "parts"), preferably 1 part by weight.
It is 0 to 300 parts.
本発明に係る製法は、具体的に次のような態様をとる。The manufacturing method according to the present invention specifically takes the following aspects.
［加水分解工程］→［濃縮工程］→Ｅ乾燥工程］この製
法について、各工程毎に説明する。[Hydrolysis step] → [Concentration step] → E-drying step] This manufacturing method will be explained for each step.
［加水分解工程１は、チタンアルコキシドを加水分解す
る工程である。この加水分解は、室温（２０ｆＩＯ’Ｃ
）！たは加熱温度（３０〜１３０℃）にて行われる。[Hydrolysis step 1 is a step of hydrolyzing titanium alkoxide. This hydrolysis is carried out at room temperature (20 fIO'C
)! or at a heating temperature (30 to 130°C).
通常の方法では、チタンアルコキシドおよび水を溶媒で
希釈した状態で加水分解することにより、水酸化チタン
の！！濁液を得、この後０．５〜２４時間還流するかま
たは還流せずにこのまま濃縮、乾燥すると、粒径が１μ
ｍ前後の凝集粉末となり、サブミクロン以下の微粒子粉
末は得られない。そこで、加水分解前または加水分解時
または加水分解終了後においてシリコーンを添加すると
、その後の濃縮、乾燥工程を経ても粒子の凝集を防ぐこ
とができ、サブミクロン以下の微粒子の粉末を得ること
ができる。この作用については、まだ不明な点が多いが
、加水分解時の過剰な水および加水分解反応により生成
した水とシリコーンの表面張力や蒸発潜熱、沸点等の違
いにより、本発明の効力を引き出しているものと考えら
れる。In the usual method, titanium hydroxide is produced by hydrolyzing titanium alkoxide and water diluted with a solvent. ! A cloudy liquid is obtained, which is then refluxed for 0.5 to 24 hours or concentrated and dried without refluxing, resulting in a particle size of 1μ.
The result is an agglomerated powder of around m, and fine powder of submicron size or less cannot be obtained. Therefore, by adding silicone before, during, or after hydrolysis, it is possible to prevent particle agglomeration even during the subsequent concentration and drying steps, making it possible to obtain powder with submicron or smaller particles. . Although there are still many unknowns regarding this effect, the effectiveness of the present invention may be brought out due to the differences in surface tension, latent heat of vaporization, boiling point, etc. between the excess water during hydrolysis and the water generated by the hydrolysis reaction and silicone. It is thought that there are.
［濃縮工程］は、加水分解工程で得られた懸濁液から余
分の水、シリコーンおよび希釈に用いたアルコールを取
り除き、次の乾燥工程の効率を上げるための工程である
。濃縮方法としては、減圧乾燥、吸引濾過、加圧濾過、
振動乾燥、スプレードライ、凍結乾燥等の方法があり、
製造するロットの大きさ、シリコーンの種類により、適
亘選択して用いる。[Concentration step] is a step for removing excess water, silicone, and alcohol used for dilution from the suspension obtained in the hydrolysis step to increase the efficiency of the next drying step. Concentration methods include vacuum drying, suction filtration, pressure filtration,
There are methods such as vibration drying, spray drying, and freeze drying.
The suitable material is selected and used depending on the size of the lot to be manufactured and the type of silicone.
［乾燥工程］は、［濃縮工程］において残留した水、ア
ルコールを完全に取り除くため、６０〜２００℃の温度
範囲で乾燥きせる工程である。乾燥温度は、製造に用い
たアルコールおよびシリコーンにより適宜選択する。[Drying step] is a step of drying at a temperature range of 60 to 200° C. in order to completely remove water and alcohol remaining in the [concentration step]. The drying temperature is appropriately selected depending on the alcohol and silicone used in the production.
このようにして得られた粉末は、公知の粉砕方法により
粉砕される。The powder thus obtained is pulverized by a known pulverization method.
