CN108602957A - The manufacturing method of spherical polymethyl-benzene base silsesquioxane particle - Google Patents
The manufacturing method of spherical polymethyl-benzene base silsesquioxane particle Download PDFInfo
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- CN108602957A CN108602957A CN201780009073.9A CN201780009073A CN108602957A CN 108602957 A CN108602957 A CN 108602957A CN 201780009073 A CN201780009073 A CN 201780009073A CN 108602957 A CN108602957 A CN 108602957A
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- aqueous solution
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- methyltrimethoxysilane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/32—Post-polymerisation treatment
Abstract
The manufacturing method for the spherical polymethyl-benzene base silsesquioxane particle that volume average particle size is 1~5 μm, it includes：(i) methyltrimethoxysilane is added in the water that pH is 4.0~7.0, reaction is hydrolyzed, the process for obtaining transparent aqueous solution；(ii) phenyltrimethoxysila,e is added in the aqueous solution obtained in process (i), reaction is hydrolyzed, the process for obtaining transparent silane-water solution；(iii) aqueous solution obtained in process (ii) is adjusted to 0~15 DEG C of temperature, add alkaline matter thereto or has dissolved the aqueous solution of alkaline matter, is stirred the process for obtaining mixed liquor；(iv) makes the mixed liquor obtained in process (iii) become static condition, the process for making polymethyl-benzene base silsesquioxane particle be precipitated.
Description
Technical field
The present invention relates to the manufacturing methods of spherical polymethyl-benzene base silsesquioxane particle.
Background technology
Polymethylsilsesquioxane particle as the light of the backlight of liquid crystal display diffusion with light diffusing sheet, sheet material and
The light diffusing agent of the light diffusion shell of LED illumination uses.Due in substrate resin and light diffusing agent particle there are refringence, because
The refraction and reflection of light occurs in this, shows light diffusing.Refringence is bigger, and light diffusing more improves, on the other hand, reflection
Light increases, therefore the permeability of light reduces.In the case where paying attention to the permeability of light, it is desirable to which refringence is small.In substrate resin
It is middle using polymethyl methacrylate, polystyrene, makrolon etc., but polymethylsilsesquioxane relative to these resins,
Refractive index is low, and refringence to be made to become smaller it is necessary to improve refractive index.By introducing phenyl silicon times in polymethylsilsesquioxane
Half oxygen alkane unit, so as to improve refractive index.By changing methyl silsesquioxane unit and phenylsilsesquioxane unit
Composition ratio, so as to make range of the refractive index 1.43~1.57.
As the spherical polymethyl-benzene base silsesquioxane particle for obtaining introducing the phenylsilsesquioxane unit
Method instantiates following method in Japanese Unexamined Patent Publication 4-202325 bulletins (patent document 1)：By methyltrimethoxysilane
The aqueous solution for instilling alkaline matter under stiring with the uniform mixed liquor of phenyltrimethoxysila,e makes its hydrolysis, condensation reaction.
There are problems that gelling material is attached to the inner wall of stirrer paddle, slot in this method.In addition, in Japanese Unexamined Patent Publication 2003-335860
Following method is proposed in number bulletin (patent document 2)：Make the mixing of methyl trialkoxysilane and phenyl trialkoxysilane
Object hydrolyzes in acidic aqueous solution, next, addition alkaline aqueous solution, after mixing, stops stirring, makes its condensation anti-under standing
It answers.In the autofrettage illustrated at this, gelling material is not generated, but volume average particle size is bigger than 5 μm.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 4-202325 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2003-335860 bulletins
Invention content
The subject that the invention solves
As light diffusing agent, the particle that substantially 1~5 μm of volume average particle size is suitble to, if it is the range of the grain size outside,
Then light diffusing reduces.The polymethyl-benzene base silsesquioxane grain illustrated in above-mentioned Japanese Unexamined Patent Publication 2003-335860 bulletins
The volume average particle size of son is bigger than 5 μm, and uncomfortable closing light spreads purposes.The present invention completes, purpose in view of above-mentioned actual conditions
It is to provide and manufactures 1~5 μm of volume average particle size for being suitable as light diffusing agent in the case where gelling material is without generating
The method of spherical polymethyl-benzene base silsesquioxane particle.
Means for solving the problems
The present inventor furthers investigate to achieve the goals above, as a result knows：By the way that methyltrimethoxysilane is added
It is added in the water that pH is 4.0~7.0, obtains transparent aqueous solution, add phenyltrimethoxysila,e thereto, obtain transparent
Silane-water solution adds alkaline matter thereto or has dissolved the aqueous solution of alkaline matter, so that mixed liquor is become static condition, makes
Polymethyl-benzene base silsesquioxane particle is precipitated, and water, methyltrimethoxysilane, phenyltrimethoxysila,e is made to become appropriate,
To obtain the spherical of 1~5 μm of volume average particle size for being suitable as light diffusing agent in the case where gelling material is without generating
Polymethyl-benzene base silsesquioxane particle, completes the present invention.
Therefore, the present invention provides following manufacturing methods.
[1] manufacturing method for the spherical polymethyl-benzene base silsesquioxane particle that volume average particle sizes are 1~5 μm, packet
Contain：
(i) methyltrimethoxysilane is added in the water of pH 4.0~7.0, reaction is hydrolyzed, obtained transparent
The process of aqueous solution；
(ii) phenyltrimethoxysila,e is added in the aqueous solution obtained in process (i), reaction is hydrolyzed, obtains
The process of bright silane-water solution；
(iii) aqueous solution obtained in process (ii) is adjusted to 0~15 DEG C of temperature, thereto add alkaline matter or
The aqueous solution for having dissolved alkaline matter is stirred the process for obtaining mixed liquor；With
(iv) so that the mixed liquor obtained in process (iii) is become static condition, make polymethyl-benzene base silsesquioxane particle
The process of precipitation,
It is following use level in above-mentioned operation (i) and (ii)：Relative to 100 mass parts of water, methyltrimethoxysilane
Total amount with phenyltrimethoxysila,e is 5~30 mass parts, uses methyltrimethoxysilane：Phenyltrimethoxysila,e table
The mass ratio shown is 90：10~20：80.
