CN108484874A - A kind of polyurethane material, high-elastic Antibacterial polyurethane class powder puff and preparation method thereof - Google Patents
A kind of polyurethane material, high-elastic Antibacterial polyurethane class powder puff and preparation method thereof Download PDFInfo
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- CN108484874A CN108484874A CN201810247976.7A CN201810247976A CN108484874A CN 108484874 A CN108484874 A CN 108484874A CN 201810247976 A CN201810247976 A CN 201810247976A CN 108484874 A CN108484874 A CN 108484874A
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D33/00—Containers or accessories specially adapted for handling powdery toiletry or cosmetic substances
- A45D33/34—Powder-puffs, e.g. with installed container
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3897—Low-molecular-weight compounds having heteroatoms other than oxygen containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- Polyurethanes Or Polyureas (AREA)
Abstract
A kind of polyurethane material of present invention proposition, high-elastic Antibacterial polyurethane class powder puff and preparation method thereof, the polyurethane material includes each raw material of following parts by weight：100 parts of polyether polyol mixture, 36 parts of wollastonite in powder, 12 parts of mildewproof additive, 60 80 parts of isocyanates mixture, 30 40 parts of hardening agent, 35 45 parts of foaming agent, 40 50 parts of filler, 58 parts of antiseptic, 14 parts of slipping agent, 2.5 6 parts of cross-linking catalyst.Polyurethane powder puff provided by the invention is researched and developed specifically for that can provide human skin good mutually suitable compatibility performance, there are the unique advantages such as more preferable, not scaling-off, the tasteless antibacterial of skin-friendly, high resiliency, oil-control is more preferable, cleaning is more convenient, feel exquisiteness, environmental protection relative to traditional latex and the existing powder puff prepared using technical polyurethane, there is wide popularizing application prospect.
Description
Technical field
The invention belongs to cosmetic technical fields, and in particular to a kind of powder puff used for cosmetic, especially a kind of powder puff are used poly-
Urethane material and preparation method thereof, especially a kind of polyurethanes powder puff and preparation method thereof with high resiliency, antibiotic property.
Background technology
Traditional powder puff product is varied, from purposes for, wash one's face with powder puff, powder puff etc., in shape
For upper, there is a sheet powder puff (various thickness), blocky powder puff (it is variously-shaped, diamond shape, triangle) etc..Traditional powder puff
Material is mainly natural emulsion and chemical synthesis latex, and this powder puff based on latex has following defect in actual use：
(1) natural emulsion powder puff is easy aging, and service life is shorter, and falls bits during use seriously, and water imbibition is general,
It is kind of an anaphylactogen to have the taste of latex and latex simultaneously, be easy to cause skin allergy.
(2) chemical synthesis latex powder puff is poisoned bigger in process of production, and the toxic gas distributed is relatively more, so raw
It more or less can all contain a certain amount of toxic gas, potential hazard health in the finished product powder puff of production；And fall bits in
Opposite natural emulsion powder puff wants better, but falling bits problem can not solve always.
Therefore the powder puff of latex class is either for the practical effect of the environmental requirement of production or user, all
It is not a selection well.Also there is the powder puff for being based partially on polyurethane in the prior art, as number of patent application is
The existing patent of CN201310404967.1 and CN201710621139.1, powder puff are based on polyurethane polymerization and prepare, prepare former
It all includes polyether polyol, isocyanates, hardening agent, foaming agent, catalyst etc. that material is general, but polyurethane in the prior art
Powder puff performance is very limited relative to the improvement of traditional latex powder puff performance, such as in the selection of polyether polyol and isocyanates
On, common raw material prescription is only selected, there is no be combined into material to polyether polyol and isocyanates to promote poly- ammonia
The performance of ester prepolymer, hardening agent therein are substantially common polyalcohol, this polyalcohol hardening agent belong in chemical industry at
Ripe hardening auxiliary agent, there is no technique effect outstanding in being prepared for polyurethane powder puff, foaming agent distilled water therein with
There are commonly organic silicon surface active agent outfit, same this common organic silicon surfactant for polyurethane powder puff in preparing
Also there is no special performance is played, the most key is the selection of catalyst, in the prior art multiselect ethers catalyst, catalysis
It is active general and there is hypotoxicity, thus polyurethane powder puff in the prior art to prepare raw material substantially be all to use industry
Raw material is prepared with polyurethane, that is to say, that polyurethane powder puff in the prior art is substantially only that polyurethane working stock exists
Molding application in powder puff mold, there is no specialize in for human skin and can have friend to human skin in the prior art
Good performance while the polyurethane powder puff technology of preparing that traditional latex can be clearly distinguishable from again.