加水分解時におけるチタンアルコキシドと水との量的関
係については、極めて広範囲に選択できるが、通常チタ
ンアルコキシド１００部に対して水１０〜１５０部であ
り、好ましくは４０〜８０部である。The quantitative relationship between titanium alkoxide and water during hydrolysis can be selected within a very wide range, but it is usually 10 to 150 parts of water, preferably 40 to 80 parts, per 100 parts of titanium alkoxide.
加水分解時におけるチタンアルコキシドと水は、このま
ま使用してもよいか、通常、溶媒により希釈して用いる
。Titanium alkoxide and water during hydrolysis may be used as they are, or they are usually diluted with a solvent.
Ｏ本発明に使用する希釈溶媒は、メタノール、エタノー
ル、ｎ−プロパツール、ｉ−プロパツール、ｎ−ブタノ
ール、ｉ−ブタノール、５ｅｃ−ブタノール、ｔ−ブタ
ノールなどのアルコール類である。The diluting solvent used in the present invention is alcohol such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, 5ec-butanol, t-butanol, and the like.
［実施例１
次に比較例と実施例を挙げて本発明をざらに詳細に説明
するが、本発明はこれら実施例にのみ限定されるもので
はない。なお、比較例および実施例中に、親水性と疎水
性とあるが、これは、粉末と水を接触させ、その時の水
の弾き具合で判断したものである。[Example 1] Next, the present invention will be explained in detail with reference to comparative examples and examples, but the present invention is not limited only to these examples. In the Comparative Examples and Examples, hydrophilicity and hydrophobicity are referred to as hydrophilicity and hydrophobicity, but this is determined by bringing the powder into contact with water and determining how water is repelled at that time.
比較例
テトラ−１−プロポキシチタン１００部をｉ −プロパ
ツール５００部で希釈した溶液を攪拌しながら、水５０
部をｉ−プロパツール５００部で希釈した溶液を加えて
２５℃で加水分解を行った。Comparative Example A solution prepared by diluting 100 parts of tetra-1-propoxy titanium with 500 parts of i-propanol was mixed with 50 parts of water while stirring.
A solution prepared by diluting 1 part with 500 parts of i-propatool was added to carry out hydrolysis at 25°C.
この懸濁液を吸引濾過の手段を用いて濃縮した後、１１
０℃にて乾燥し、３４．５部の粉末を得た。After concentrating this suspension using means of suction filtration, 11
It was dried at 0°C to obtain 34.5 parts of powder.
この粉末は、親水性を示した。This powder exhibited hydrophilic properties.
実施例１
テトラ−ｉ−プロポキシチタン１００部をｉ−プロパツ
ール５００部で希釈した溶液にオクタメチルシクロテト
ラシロキサン１００部を加え、攪拌しながら水５０部を
ｉ−プロパツール５００部で希釈した溶液を加えて２５
℃で加水分解を行った。この懸濁液を吸引濾過の手段を
用いて濃縮した後、１３０℃にて乾燥し、４０部の安定
な微粒子粉末を得た。この粉末は、疎水性を示した。Example 1 100 parts of octamethylcyclotetrasiloxane was added to a solution of 100 parts of tetra-i-propoxytitanium diluted with 500 parts of i-propanol, and while stirring, a solution was prepared by diluting 50 parts of water with 500 parts of i-propanol. Add 25
Hydrolysis was carried out at °C. This suspension was concentrated using suction filtration and then dried at 130°C to obtain 40 parts of stable fine particle powder. This powder exhibited hydrophobic properties.
実施例２
オクタメチルシクロテトラシロキシチタンの添加量を５
部とし、他は実施例１と同様にして３３部の安定な微粒
子粉末を得た。この粉末は、疎水性を示した。Example 2 The amount of octamethylcyclotetrasiloxytitanium added was 5
33 parts of stable fine particle powder was obtained in the same manner as in Example 1 except that 33 parts of stable fine powder were obtained. This powder exhibited hydrophobic properties.
実施例３
オクタメチルシクロテトラシロキシチタンの添加量を５
００部とし、他は実施例１と同様にして４０部の安定な
微粒子粉末を得た。この粉末は、疎水性を示した。Example 3 The amount of octamethylcyclotetrasiloxytitanium added was 5
00 parts, and in the same manner as in Example 1 except that 40 parts of stable fine particle powder was obtained. This powder exhibited hydrophobic properties.