[2] manufacturing method described in [1], it includes following process：After (iv) process, mixed liquor is added under stiring
Heat adds alkaline matter or has dissolved the aqueous solution of alkaline matter to 40~100 DEG C.
The effect of invention
In accordance with the invention it is possible to provide the body that the manufacture in the case where gelling material is without generating is suitable as light diffusing agent
The method of the spherical polymethyl-benzene base silsesquioxane particle of 1~5 μm of average grain diameter of product.
Specific implementation mode
The present invention is explained in detail below.The manufacturing method of the present invention is that volume average particle size is 1~5 μm spherical poly-
The manufacturing method of aminomethyl phenyl silsesquioxane particle, it includes：
(i) methyltrimethoxysilane is added in the water of pH 4.0~7.0, reaction is hydrolyzed, obtained transparent
The process of aqueous solution；
(ii) phenyltrimethoxysila,e is added in the aqueous solution obtained in process (i), reaction is hydrolyzed, obtains
The process of bright aqueous solution；
(iii) aqueous solution obtained in process (ii) is adjusted to 0~15 DEG C of temperature, thereto add alkaline matter or
The aqueous solution for having dissolved alkaline matter is stirred the process for obtaining mixed liquor；With
(iv) so that the mixed liquor obtained in process (iii) is become static condition, make polymethyl-benzene base silsesquioxane particle
The process of precipitation,
It is following use level in above-mentioned operation (i) and (ii)：Relative to 100 mass parts of water, methyltrimethoxysilane
Total amount with phenyltrimethoxysila,e is 5~30 mass parts, uses methyltrimethoxysilane：Phenyltrimethoxysila,e table
The mass ratio shown is 90：10~20：80.
(i) methyltrimethoxysilane is added in the water of pH 4.0~7.0, reaction is hydrolyzed, obtained transparent
The process of silane-water solution
Methyltrimethoxysilane CH3Si(OCH3)3It indicates.For the water used in process (i), in order to make first
The phenyltrimethoxysila,e hydrolysis used in base trimethoxy silane and process (ii), need to make (25 DEG C) of pH become 4.0~
7.0.If pH is high less than 4.0 or than 7.0, condensation reaction carries out, and gel generates.Preferably 5.0~6.8 range.For example,
If it is ion exchange water, due to the dissolving of the carbon dioxide in air, pH becomes above range, therefore can directly make
With.In order to become the pH of above range, a small amount of acidic materials can be added.Acidic materials are not particularly limited, such as
It can be by the carboxylic acids such as formic acid, acetic acid, oxalic acid, malonic acid, lactic acid, malic acid, hydrochloric acid；Phosphoric acid；Sulfuric acid；Methanesulfonic acid；Trifluoro methylsulphur
1 kind of acid etc. is used alone or two or more is appropriately combined use.
For the hydrolysis speed of raising methyltrimethoxysilane, control polymethyl-benzene base silsesquioxane particle
The purpose etc. of grain size can add water-soluble organic solvent in water.Organic solvent is not particularly limited, first can be enumerated
The ketones such as the alcohols such as alcohol, ethyl alcohol, propyl alcohol, butanol, acetone, can a kind be used alone or be appropriately combined two or more and make
With.
In process (i), methyltrimethoxysilane is added in water, it is logical using helical blade, turbo blade, blade etc.
Normal blender carries out the hydrolysis of methyltrimethoxysilane under stiring.Methyltrimethoxysilane can add simultaneously,
Also it can spend and temporally gradually add.In addition, can add water in methyltrimethoxysilane on the contrary, also can simultaneously exist
Mixing is added in slot.To temperature at this time and be not limited, can 1~100 DEG C range carry out, also may be designated as 1~30 DEG C, 18
~30 DEG C of range.By hydrolysis, methyltrimethoxysilane becomes by formula CH3Si(OH)3The methyl-monosilane three of expression
Alcohol, in addition by-product methanol.Therefore, silane becomes dissolubility for the water containing methanol, becomes transparent aqueous solution.
Being stirred continuously until becomes transparent aqueous solution.Its time because hydrolysis speed, the i.e. pH of water, reaction temperature and
Stirring intensity and it is different.In addition, also different because of the additive amount of methyltrimethoxysilane.It should be noted that it is so-called " transparent ", refer to pair
In luminous ray without it is muddy, pass through the state of the see-through offside of substance.
(ii) phenyltrimethoxysila,e is added in the aqueous solution obtained in process (i), reaction is hydrolyzed, obtains
The process of bright aqueous solution
Phenyltrimethoxysila,e formula C6H5Si(OCH3)3It indicates.Further more, in aqueous solution, for raising phenyl front three
The purpose of hydrolysis speed of oxysilane, acidic materials can be added.Acidic materials are not particularly limited, such as can be incited somebody to action
The carboxylic acids such as formic acid, acetic acid, oxalic acid, malonic acid, lactic acid, malic acid, hydrochloric acid；Phosphoric acid；Sulfuric acid；Methanesulfonic acid；The 1 of trifluoromethanesulfonic acid etc.