Invention content
The present invention proposes a kind of completely new powder puff technology of preparing and a kind of completely new polyurethane stock material technology of preparing,
This polyurethane stock material is researched and developed specifically for that can provide human skin good mutually suitable compatibility performance, and based on completely new
Polyurethane material is prepared for a kind of completely new polyurethanes powder puff with high resiliency and high antibiotic property, relative to traditional latex with
And the existing powder puff prepared using technical polyurethane has more preferable, not scaling-off, the tasteless antibacterial of skin-friendly, high resiliency, oil-control more
The unique advantages such as good, cleaning is more convenient, feel exquisiteness, environmental protection, have wide popularizing application prospect.
It is as follows that the present invention solves the technical solution that above-mentioned technical problem is taken：
A kind of polyurethane material includes each raw material of following parts by weight：
A kind of high-elastic Antibacterial polyurethane class powder puff, wherein being made of each raw material of following parts by weight：
Further high-elastic Antibacterial polyurethane class powder puff according to the present invention, wherein by each original of following parts by weight
Material is made：
Further high-elastic Antibacterial polyurethane class powder puff according to the present invention, wherein the polyether polyol mixes
Material is mixed to prepare by each raw material of following parts by weight：
Further high-elastic Antibacterial polyurethane class powder puff according to the present invention, wherein the mildewproof additive is by preventing
Mould dose and palm wax in mass ratio 1:1 is mixed to prepare, and the mould inhibitor is mixed to prepare by each raw material of following parts by weight：
Further high-elastic Antibacterial polyurethane class powder puff according to the present invention, wherein the isocyanates mixture
It is made by each raw material hybrid reaction of following parts by weight：
Further high-elastic Antibacterial polyurethane class powder puff according to the present invention, wherein the hardening agent is by following heavy
Each raw material hybrid reaction for measuring part is made：
The wherein described silane coupling agent by any one of triethylvinylsilane silane, triple phenoxyl vinyl silanes with
Gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, phenylaminomethyl trimethoxy silane,
Any one of aminoethyl amino propyl trimethoxy silane and methacryloxypropyl trimethoxy silane are according to molar ratio
1.5:1 is mixed to prepare.
Further high-elastic Antibacterial polyurethane class powder puff according to the present invention, wherein the foaming agent is by distilled water
With easy foaming emulsifier according to mass ratio 10:1 mixing composition, the easy foaming emulsifier are mixed by each raw material of following parts by weight
Reaction is made：
Wherein described high hydroxyl value active constituent equimolar hybrid reaction 3~7 under weakly alkaline environment by oleic acid and sorbierite
Hour is made, and reaction condition is 200~250 DEG C of temperature, 0.05~0.1MPa of negative pressure.
Further high-elastic Antibacterial polyurethane class powder puff according to the present invention, wherein the antiseptic is received for metal
Nano antibacterial agent, by silver powder and anatase titanium dioxide TiO2Powder is 1-1.6 according to weight ratio:100 doping compositions, and the silver powder and rutile titania
Type TiO2The grain size of powder is between 8-30nm；The slipping agent is selected from erucyl amide, stearmide, zinc stearate or oleic acid acyl
One kind in amine；The filler selects villus fiber silk.
Further high-elastic Antibacterial polyurethane class powder puff according to the present invention, wherein the antiseptic is modified lives
Change metal nano antiseptic, the modified active metal nano antiseptic is by the NCO group of isocyanates to photo catalytic activation
The surface-active hydroxyl of lower metal nano antiseptic carries out following modified-reaction and obtains：
；The modified active metal nano antiseptic by grafting method be grafted to by polyether polyol composition, foam with
In the polyurethane prepolymer strand of Isocyanate prepolymers body synthesis, graft reaction is as follows：
Further high-elastic Antibacterial polyurethane class powder puff according to the present invention, wherein the cross-linking catalyst has
Following general structure：
Wherein R1And R2It is the independent alkyl containing 1-3 carbon atom, Y is methyl, and the structural formula of Z is as follows：
Wherein R3It is hydrogen, R4It is the alkyl containing 1 to 18 carbon atom, n is the integer of the 1-7 including endpoint.