実施例４
テトラメトキシチタン１００部をｉ−プロパツール５０
０部で希釈した溶液にデカメチルシクロペンタシロキサ
ン１００部を加え、攪拌しながら水５０部をｉ−プロパ
ツール５００部で希釈した溶液を加えて２５℃で加水分
解を行った。この懸濁液を吸引濾過の手段を用いて濃縮
した後、１５０℃にて乾燥し、４０部の安定な微粒子粉
末を得た。Example 4 100 parts of tetramethoxy titanium was added to 50 parts of i-propatool.
100 parts of decamethylcyclopentasiloxane was added to the solution diluted with 0 parts, and while stirring, a solution prepared by diluting 50 parts of water with 500 parts of i-propatool was added to perform hydrolysis at 25°C. This suspension was concentrated using suction filtration and then dried at 150°C to obtain 40 parts of stable fine particle powder.
この粉末は、疎水性を示した。This powder exhibited hydrophobic properties.
実施例５
テトラエトキシチタン１００部をｉ−プロパツール５０
０部で希釈した溶液にヘキサメチルジシロキサン１００
部を加え、攪拌しながら水５０部をｉ−プロパツール５
００部で希釈した溶液を加えて２５℃で加水分解を行っ
た。この懸濁液を吸引濾過の手段を用いて濃縮した後、
１２０℃にて乾燥し、３５部の安定な微粒子粉末を得た
。この粉末は、疎水性を示した。Example 5 100 parts of tetraethoxy titanium was added to 50 parts of i-propatool.
100 parts of hexamethyldisiloxane in a solution diluted with 0 parts
50 parts of water with stirring.
A solution diluted with 0.00 parts was added and hydrolysis was carried out at 25°C. After concentrating this suspension using means of suction filtration,
It was dried at 120°C to obtain 35 parts of stable fine powder. This powder exhibited hydrophobic properties.
実施例６
テトラ−ｎ−プロポキシチタン１００部をｉ −プロパ
ツール５００部で希釈した溶液にオクタメチルトリシロ
キサン１００部を加え、攪拌しながら水５０部をｉ−プ
ロパツール５００部で希釈した溶液を加えて２５℃で加
水分解を行った。この懸濁液を吸引濾過の手段を用いて
濃縮した後、１３０℃にて乾燥し、３７部の安定な微粒
子粉末を得た。この粉末は、疎水性を示した。Example 6 100 parts of octamethyltrisiloxane was added to a solution of 100 parts of tetra-n-propoxytitanium diluted with 500 parts of i-propanol, and while stirring, a solution of 50 parts of water diluted with 500 parts of i-propanol was added. In addition, hydrolysis was performed at 25°C. This suspension was concentrated using suction filtration and then dried at 130°C to obtain 37 parts of stable fine powder. This powder exhibited hydrophobic properties.
実施例７
テトラ−ｎ−ブトキシチタン１００部をｉ−プロパツー
ル５００部で希釈した溶液にヘキサメチルテトラフェニ
ルペンタシロキサン１００部を加え、攪拌しながら水５
０部をｉ−プロパツール５００部で希釈した溶液を加え
て２５℃で加水分解を行った。この懸濁液を吸引濾過の
手段を用いて濃縮した後、１３０℃にて乾燥し、４０部
の安定な微粒子粉末を得た。この粉末は、疎水性を示し
た。Example 7 100 parts of hexamethyltetraphenylpentasiloxane was added to a solution of 100 parts of tetra-n-butoxytitanium diluted with 500 parts of i-propatool, and 5 parts of water was added with stirring.
A solution prepared by diluting 0 parts with 500 parts of i-propatool was added to perform hydrolysis at 25°C. This suspension was concentrated using suction filtration and then dried at 130°C to obtain 40 parts of stable fine particle powder. This powder exhibited hydrophobic properties.