Kind is used alone or two or more is appropriately combined use.In turn, for the hydrolysis for improving phenyltrimethoxysila,e
Speed, control polymethyl-benzene base silsesquioxane particle grain size purpose etc., can add in aqueous solution water-soluble organic
Solvent.Organic solvent is not particularly limited, the ketones such as the alcohols such as methanol, ethyl alcohol, propyl alcohol, butanol, acetone can be enumerated, it can
1 kind is used alone or two or more is appropriately combined use.
In process (ii), phenyltrimethoxysila,e is added in the aqueous solution of the silane obtained in process (i), is used
The common blender such as helical blade, turbo blade, blade carries out the hydrolysis of phenyltrimethoxysila,e under stiring.Benzene
Base trimethoxy silane can add simultaneously, can also spend and temporally gradually add.To temperature at this time and be not limited, can 0~
100 DEG C of range carries out.By hydrolysis, phenyltrimethoxysila,e becomes by formula C6H5Si(OH)3The phenyl silane of expression
Triol, in addition by-product methanol.Therefore, silane becomes dissolubility for the water comprising methanol, becomes transparent aqueous solution.
Being stirred continuously until becomes transparent aqueous solution.Its time because hydrolysis speed, the i.e. pH of water, reaction temperature and
Stirring intensity and it is different.In addition, also different because of the additive amount of phenyltrimethoxysila,e.
With regard to the use level of in process (i) and process (ii), methyltrimethoxysilane and phenyltrimethoxysila,e
Speech, relative to 100 mass parts of water, the total amount of methyltrimethoxysilane and phenyltrimethoxysila,e is 5~30 mass parts,
It is preferred that 13~28 mass parts.If the total amount of methyltrimethoxysilane and phenyltrimethoxysila,e is few, production efficiency
It is deteriorated, if more, the volume average particle size of polymethyl-benzene base silsesquioxane particle is made to be become difficult below as 5 μm.
By methyltrimethoxysilane：The mass ratio that phenyltrimethoxysila,e indicates is 90：10~20：80 range,
More preferable 85：15~40：60、80：20~50：50, further preferred 80：20~55：45.If the benzene in trimethoxy silane
The ratio of base trimethoxy silane is few, then refractive index excessively reduces, if more, refractive index is possible to excessively increase.
In the total use level and methyltrimethoxysilane of methyltrimethoxysilane and phenyltrimethoxysila,e
Fit quality ratio with phenyltrimethoxysila,e is in the case of above-mentioned range, if adding methyl trimethoxy simultaneously in water
Oxysilane and phenyltrimethoxysila,e are hydrolyzed, then obtain transparent aqueous solution and become difficult.In addition, even if in water
Phenyltrimethoxysila,e is first added, transparent aqueous solution is obtained and also becomes difficult.This is because phenyltrimethoxysila,e water
Xie Hou further carries out condensation reaction and becomes in water insoluble.If the process for carrying out front using the liquid of the state,
Its is insoluble to be divided into gel.
(iii) aqueous solution obtained in process (ii) is adjusted to 0~15 DEG C of temperature, thereto add alkaline matter or
The aqueous solution for having dissolved alkaline matter is stirred the process for being obtained by mixing mixed liquor
Alkaline matter as hydrolysis methyltrimethoxysilane and phenyltrimethoxysila,e, i.e. methyl-monosilane triol and
The condensation catalyst of phenyl silane triol plays a role, and polymethyl-benzene base silsesquioxane is thus generated in process (iv)
Particle.Alkaline matter can a kind be used alone, also two or more may be used.Alkaline matter can be added directly, due to needing to use
Short time makes it equably dissolve in water, therefore solid-like and gasiform alkaline matter is made to be added as aqueous solution.Only
It is solvable in water, then its concentration is not particularly limited.For the amount of alkaline matter, at least condensation is anti-in process (iv)
It should carry out, the amount that polymethyl-benzene base silsesquioxane particle generates is necessary.Minimum necessary amount is because of the water in process (i)
PH, the type of alkaline matter, reaction temperature and it is different.If alkaline matter is excessive, condensation reaction speed accelerates, process (iii)
Middle polymethyl-benzene base silsesquioxane particle starts to generate, and generates cohesion grain, gel.Therefore, it is necessary to control to be formed in process
(iii) amount that polymethyl-benzene base silsesquioxane particle does not generate in.Its maximum is because of methyltrimethoxysilane and phenyl
The use level of trimethoxy silane, the match ratio of methyltrimethoxysilane and phenyltrimethoxysila,e, the kind of alkaline matter
Class, reaction temperature and it is different.For example, in the case of the ammonia spirit of 28 mass %, relative to the water 100 used in process (i)
Mass parts properly select in 0.01~0.20 mass parts, the preferably range of 0.03~0.10 mass parts.
Alkaline matter is not particularly limited, such as the alkali metal such as potassium hydroxide, sodium hydroxide, lithium hydroxide can be used
Hydroxide；The alkaline earth metal hydroxides such as calcium hydroxide, barium hydroxide；The alkali carbonates such as potassium carbonate, sodium carbonate；Ammonia
Water；The tetra-alkyl ammonium hydroxides such as tetramethylammonium hydroxide, tetraethyl ammonium hydroxide；Monomethyl amine, monoethyl amine, a propylamine, monobutylamine (MBA),
Amines such as one amylamine, dimethylamine, diethylamine, trimethylamine, triethanolamine, ethylenediamine etc..Wherein, from by making its volatilization, to
It being capable of easily removing, preferably ammonium hydroxide from obtained polymethyl-benzene base silsesquioxane particle.
When adding alkaline matter or having dissolved the aqueous solution of alkaline matter, the temperature of the aqueous solution of silane is 0~15 DEG C, excellent
Select 0~10 DEG C.If temperature is high, condensation reaction speed is accelerated, the polymethyl-benzene base silsesquioxane particle in process (iii)
Start to generate, and agglomerates grain, gel generation.