A kind of preparation method of high-elastic Antibacterial polyurethane class powder puff of the present invention, includes the following steps：
Step 1 prepares each material component according to above-mentioned setting weight part；
Step 2, the preparation of polyether polyol composition, foam：By the polyether polyol mixture, wollastonite in powder, prevent
Mould additive, filler, slipping agent and foaming agent are successively put into the first reaction kettle by setting weight part, at 30-40 DEG C
Stirring 1.5 hours, speed of agitator are that 60-120 turns/min, and polyether polyol composition, foam is made after the completion of stirring；
Step 3, the preparation of Isocyanate prepolymers body：By the isocyanates mixture, antiseptic and hardening agent by setting
Parts by weight are put into the second reaction kettle, and it is that 80-120 turns/min to open and stir and control speed of agitator, is gradually warming up to 70-80
DEG C, and insulated and stirred 2 hours at this temperature, then the cross-linking catalyst is put by setting weight part to warm 2
In the second reaction kettle of hour, continue to stir and keep the temperature 2 hours at 70-80 DEG C, measure nco value, reaches theoretical value and open later
Beginning is cooled to 40 DEG C hereinafter, Isocyanate prepolymers body is made；
Step 4, by Isocyanate prepolymers body made from polyether polyol composition, foam made from step 2, step 3
In input to third reaction kettle, it is that 2000-2500 turns/min to open and stir and control speed of agitator, finally directly pours into powder puff mould
High-elastic Antibacterial polyurethane class powder puff is made in tool.
Technical scheme of the present invention has following innovative technology characteristic and prominent technique effect：
First, the present invention has initiated a kind of completely new powder puff polyurethane material and preparation method thereof, and the powder puff is with poly-
Urethane material is added to mildewproof additive and antibacterial with innovation component on preparing raw material relative to traditional industry polyurethane
Agent, it is not mouldy that the pioneering synthesis of the mildewproof additive can ensure that powder puff uses under moist environment for a long time, this is to be directed to powder puff
The unique design that application environment is taken, and good validation is obtained as a result, the antiseptic selects the metal nano that modified active is crossed
Antiseptic changes the surface-active hydroxyl of metal nano antiseptic under photo catalytic activation by the NCO group of isocyanates
Property reaction so that the modified active metal nano antiseptic can easily be grafted to base polyurethane prepolymer for use as strand
In, the antibacterial effect of material profound level is realized, the bacteria breed inside powder puff is avoided, this is also to be directed to powder puff use environment
The innovation taken improves.
Secondly, powder puff of the present invention fully optimized with polyurethane material it is each prepare raw material, such as by the abundant polyethers of key
Polyalcohol and isocyanates have carried out Combinatorial Optimization in advance, and relative to traditional industry polyurethane technique, fully having chosen can
There are a variety of polyether polyol and isocyanates formula of good skin-friendly to human skin, and carried out innovation collocation, belong to
In the urethane raw proposed specifically for human skin, it is totally different from and directly uses technical polyurethane raw material in the prior art
Scheme, be highly suitable for the preparation of powder puff, also reformed application of the polyurethane in powder puff.
Again, powder puff of the present invention has innovated key component hardening agent, foaming agent and catalytic crosslinking with polyurethane material
Agent, hardening agent therein is by Ludox, ethyl alcohol, silane coupling agent and 1, and 6- hexanediyl esters are based on completely new method
It prepares, belongs to a kind of hardening agent of hybrid, be totally different from traditional polyalcohol hardening agent, can be good at different
Cyanate mixture carries out hardening reaction, has effect outstanding in the preparation of polyurethane powder puff；The foaming agent changes tradition
Organic silicon surfactant, using with innovation component foaming emulsifier prepare, foaming effect can be obviously improved so that
Final polyurethane powder puff feel obtained is very fine and smooth；The cross-linking catalyst belongs to complete innovation, has very outstanding
Catalytic activity can promote polyether polyol and the pre-polymerization effect and performance of isocyanates.These key components finally affect
The performance of powder puff polyurethane material is that it is essentially different with traditional latex and industrial polyurethane material, is special
Door can be widely applied to for the polyurethane material of human skin innovation on all kinds of skin contact type cosmetic products.