実施例８
テトラ−１−ブトキシチタン１００部をｉ−プロパツー
ル５００部で希釈した溶液にオクタメチルシクロテトラ
シロキサン５０部およびオクタメチルトリシロキサン５
０部を加え、攪拌しながら水５・０部をｉ−プロパツー
ル５００部で希釈した溶液を加えて２５℃で加水分解を
行った。この懸濁液を吸引濾過の手段を用いて濃縮した
後、１３０℃にて乾燥し、３７部の安定な微粒子粉末を
得た。この粉末は、疎水性を示した。Example 8 50 parts of octamethylcyclotetrasiloxane and 5 parts of octamethyltrisiloxane were added to a solution of 100 parts of tetra-1-butoxytitanium diluted with 500 parts of i-propanol.
0 parts were added thereto, and while stirring, a solution prepared by diluting 5.0 parts of water with 500 parts of i-propatool was added to carry out hydrolysis at 25°C. This suspension was concentrated using suction filtration and then dried at 130°C to obtain 37 parts of stable fine powder. This powder exhibited hydrophobic properties.
実施例９
テトラ−５ｅｃ−ブトキシチタン１００部をｉ−プロパ
ツール５００部で希釈した溶液にヘキサメチルジシロキ
サン５０部およびオクタメチルトリシロキサン５０部を
加え、攪拌しながら水５０部をｉ−プロパツール５００
部で希釈した溶液を加えて２５℃で加水分解を行った。Example 9 50 parts of hexamethyldisiloxane and 50 parts of octamethyltrisiloxane were added to a solution of 100 parts of tetra-5ec-butoxytitanium diluted with 500 parts of i-propanol, and while stirring, 50 parts of water was added with i-propanol. 500
A diluted solution was added to carry out hydrolysis at 25°C.
この懸濁液を吸引濾過の手段を用いて濃縮した後、１３
０℃にて乾燥し、４０部の安定な微粒子粉末を得た。こ
の粉末は、疎水性を示した。After concentrating this suspension using means of suction filtration, 13
It was dried at 0°C to obtain 40 parts of stable fine particle powder. This powder exhibited hydrophobic properties.
実施例１０
水５０部をｉ−プロパツール５００部で希釈した溶液に
、オクタメチルシクロテトラシロキサン１００部を加え
攪拌し、この溶液をチタンイソプロポキシド１００部を
ｉ−プロパツール５００部で希釈した溶液に加えて、２
５℃で加水分解を行った。この懸濁液を吸引濾過の手゛
段を用いて濃縮した後、１３０℃にて乾燥し、４０部の
安定な微粒子粉末を得た。この粉末は、疎水性を示した
。Example 10 100 parts of octamethylcyclotetrasiloxane was added to a solution of 50 parts of water diluted with 500 parts of i-propanol and stirred, and this solution was diluted with 100 parts of titanium isopropoxide and 500 parts of i-propanol. In addition to the solution, 2
Hydrolysis was carried out at 5°C. This suspension was concentrated using suction filtration and then dried at 130°C to obtain 40 parts of stable fine powder. This powder exhibited hydrophobic properties.
実施例１１
チタンイソプロポキシド１００部をｉ−プロパツール５
００部で希釈した溶液に、攪拌しながら水５０部をｉ−
プロパツール５００部で希釈した溶液を加えて２５℃で
加水分解を行った。この懸濁液にオクタメチルシクロテ
トラシロキサン１００部を加え攪拌した。この懸濁液を
吸引濾過の手段を用いて濃縮した後、１３０℃で乾燥し
、４０部の安定な微粒子粉末を得た。この粉末は、疎水
性を示した。Example 11 100 parts of titanium isopropoxide was added to i-propatool 5
Add 50 parts of water to the solution diluted with 0.00 parts while stirring.
A solution diluted with 500 parts of propatool was added to carry out hydrolysis at 25°C. 100 parts of octamethylcyclotetrasiloxane was added to this suspension and stirred. This suspension was concentrated using suction filtration and then dried at 130°C to obtain 40 parts of stable fine particle powder. This powder exhibited hydrophobic properties.