The aqueous solution obtained under stiring in (ii) using the common blender such as helical blade, turbo blade, blade
Middle addition alkaline matter or the aqueous solution for having dissolved alkaline matter.With regard to alkaline matter or dissolved alkaline matter aqueous solution and
Speech, preferably adds, so that it is equably dissolved in water with the short time simultaneously.If until equably dissolving expends the time, have
Possible size distribution broadens or gel generates.
It needs to be stirred until at least alkaline matter or having dissolved the aqueous solution of alkaline matter in the aqueous solution of silane
It equably dissolves, if polymethyl-benzene base silsesquioxane particle starts to generate, generates cohesion, the gel of particle, therefore
Polymethyl-benzene base silsesquioxane particle stops stirring before generating.Polymethyl-benzene base silsesquioxane particle generate time because
The use level of methyltrimethoxysilane and phenyltrimethoxysila,e, methyltrimethoxysilane and phenyltrimethoxysila,e
Match ratio, the type of alkaloid substance and amount, temperature and it is different.In general, in 5 seconds~10 minutes, preferably 10 seconds~5 minutes ranges
It properly selects.
(iv) so that the mixed liquor obtained in process (iii) is become static condition, make polymethyl-benzene base silsesquioxane particle
The process of precipitation
If polymethyl-benzene base silsesquioxane particle generates, liquid gonorrhoea.Even if without fully if gonorrhoea particle
Solidification, therefore stand like this little while.If be stirred in the uncured state, particle coacervation or generation are solidifying
Glue.Required time of repose is different because of condensation reaction speed, the i.e. type and amount, reaction temperature of alkaloid substance.Usually at 30 minutes
It is properly selected in~24 hours, preferably 1 hour~12 hours ranges.By operating above, volume can be obtained and be averaged grain
The spherical polymethyl-benzene base silsesquioxane particle that diameter is 1~5 μm.
(iv) it after process, in order to which the surface to spherical polymethyl-benzene base silsesquioxane particle is modified, can stir
Lower addition is mixed by general formula R1Si(OR2)3The organotrialkoxysilane of expression, by general formula R3 2Si(OR2)2Two organic two indicated
Alkoxy silane, by general formula R3 3SiOR2Indicate three organoalkoxysilanes, by general formula Si (OR2)4The tetraalkoxy silicon of expression
Alkane, by general formula R2 3SiOH indicate three organosilanols and by formula [(CH3)3Si]21 in the hexamethyldisilazane that NH is indicated
Kind or more, so that it is carried out condensation reaction.In formula, R1It is 1 of the unsubstituted or substituted carbon number 1~20 in addition to methyl and phenyl
Valency alkyl, R2For 1 valency alkyl of unsubstituted carbon atom number 1~6, R3For 1 valency alkyl of unsubstituted or substituted carbon number 1~20.
(iv) after process, in order to make condensation reaction complete, alkaline matter can be added under stiring or dissolve basic species
The aqueous solution of matter, or heated at 40~100 DEG C.For example, can the mixed liquor after (iv) process be heated to 40 under stiring~
It 100 DEG C, adds alkaline matter or has dissolved the aqueous solution of alkaline matter.As alkaline matter or the water-soluble of alkaline matter is dissolved
Liquid can use the above-mentioned alkaline matter enumerated or the aqueous solution for having dissolved alkaline matter.As the time being stirred, have no
It is particularly limited to, is properly selected in 30 minutes~12 hours.(iv) after process, as needed, acid can be put under stiring
Property substance is neutralized.
By from the dispersion liquid of the polymethyl-benzene base silsesquioxane particle obtained in process (iv) by moisture and hydrolysis
The alcohol of by-product removes in reaction, so as to obtain spherical polymethyl-benzene base silsesquioxane particle.The removing of moisture is for example
It can be carried out by heating the aqueous dispersions after reaction under normal pressure or under reduced pressure, specifically, can be enumerated dispersion liquid
Stand under heating and by method that moisture removes, while the method for making to remove moisture when dispersion liquid stirring flowing under heating,
Make dispersion liquid spraying, the method for dispersion, the method etc. using flowing heat medium in hot-air flow as spray dryer.Again
Have, as the pre-treatment of the operation, the methods of thermal dehydration can be used, be separated by filtration, centrifuge, be decanted and dispersion liquid is dense
Contracting, as needed can clean dispersion liquid water, alcohol.
After moisture is removed in the aqueous dispersions after reaction, the spherical polymethyl-benzene for being 1~5 μm in volume average particle size
In the case of base silsesquioxane particle coacervation, the pulverizers such as jet mill, ball mill, hammer-mill can be used and be crushed.
It should be noted that in the present invention, so-called volume average particle size, it is intended that the volume reference found out using electric-resistivity method is averaged
Grain size.Volume average particle size can use electric-resistivity method particle size distribution device to measure.Such as BECKMAN can be used
The MULTISIZER of COULTER CO., LTD. manufactures is measured.
Embodiment
Embodiment described below and comparative example, specifically describe the present invention, but the present invention is not by following embodiments
Limitation.
[measurement of mean refractive index]
The methyl phenyl silicone that the decamethylcyclopentaandoxane and refractive index for the use of refractive index being 1.40 are 1.51, changes
Become its compounding ratio, prepares the mixed dissolution liquid that refractive index is 1.46,1.47,1.48,1.49,1.50.In addition, having prepared folding
Penetrate the methyl phenyl silicone that rate is 1.51.The liquid 20g of preparation is weighed respectively into 25ml vials, and then is respectively added
The powder for adding 1g, closes the lid, and vibrates 5 minutes, powder is made to be uniformly dispersed in a liquid.Standing is observed transparent after ten minutes
Property, using the refractive index of the highest liquid of the transparency as the mean refractive index of powder.