In addition, being had in actual use based on polyurethanes powder puff prepared by polyurethane material of the present invention following only
Special advantage：(1) latex is free of：Latex is one kind of rubber, typically harmful minerals, and poly- ammonia of the present invention
Esters powder puff does not have any side effect to human body.(2) not scaling-off：Latex class powder puff encounters oil-based cosmetic preparation can be scaling-off, after aging
Also easy to be scaling-off, and powder puff of the present invention is entirely without this phenomenon.(3) tasteless：Latex class powder puff has latex taste, and latex
Taste can stay on the face, and powder puff of the present invention is completely tasteless.(4) environmentally friendly：Relative to latex powder puff, powder puff of the present invention is in nature
It can slowly melt decomposition in boundary.(5) density is thin：The powder puff holes of products size that traditional latex is produced with technical polyurethane
Differ, and polyurethanes powder puff appearance of the present invention is flexible smooth, abscess fine uniform, feel is fine and smooth.(6) oil-control is good：
Relative to traditional latex and technical polyurethane powder puff, powder puff oil-control performance of the present invention protrudes, and dresss up skin and does not injure
Skin outer layer tempered oil film can absolutely trust healthy use.(7) product is cleaned：Hold in powder puff cleaning process of the present invention
Easily dirt is cleaned up and is but not easy to be swollen, is easy to restore as former state after doing.(8) skin-friendly is good：Powder puff of the present invention is based on
Prepared by hydrophilic polyurethane raw material, can be suitble to anyone skin, and will not allergy after use.
Finally, polyurethane material of the present invention applies also for other and is connect with human skin in addition to it can be applied to powder puff
Tactile product scope, such as be applicable to make shoulder pad, chest pad dress material product, amenities such as napkin, paper nappy, etc. are made, are had
There is good marketing application prospect.
Specific implementation mode
Technical scheme of the present invention is described in detail below, so that those skilled in the art can more clearly
Understand the present invention, but the protection domain being not intended to limit the present invention.
A kind of high-elastic Antibacterial polyurethane class powder puff, is made of the raw material hybrid reaction of following parts by weight：
Wherein the polyether polyol mixture is made by each raw material hybrid reaction of following parts by weight：PolyTHF
10 parts of ether glycol, 5-8 parts of polyoxypropyleneglycol, 2-5 parts of polypropylene oxide triol and THF-PO copolymer
1.5-4 parts and 4-6 parts of propylene oxide, the preferred polyether polyol are to pass through sudden reaction by each raw material of above-mentioned parts by weight
Average molecular weight obtained is the polyether polyol of 1000-3000.
The wollastonite in powder is wollastonite Ca3〔Si3O9) powder, belong to single chain silicate mineral, powder puff can be improved
Toughness.
The mildewproof additive presses quality 1 by mould inhibitor and palm wax:1 is mixed to prepare, and the mould inhibitor is by following
Each raw material of parts by weight is mixed to prepare：8-10 parts of dodecyl-α-D glucosides, 6-8 parts of isothiazolinone, refined jasmine oil 2-4
Part, 0.5-1 parts of dimethicone, 3-6 parts of ketoconazole, 6-9 parts of sodium benzoate, 0.5-1 parts of sorbic acid, hydroxyethyl cellulose 9-12
Part is mixed to prepare.
The isocyanates mixture is made by each raw material hybrid reaction of following parts by weight：Toluene di-isocyanate(TDI)
(TDI) 10 parts, it is 3-5 parts of methyl diphenylene diisocyanate (MDI), 3-5 parts of 1,5- naphthalene diisocyanates (NDI), different to benzene two
1-4 parts of cyanate (PPDI) and dimethyl diphenyl diisocyanate (TODI) 5-8 parts by weight.
The hardening agent is made by each raw material hybrid reaction of following parts by weight：10 parts of Ludox, 8-12 parts of ethyl alcohol, silane
5-8 parts of 2-4 parts of coupling agent and 1,6- hexanediyl esters, can be added appropriate dilute hydrochloric acid or dilute sulphur during reaction
Acid provides acid hydridization reaction environment.The specific preparation method of the hardening agent includes：Described in being added first into three-necked flask
The Ludox and ethyl alcohol of parts by weight, then the silane coupling agent is added dropwise, can be used during the reaction dilute hydrochloric acid or
Dilute sulfuric acid carries out pH value adjusting, and preferred pH value is adjusted to 3~4, under stirring conditions, after reacting 3~6 hours, institute is added
1, the 6- hexanediyl esters of parts by weight are stated, then mixed liquor are added in single-necked flask, in 80-100 DEG C of temperature strip
Under part, rotary evaporation to white solid occurs, and appropriate solvent is added again after cooling, continues to be evaporated to no fraction steaming, then warp thread
After cloth filtering, it is spare that the hardening agent is made in bottling ageing 24 hours.The silane coupling agent used in the hardening agent is by three second
Any one of base vinyl silanes, triple phenoxyl vinyl silanes and gamma-aminopropyl-triethoxy-silane, γ-glycidol
Ether oxygen propyl trimethoxy silicane, phenylaminomethyl trimethoxy silane, aminoethyl amino propyl trimethoxy silane and methyl-prop
Any one of alkene acryloxypropylethoxysilane trimethoxy silane is according to molar ratio 1.5:1 is mixed to prepare.