実施例１２
テトラ−ｔ−ブトキシチタン１００部をｉ−プロパツー
ル５００部で希釈した溶液にオクタメチルシクロテトラ
シロキサン１００部を加え攪拌しながら水５０部をｉ−
プロパツール５００部で希釈した溶液を加えて２５℃で
加水分解を行い、この後９０℃で１０時間還流した。こ
の懸濁液を吸引濾過の手段を用いて濃縮した後、１３０
℃にて乾燥し、４０部の安定な微粒子粉末を得た。この
粉末は、疎水性を示した。Example 12 100 parts of octamethylcyclotetrasiloxane was added to a solution of 100 parts of tetra-t-butoxytitanium diluted with 500 parts of i-propanol, and while stirring, 50 parts of water was added to the i-propanol solution.
A solution diluted with 500 parts of propatool was added to carry out hydrolysis at 25°C, followed by refluxing at 90°C for 10 hours. After concentrating this suspension using means of suction filtration,
It was dried at ℃ to obtain 40 parts of stable fine particle powder. This powder exhibited hydrophobic properties.
実施例１３
テトラオクタデシロキシチタン１００部をｉ −プロパ
ツール５００部で希釈した溶液にオクタメチルシクロテ
トラシロキサン１００部を加え５０℃に加温した。この
溶液を水５０部をｉ−プロパツール５００部で希釈した
溶液に攪拌しながら加えて５０℃で加水分解を行った。Example 13 100 parts of octamethylcyclotetrasiloxane was added to a solution prepared by diluting 100 parts of tetraoctadecyloxytitanium with 500 parts of i-propanol, and the mixture was heated to 50°C. This solution was added to a solution prepared by diluting 50 parts of water with 500 parts of i-propertool while stirring, and hydrolysis was carried out at 50°C.
この懸濁液を吸引濾過の手段を用いて濃縮した後、１３
０℃で乾燥し、４０部の安定な微粒子粉末を得た。この
粉末は、疎水性を示した。After concentrating this suspension using means of suction filtration, 13
It was dried at 0°C to obtain 40 parts of stable fine powder. This powder exhibited hydrophobic properties.
比較例および実施例１〜１３で得られた粉末および市販
品について、紫外部（３００部ｍ）の吸光度、可視部（
４２０，５５０部ｍ）の反射率を表に示す。紫外部の吸
光度は、粉末１重量％をヒマシ油に分散させ、石英板上
に５μｍの厚きで塗布し、分光光度計にて測定した。可
視部の反射率は、粉末１０重量％をヒマシ油に分散させ
、黒色の隠蔽率試験紙に０．１．０１ｍｍの厚ざで塗布
し、測色計にて測定した。Regarding the powders and commercial products obtained in Comparative Examples and Examples 1 to 13, the absorbance in the ultraviolet region (300 parts m) and the visible region (
The reflectance of 420,550 parts m) is shown in the table. The absorbance in the ultraviolet region was measured by dispersing 1% by weight of the powder in castor oil, coating it on a quartz plate to a thickness of 5 μm, and using a spectrophotometer. The reflectance in the visible region was measured by dispersing 10% by weight of the powder in castor oil, applying it to a black hiding rate test paper in a thickness of 0.1.01 mm, and using a colorimeter.
（以下余白）
〈発明の効果〉
本発明に従えば、紫外線散乱効果が大きく、疎水性で透
明性があり、凝集することのない安定な微粒子水酸化チ
タン粉末を製造することができ、この発明で得られた粉
末は、化粧品をはじめとして紫外線を防御する必要のあ
る用具などに有効である。(The following is a blank space) <Effects of the Invention> According to the present invention, it is possible to produce a stable fine particle titanium hydroxide powder that has a large ultraviolet scattering effect, is hydrophobic, transparent, and does not agglomerate. The powder obtained is useful in cosmetics and other products that require protection from ultraviolet rays.
特許出願人 株式会社 資生堂 手続補正書（自発） １．事件の表示 平成１年特許願第９７７４５号 ２゜ 発明の名称 微粒子水酸化チタン粉末の製造法 ３、補正をする者 事件との関係 特許出願人 住所 東京都中央区銀座７丁目５番５号４゜ ネ＋ｔｌ正の対象 明細書の１発明の詳細な説明、の欄 ５、補正の内容 明細書の発明の詳細な説明を下記の通り補正します。Patent applicant: Shiseido Co., Ltd. Procedural amendment (voluntary) 1. Display of incidents 1999 Patent Application No. 97745 2゜ name of invention Manufacturing method of fine particle titanium hydroxide powder 3. Person who makes corrections Relationship to the incident: Patent applicant Address: 7-5-5-4 Ginza, Chuo-ku, Tokyo ne + tl positive object 1. Detailed explanation of the invention in the specification 5. Contents of correction The detailed description of the invention in the specification is amended as follows.