[embodiment 1]
It is packed into ion exchange water 801g in 1 liter of glass flask, water temperature is made to become 20 DEG C.Determine ion exchange water
PH, result 5.9.It is stirred using anchor type agitating paddle under conditions of blade rotating speed 150rpm, has put into methyl trimethoxy oxygen
As a result base silane 95.5g generates fever, temperature rise is to 24 DEG C.Become transparent state after 3 minutes, futher stirs 7 points
Clock.Then, put into phenyltrimethoxysila,e 62.5g, keep 20~25 DEG C of temperature, continue to stir, after as a result 50 minutes at
For transparent state, and then stir 5 minutes.25 minutes are lasted, is cooled to 5 DEG C.Put into 28 mass % ammonia spirits 0.53g and
The mixed dissolution liquid of ion exchange water 2.65g after having stirred 30 seconds, stops stirring.Gonorrhoea has occurred after stopping 12 seconds in stirring.
The use level of methyltrimethoxysilane and phenyltrimethoxysila,e is：Relative to 100 mass parts of water, methyl three
The total amount of methoxy silane and phenyltrimethoxysila,e is 19.7 mass parts, in addition, methyltrimethoxysilane and phenyl
The mass ratio of trimethoxy silane becomes 60.4：39.6.
After standing 3 hours, stirring is started under conditions of blade rotating speed 150rpm.75 DEG C are heated to, 28 matter are added
% ammonia spirit 38g are measured, and then at a temperature of 73~77 DEG C stir within 1 hour.After being cooled to 30 DEG C or less, it is transferred to
1 liter of glass beaker observes the inner wall and agitating paddle of glass flask, as a result without the attachment of discovery gel.Use pressure filtration
Device carries out de- liquid to obtained liquid, and pie is made, by the pie in hot air circular drying machine 105 DEG C at a temperature of
It is dry, dried object is crushed with jet mill, has obtained polymethyl-benzene base silsesquioxane particle.
With the shape of the electron microscope observation polymethyl-benzene base silsesquioxane particle, result is spherical.Use resistance
Method particle size distribution device " Multisizer 3 " (Beckman Coulter (strain) manufactures) measures polymethyl-benzene base silicon sesquialter
The volume average particle size of oxygen alkane particle, result are 2.1 μm.In addition, standard deviation (S.D.) is 0.29 μm, coefficient of alteration (C.V.)
It is 13.6%.It adopts and determines mean refractive index with the aforedescribed process, result 1.49.
[embodiment 2]
It is packed into ion exchange water 815g in 1 liter of glass flask, water temperature is made to become 20 DEG C.Determine ion exchange water
PH, result 5.9.It is stirred using anchor type agitating paddle under conditions of blade rotating speed 150rpm, has put into methyl trimethoxy oxygen
As a result base silane 77.6g generates fever, temperature rise is to 24 DEG C.Become transparent state after 3 minutes, futher stirs 7 points
Clock.Then, put into phenyltrimethoxysila,e 66.4g, keep 20~25 DEG C of temperature, continue to stir, after as a result 55 minutes at
For transparent state, and then stir 5 minutes.25 minutes are lasted, is cooled to 5 DEG C.Put into 28 mass % ammonia spirits 0.54g and
The mixed dissolution liquid of ion exchange water 2.7g after having stirred 20 seconds, stops stirring.Gonorrhoea has occurred after stopping 12 seconds in stirring.
The use level of methyltrimethoxysilane and phenyltrimethoxysila,e is：Relative to 100 mass parts of water, methyl three
The total amount of methoxy silane and phenyltrimethoxysila,e is 17.7 mass parts, in addition, methyltrimethoxysilane and phenyl
The mass ratio of trimethoxy silane becomes 53.9：46.1.
After standing 3 hours, stirring is started under conditions of blade rotating speed 150rpm.75 DEG C are heated to, 28 matter are added
% ammonia spirit 38g are measured, and then at a temperature of 73~77 DEG C stir within 1 hour.After being cooled to 30 DEG C or less, it is transferred to
1 liter of glass beaker observes the inner wall and agitating paddle of glass flask, as a result without the attachment of discovery gel.Use pressure filtration
Device carries out de- liquid to obtained liquid, and pie is made, by the pie in hot air circular drying machine 105 DEG C at a temperature of
It is dry, dried object is crushed with jet mill, has obtained polymethyl-benzene base silsesquioxane particle.
With the shape of the electron microscope observation polymethyl-benzene base silsesquioxane particle, result is spherical.Use resistance
Method particle size distribution device " Multisizer 3 " (Beckman Coulter (strain) manufactures) measures polymethyl-benzene base silicon sesquialter
The volume average particle size of oxygen alkane particle, result are 2.1 μm.In addition, standard deviation (S.D.) is 0.19 μm, coefficient of alteration (C.V.)
It is 8.6%.It adopts and determines mean refractive index with the aforedescribed process, result 1.50.
[embodiment 3]
It is packed into ion exchange water 789g in 1 liter of glass flask, water temperature is made to become 20 DEG C.Determine ion exchange water
PH, result 5.8.It is stirred using anchor type agitating paddle under conditions of blade rotating speed 150rpm, has put into methyl trimethoxy oxygen
As a result base silane 110.5g generates fever, temperature rise is to 24 DEG C.Become transparent state after 4 minutes, futher stirs 6
Minute.Then, phenyltrimethoxysila,e 59.5g is put into, 20~25 DEG C of temperature is kept, continues to stir, after as a result 45 minutes
As transparent state, and then stir 5 minutes.25 minutes are lasted, is cooled to 5 DEG C.Put into 28 mass % ammonia spirits 0.52g
With the mixed dissolution liquid of ion exchange water 2.6g, after having stirred 30 seconds, stop stirring.Gonorrhoea has occurred after stopping 30 seconds in stirring.