The foaming agent is by distilled water and easily foaming emulsifier according to mass ratio 10:1 mixing composition, wherein the easy hair
Bubble emulsifier is made by each raw material hybrid reaction of following parts by weight：10 parts of acrylate, 3-6 parts of atoleine, xanthans 4-6
Part, 1.5-3 parts of lecithin, 2-4 parts of polyisobutene succinimide, 3-5 parts of Dehydrated Xylitol Monooleate and high hydroxyl value activity
6-8 parts of ingredient.Reaction is wherein formed by the acrylate, atoleine, xanthans and lecithin and soaks stabilizer, by institute
It states polyisobutene succinimide, Dehydrated Xylitol Monooleate and high hydroxyl value active constituent and forms reaction surfactant,
Wherein preferably by oleic acid and sorbierite, equimolar hybrid reaction is made the high hydroxyl value active constituent under weakly alkaline environment,
Reaction effecting reaction under conditions of 200~250 DEG C of temperature, 0.05~0.1MPa of negative pressure can be prepared by the high hydroxyl for 3~7 hours
It is worth active constituent.Also other high hydroxyl value active constituents well known in the art can be selected.
Villus fiber silk can be selected in the filler.
The antiseptic is preferably metal nano antiseptic, by anatase titanium dioxide TiO2Powder adulterates trace silver composition, and silver
With TiO2The doping weight ratio of powder is 1-1.6:100, while silver and TiO2The grain size of powder is between 8-30nm.It is further excellent
Choosing, to carry out effective activation crosslinking with the isocyanates mixture, the antiseptic is further by receiving the metal
Nano antibacterial agent carries out photocatalysis improvement, i.e., the preferred antiseptic selects modified active metal nano antiseptic, the modification
Activated metal nano antibacterial agent is by the NCO group of isocyanates to the surface-active of metal nano antiseptic under photo catalytic activation
Hydroxyl carries out following modified-reaction and obtains：
.In this way by using the pioneering this modified active metal nano antiseptic of the present invention so that this modified active
Metal nano antiseptic can be grafted to the end synthesized by the polyether polyol, isocyanates mixture by the method for grafting
Isocyanate based polyurethane performed polymer, the specific modified active metal nano antiseptic are grafted to poly- ammonia by grafting method
Fundamental reaction formula in ester prepolymer molecule chain is as follows：
The one kind of the slipping agent in erucyl amide, stearmide, zinc stearate or oleamide.
The cross-linking catalyst is that the foaming for being exclusively used in production polyurethane powder puff containing hydroxyl and surface active groups is urged
Agent, the catalyst react preparation with ethylene amines by alkyl glycidyl ether, and the specific catalyst has as follows
General structure：
Wherein R1And R2It is the independent alkyl containing 1-3 carbon atom, preferably methyl, Y are methyl；R3It is hydrogen；R4It is to contain
It is the integer of the 1-7 including endpoint to have the alkyl of 1 to 18 carbon atom, n, and preferably the integer of 2-3, Z structures are as follows：
The preparation method of high-elastic Antibacterial polyurethane class powder puff of the present invention includes：
Step 1 weighs each material component according to following parts by weight：100 parts of polyether polyol mixture, wollastonite in powder 3-6
Part, 1-2 parts of mildewproof additive, 60-80 parts of isocyanates mixture, 30-40 parts of hardening agent, 35-45 parts of foaming agent, filler
40-50 parts, 5-8 parts of antiseptic, 1-4 parts of slipping agent, 1.5-4 parts of cross-linking catalyst.Wherein each raw material part is according to respective composition
It is made in the manner previously described.