（１）明細書第７頁第１９〜２０行目の１アルコール」
を「溶媒」に訂正します。(1) 1 alcohol on page 7, lines 19-20 of the specification.”
Correct it to "solvent".
（２）明細書第８頁第９行目の １アルコール」を「溶媒」に訂正します。(2) Page 8, line 9 of the specification 1 Correct "alcohol" to "solvent".
（３）明細書第１０頁第１２行目の
「オクタメチルシクロテトラシロキシチタン」を「オク
タメチルシクロテトラシロキサン」に訂正します。(3) "Octamethylcyclotetrasiloxytitanium" on page 10, line 12 of the specification will be corrected to "octamethylcyclotetrasiloxane."
（４）明細書第１０頁第１７行目の
「オクタメチルシクロテトラシロキシチタン」を「オク
タメチルシクロテトラシロキサン」に訂正します。(4) "Octamethylcyclotetrasiloxytitanium" on page 10, line 17 of the specification will be corrected to "octamethylcyclotetrasiloxane."
（５）明細書第１４頁第４〜５行目の １チタンイソプロポキシド」を １テトラ−１−プロポキシチタン」に訂正します。(5) Lines 4-5 of page 14 of the specification 1 titanium isopropoxide” 1 tetra-1-propoxy titanium”.
（６）明細書第１４頁第１１行目の １チタンイソプロポキシド」を ｒテトラ−１−プロポキシチタン」に訂正します。(6) Page 14, line 11 of the specification 1 titanium isopropoxide” rTetra-1-propoxytitanium".
以上that's all
Claims (1)
を製造する際に、下記一般式（ I ）及び（II） ［（ＣＨ＿３）＿２ＳｉＯ］ｎ （式中、ｎは３〜７の整数である）・・・（ I ）ＣＨ
＿３［Ｒ＿２ＳｉＯ］ｎＳｉ（ＣＨ＿３）＿３（式中、
ｎは１〜４の整数、Ｒはメチル基、フェニル基を表わす
）・・・（II） で表わされるシリコーンから選ばれる１種または２種以
上を加えることを特徴とする微粒子水酸化チタン粉末の
製造法。(1) When producing titanium hydroxide by hydrolyzing titanium alkoxide, the following general formulas (I) and (II) [(CH_3)_2SiO]n (wherein n is an integer from 3 to 7) ...(I)CH
_3[R_2SiO]nSi(CH_3)_3 (in the formula,
n is an integer of 1 to 4, R is a methyl group or a phenyl group)... (II) A fine particle titanium hydroxide powder characterized by adding one or more silicones selected from the following: Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1097745A JP2855442B2 (en) | 1989-04-18 | 1989-04-18 | Manufacturing method of fine particle titanium hydroxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1097745A JP2855442B2 (en) | 1989-04-18 | 1989-04-18 | Manufacturing method of fine particle titanium hydroxide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02279519A true JPH02279519A (en) | 1990-11-15 |
| JP2855442B2 JP2855442B2 (en) | 1999-02-10 |
Family
ID=14200425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1097745A Expired - Fee Related JP2855442B2 (en) | 1989-04-18 | 1989-04-18 | Manufacturing method of fine particle titanium hydroxide powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2855442B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182204A (en) * | 1987-01-22 | 1988-07-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of monodisperse body of fine inorganic oxide particle in organic solvent |
-
1989
- 1989-04-18 JP JP1097745A patent/JP2855442B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182204A (en) * | 1987-01-22 | 1988-07-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of monodisperse body of fine inorganic oxide particle in organic solvent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2855442B2 (en) | 1999-02-10 |
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| LAPS | Cancellation because of no payment of annual fees |