The use level of methyltrimethoxysilane and phenyltrimethoxysila,e is：Relative to 100 mass parts of water, methyl three
The total amount of methoxy silane and phenyltrimethoxysila,e is 21.5 mass parts, in addition, methyltrimethoxysilane and phenyl
The mass ratio of trimethoxy silane becomes 65.0：35.0.
After standing 3 hours, stirring is started under conditions of blade rotating speed 150rpm.75 DEG C are heated to, 28 matter are added
% ammonia spirit 38g are measured, and then at a temperature of 73~77 DEG C stir within 1 hour.After being cooled to 30 DEG C or less, it is transferred to
1 liter of glass beaker observes the inner wall and agitating paddle of glass flask, as a result without the attachment of discovery gel.Use pressure filtration
Device carries out de- liquid to obtained liquid, and pie is made, by the pie in hot air circular drying machine 105 DEG C at a temperature of
It is dry, dried object is crushed with jet mill, has obtained polymethyl-benzene base silsesquioxane particle.
With the shape of the electron microscope observation polymethyl-benzene base silsesquioxane particle, result is spherical.Use resistance
Method particle size distribution device " Multisizer 3 " (Beckman Coulter (strain) manufactures) measures polymethyl-benzene base silicon sesquialter
The volume average particle size of oxygen alkane particle, result are 2.2 μm.In addition, standard deviation (S.D.) is 0.27 μm, coefficient of alteration (C.V.)
It is 12.0%.It adopts and determines mean refractive index with the aforedescribed process, result 1.48.
[embodiment 4]
It is packed into ion exchange water 754g in 1 liter of glass flask, water temperature is made to become 20 DEG C.Determine ion exchange water
PH, result 5.9.It is stirred using anchor type agitating paddle under conditions of blade rotating speed 150rpm, has put into methyl trimethoxy oxygen
As a result base silane 142.9g generates fever, temperature rise is to 24 DEG C.Become transparent state after 7 minutes, futher stirs 8
Minute.Then, phenyltrimethoxysila,e 62.1g is put into, 20~25 DEG C of temperature is kept, continues to stir, after as a result 35 minutes
As transparent state, and then stir 5 minutes.25 minutes are lasted, is cooled to 5 DEG C.Put into 28 mass % ammonia spirits 0.50g
With the mixed dissolution liquid of ion exchange water 2.5g, after having stirred 30 seconds, stop stirring.Stirring stop 1 point have occurred after 15 seconds it is white
It is turbid.
The use level of methyltrimethoxysilane and phenyltrimethoxysila,e is：Relative to 100 mass parts of water, methyl three
The total amount of methoxy silane and phenyltrimethoxysila,e is 27.2 mass parts, in addition, methyltrimethoxysilane and phenyl
The mass ratio of trimethoxy silane becomes 69.7：30.3.
After standing 3 hours, stirring is started under conditions of blade rotating speed 150rpm.75 DEG C are heated to, 28 matter are added
% ammonia spirit 38g are measured, and then at a temperature of 73~77 DEG C stir within 1 hour.After being cooled to 30 DEG C or less, it is transferred to
1 liter of glass beaker observes the inner wall and agitating paddle of glass flask, as a result without the attachment of discovery gel.Use pressure filtration
Device carries out de- liquid to obtained liquid, and pie is made, by the pie in hot air circular drying machine 105 DEG C at a temperature of
It is dry, dried object is crushed with jet mill, has obtained polymethyl-benzene base silsesquioxane particle.
With the shape of the electron microscope observation polymethyl-benzene base silsesquioxane particle, result is spherical.Use resistance
Method particle size distribution device " Multisizer 3 " (Beckman Coulter (strain) manufactures) measures polymethyl-benzene base silicon sesquialter
The volume average particle size of oxygen alkane particle, result are 2.8 μm.In addition, standard deviation (S.D.) is 0.37 μm, coefficient of alteration (C.V.)
It is 13.4%.It adopts and determines mean refractive index with the aforedescribed process, result 1.47.
[embodiment 5]
It is packed into ion exchange water 759g in 1 liter of glass flask, water temperature is made to become 20 DEG C.Determine ion exchange water
PH, result 6.0.It is stirred using anchor type agitating paddle under conditions of blade rotating speed 150rpm, has put into methyl trimethoxy oxygen
As a result base silane 151.6g generates fever, temperature rise is to 24 DEG C.Become transparent state after 8 minutes, futher stirs 7
Minute.Then, phenyltrimethoxysila,e 48.4g is put into, 20~25 DEG C of temperature is kept, continues to stir, after as a result 30 minutes
As transparent state, and then stir 5 minutes.25 minutes are lasted, is cooled to 5 DEG C.Put into 28 mass % ammonia spirits 0.50g
With the mixed dissolution liquid of ion exchange water 2.5g, after having stirred 30 seconds, stop stirring.Stirring stop 1 point have occurred after 40 seconds it is white
It is turbid.
The use level of methyltrimethoxysilane and phenyltrimethoxysila,e is：Relative to 100 mass parts of water, methyl three
The total amount of methoxy silane and phenyltrimethoxysila,e is 26.3 mass parts, in addition, methyltrimethoxysilane and phenyl
The mass ratio of trimethoxy silane becomes 75.8：24.2.
After standing 3 hours, stirring is started under conditions of blade rotating speed 150rpm.75 DEG C are heated to, 28 matter are added
% ammonia spirit 38g are measured, and then at a temperature of 73~77 DEG C stir within 1 hour.After being cooled to 30 DEG C or less, it is transferred to
1 liter of glass beaker observes the inner wall and agitating paddle of glass flask, as a result without the attachment of discovery gel.Use pressure filtration
Device carries out de- liquid to obtained liquid, and pie is made, by the pie in hot air circular drying machine 105 DEG C at a temperature of
It is dry, dried object is crushed with jet mill, has obtained polymethyl-benzene base silsesquioxane particle.
With the shape of the electron microscope observation polymethyl-benzene base silsesquioxane particle, result is spherical.Use resistance
Method particle size distribution device " Multisizer 3 " (Beckman Coulter (strain) manufactures) measures polymethyl-benzene base silicon sesquialter
The volume average particle size of oxygen alkane particle, result are 3.2 μm.In addition, standard deviation (S.D.) is 0.52 μm, coefficient of alteration (C.V.)
It is 16.3%.It adopts and determines mean refractive index with the aforedescribed process, result 1.46.
[comparative example 1]
It is packed into ion exchange water 801g in 1 liter of glass flask, water temperature is made to become 20 DEG C.Determine ion exchange water
PH, result 5.9.It is stirred using anchor type agitating paddle under conditions of blade rotating speed 150rpm, has put into methyl trimethoxy oxygen
As a result the mixed dissolution liquid of base silane 95.5g and phenyltrimethoxysila,e 62.5g generates fever, temperature rise is to 24 DEG C.It protects
The temperature for holding 20~25 DEG C continues stirring 300 minutes, but is the state of cloudy grey, does not become transparent.
The use level of methyltrimethoxysilane and phenyltrimethoxysila,e is：Relative to 100 mass parts of water, methyl three
The total amount of methoxy silane and phenyltrimethoxysila,e is 19.7 mass parts, in addition, methyltrimethoxysilane and phenyl
The mass ratio of trimethoxy silane becomes 60.4：39.6.
25 minutes are lasted, is cooled to 5 DEG C.Put into the mixing of 28 mass % ammonia spirits 0.54g and ion exchange water 2.7g
Lysate after having stirred 20 seconds, stopped stirring.Stirring produces gonorrhoea after stopping 10 seconds.After standing 3 hours, turn in blade
Stirring is started under conditions of fast 150rpm.75 DEG C are heated to, adds 28 mass % ammonia spirit 38g, and then at 73~77 DEG C
At a temperature of carried out 1 hour stir.After being cooled to 30 DEG C or less, it is transferred to 1 liter of glass beaker, observes the interior of glass flask
As a result wall and agitating paddle are found that the attachment of hard gel in the bottom of glass flask and agitating paddle.
[comparative example 2]
It is packed into ion exchange water 801g in 1 liter of glass flask, water temperature is made to become 20 DEG C.Determine ion exchange water
PH, result 5.9.It is stirred using anchor type agitating paddle under conditions of blade rotating speed 150rpm, has put into phenyl trimethoxy
Base silane 62.5g keeps 20~25 DEG C of temperature, continues to stir for 300 minutes, but be the state of cloudy grey, not become
It is bright.Then, methyltrimethoxysilane 95.5g has been put into, has as a result generated fever, temperature rise is to 26 DEG C.Kept for 20~25 DEG C
Temperature, continue 60 minutes stir, but for cloudy grey state, do not become transparent.
The use level of methyltrimethoxysilane and phenyltrimethoxysila,e is：Relative to 100 mass parts of water, methyl three
The total amount of methoxy silane and phenyltrimethoxysila,e is 19.7 mass parts, in addition, methyltrimethoxysilane and phenyl
The mass ratio of trimethoxy silane becomes 60.4：39.6.
25 minutes are lasted, is cooled to 5 DEG C.Put into the mixing of 28 mass % ammonia spirits 0.54g and ion exchange water 2.7g
Lysate after having stirred 20 seconds, stopped stirring.Stirring produces gonorrhoea after stopping 9 seconds.After standing 3 hours, in blade rotating speed
Stirring is started under conditions of 150rpm.75 DEG C are heated to, adds 28 mass % ammonia spirit 38g, and then at 73~77 DEG C
At a temperature of carried out 1 hour stir.After being cooled to 30 DEG C or less, it is transferred to 1 liter of glass beaker, observes the inner wall of glass flask
And agitating paddle, the attachment of hard gel is as a result found that in the bottom of glass flask and agitating paddle.
[comparative example 3]
It is packed into ion exchange water 722g in 1 liter of glass flask, water temperature is made to become 25 DEG C.Determine ion exchange water
PH, result 5.9.It is stirred using anchor type agitating paddle under conditions of blade rotating speed 150rpm, has put into phenyl trimethoxy
Base silane 47.9g keeps 20~25 DEG C of temperature, continues to stir for 60 minutes, but be the state of cloudy grey, not become
It is bright.Then, methyltrimethoxysilane 191.7g has been put into, has as a result generated fever, temperature rise is to 32 DEG C.Become after 38 minutes
Transparent state, and then stirred 5 minutes.25 minutes are lasted, is cooled to 20 DEG C.Put into 28 mass % ammonia spirits 0.064g and
The mixed dissolution liquid of ion exchange water 0.32g after having stirred 30 seconds, stops stirring.After stirring stops 9 minutes, gonorrhoea is produced.
The use level of methyltrimethoxysilane and phenyltrimethoxysila,e is：Relative to 100 mass parts of water, methyl three
The total amount of methoxy silane and phenyltrimethoxysila,e is 33.1 mass parts, in addition, methyltrimethoxysilane and phenyl
The mass ratio of trimethoxy silane becomes 80：20.After having stood 12 hours, start to stir under conditions of blade rotating speed 150rpm
It mixes.75 DEG C are heated to, 28 mass % ammonia spirit 38g are added, and then at a temperature of 73~77 DEG C stir within 1 hour.
After being cooled to 30 DEG C or less, it is transferred to 1 liter of glass beaker, observes the inner wall and agitating paddle of glass flask, as a result
The attachment of gel is not found.De- liquid is carried out to obtained liquid using pressure filter, pie is made, which is existed
It is dry at a temperature of 105 DEG C in hot air circular drying machine, dried object is crushed with jet mill, has obtained polymethyl-benzene base silicon times
Half oxygen alkane particle.With the shape of the electron microscope observation polymethyl-benzene base silsesquioxane particle, result is spherical.
It is measured using electric-resistivity method particle size distribution device " Multisizer 3 " (Beckman Coulter (strain) manufactures)
The volume average particle size of polymethyl-benzene base silsesquioxane particle, result are 8.4 μm.In addition, standard deviation (S.D.) is 1.13 μ
M, coefficient of alteration (C.V.) are 13.4%.It adopts and determines mean refractive index with the aforedescribed process, result 1.45.
Claims (2)
1. the manufacturing method for the spherical polymethyl-benzene base silsesquioxane particle that volume average particle size is 1~5 μm, it includes：
(i) methyltrimethoxysilane is added in the water of pH 4.0~7.0, reaction is hydrolyzed, obtained transparent water-soluble
The process of liquid；
(ii) phenyltrimethoxysila,e is added in the aqueous solution obtained in process (i), reaction is hydrolyzed, is obtained transparent
The process of silane-water solution；
(iii) aqueous solution obtained in process (ii) is adjusted to 0~15 DEG C of temperature, adds alkaline matter or dissolving thereto
The aqueous solution of alkaline matter, is stirred the process for obtaining mixed liquor；With
(iv) so that the mixed liquor obtained in process (iii) is become static condition, polymethyl-benzene base silsesquioxane particle is made to be precipitated
Process,
It is following use level in the process (i) and (ii)：Relative to 100 mass parts of water, methyltrimethoxysilane and benzene
The total amount of base trimethoxy silane is 5~30 mass parts, uses methyltrimethoxysilane：What phenyltrimethoxysila,e indicated
Mass ratio is 90：10~20：80.
2. manufacturing method according to claim 1, it includes following process：It, under stiring will mixing after (iv) process
Liquid is heated to 40~100 DEG C, adds alkaline matter or has dissolved the aqueous solution of alkaline matter.
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| JP2016-016829 | 2016-02-01 | ||
| JP2016016829A JP6439712B2 (en) | 2016-02-01 | 2016-02-01 | Method for producing spherical polymethylphenylsilsesquioxane particles |
| PCT/JP2017/001700 WO2017135045A1 (en) | 2016-02-01 | 2017-01-19 | Method for producing spherical polymethylphenylsilsesquioxane particles |
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| KR (1) | KR20180107182A (en) |
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| WO2019086094A1 (en) * | 2017-10-30 | 2019-05-09 | Wacker Chemie Ag | Method for producing spherical polysilsesquioxane particles |
| KR102114059B1 (en) * | 2018-08-17 | 2020-05-25 | 주식회사 케이씨씨 | Curable organopolysiloxane composition and reflective materials for opical semiconductor comprising the same |
| KR102212703B1 (en) * | 2018-11-28 | 2021-02-05 | 이영철 | Process for producing wrinkled polymethylsilsesquioxane particles and polymethylsilsesquioxane powder comprising the polymethylsilsesquioxane particles prepared thereby |
| WO2020119887A1 (en) * | 2018-12-10 | 2020-06-18 | Wacker Chemie Ag | Process for preparing spherical silicone resin particles |
| CN116041706A (en) * | 2022-12-30 | 2023-05-02 | 中国科学院广州能源研究所 | Microsphere hydrate inhibitor and application thereof |
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| JPS63295637A (en) * | 1987-05-28 | 1988-12-02 | Toshiba Silicone Co Ltd | Spherical polymethylsilsequioxane powder and its production |
| US6376078B1 (en) * | 1999-06-03 | 2002-04-23 | Shin-Etsu Chemical Co., Ltd | Spherical fine particles of silicone resin |
| JP2003335860A (en) * | 2002-05-20 | 2003-11-28 | Ge Toshiba Silicones Co Ltd | Spherical polymethylphenylsilsesquioxane fine particle and manufacturing method therefor |
| JP2006089514A (en) * | 2004-09-21 | 2006-04-06 | Takemoto Oil & Fat Co Ltd | Method for producing spherical silsesquioxane fine particle, spherical silsesquioxane fine particle and surface modifier for polymer material |
| CN100362042C (en) * | 2003-02-27 | 2008-01-16 | 宇部日东化成株式会社 | Method for producing polyorganosiloxane particles and for producing silica particles |
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| JPH04202325A (en) * | 1990-11-29 | 1992-07-23 | Toray Ind Inc | Spherical fine particle of silicone |
| JP3189979B2 (en) * | 1991-07-24 | 2001-07-16 | ポーラ化成工業株式会社 | Method for producing spherical or fibrous organic silicon oxide powder |
| JP5117145B2 (en) * | 2006-09-08 | 2013-01-09 | 宇部日東化成株式会社 | Method for producing polyorganosiloxane particles and method for producing silica particles |
| WO2008047654A1 (en) * | 2006-10-12 | 2008-04-24 | Sekisui Chemical Co., Ltd. | Composition for formation of film, method for production of patterned film, and insulation film for electronic device |
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| JPS63295637A (en) * | 1987-05-28 | 1988-12-02 | Toshiba Silicone Co Ltd | Spherical polymethylsilsequioxane powder and its production |
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| KR20180107182A (en) | 2018-10-01 |
| WO2017135045A1 (en) | 2017-08-10 |
| JP6439712B2 (en) | 2018-12-19 |
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