Step 2, the preparation of polyether polyol composition, foam：By the polyether polyol mixture, wollastonite in powder, prevent
Mould additive, filler, slipping agent and foaming agent are successively put into the first reaction kettle by setting weight part, at 30-40 DEG C
Stirring 1.5 hours, speed of agitator are that 60-120 turns/min, and polyether polyol composition, foam is made after the completion of stirring；
Step 3, the preparation of Isocyanate prepolymers body：By the isocyanates mixture, antiseptic and hardening agent by setting
Parts by weight are put into the second reaction kettle, and it is that 80-120 turns/min to open and stir and control speed of agitator, is gradually warming up to 70-80
DEG C, and insulated and stirred 2 hours at this temperature, then the cross-linking catalyst is put by setting weight part to warm 2
In the second reaction kettle of hour, continue to stir and keep the temperature 2 hours at 70-80 DEG C, measure nco value, reaches theoretical value and open later
Beginning is cooled to 40 DEG C hereinafter, Isocyanate prepolymers body is made；
Step 4, by Isocyanate prepolymers body made from polyether polyol composition, foam made from step 2, step 3
In input to third reaction kettle, it is that 2000-2500 turns/min to open and stir and control speed of agitator, finally directly pours into powder puff mould
High-elastic Antibacterial polyurethane class powder puff is made in tool
Specific embodiments of the present invention are given below：
Embodiment 1
A kind of high resiliency, antibiotic property powder puff polyurethane, are made of the raw material hybrid reaction of following parts by weight：
Wherein the polyether polyol mixture is made by each raw material hybrid reaction of following parts by weight：PolyTHF
1.5 parts of 10 parts of ether glycol, 5 parts of polyoxypropyleneglycol, 2 parts of polypropylene oxide triol and THF-PO copolymer
With 4 parts of propylene oxide, the polyether polyol is to pass through mean molecule made from sudden reaction by each raw material of above-mentioned parts by weight
Amount is the polyether polyol of 1000-1500.
The mildewproof additive presses quality 1 by mould inhibitor and palm wax:1 is mixed to prepare, and the mould inhibitor is by following
Each raw material of parts by weight is mixed to prepare：8 parts of dodecyl-α-D glucosides, 6 parts of isothiazolinone, 2 parts of refined jasmine oil, diformazan
0.5 part of base silicone oil, 3 parts of ketoconazole, 6 parts of sodium benzoate, 0.5 part of sorbic acid, 9 parts of hydroxyethyl cellulose are mixed to prepare.
The isocyanates mixture is made by each raw material hybrid reaction of following parts by weight：Toluene di-isocyanate(TDI)
(TDI) 10 parts, 3 parts of methyl diphenylene diisocyanate (MDI), 3 parts of 1,5- naphthalene diisocyanates (NDI), to benzene diisocyanate
5 parts of 1 part of ester (PPDI) and dimethyl diphenyl diisocyanate (TODI).
The hardening agent is made by each raw material hybrid reaction of following parts by weight：10 parts of Ludox, 8 parts of ethyl alcohol, silane are even
Join 2 parts of agent and 1, appropriate dilute hydrochloric acid is added in 5 parts of 6- hexanediyl esters during reaction.The silane coupling agent
By triethylvinylsilane silane and gamma-aminopropyl-triethoxy-silane according to molar ratio 1.5:1 is mixed to prepare.
The foaming agent is by distilled water and easily foaming emulsifier according to mass ratio 10:1 mixing composition, wherein the easy foaming
Emulsifier is made by each raw material hybrid reaction of following parts by weight：10 parts of acrylate, 3 parts of atoleine, 4 parts of xanthans, ovum
6 parts of .5 parts of phosphatidase 1,2 parts of polyisobutene succinimide, 3 parts of Dehydrated Xylitol Monooleate and high hydroxyl value active constituent.It is described
By oleic acid and sorbierite, the equimolar hybrid reaction under weakly alkaline environment is made high hydroxyl value active constituent.
Villus fiber silk can be selected in the filler.
The antiseptic is metal nano antiseptic, by anatase titanium dioxide TiO2Powder adulterates trace silver composition, and silver and TiO2Powder
The doping weight ratio of body is 1:100, while silver and TiO2The grain size of powder is between 8-30nm.
The slipping agent is selected from erucyl amide.
The cross-linking catalyst has the following structure general formula：
Wherein R1And R2It is methyl, Y is methyl；R3It is hydrogen；R4It is methyl, n is that 2, Z structures are as follows：
Embodiment 2
A kind of high-elastic Antibacterial polyurethane class powder puff, is made of the raw material hybrid reaction of following parts by weight：
Wherein the polyether polyol mixture is made by each raw material hybrid reaction of following parts by weight：PolyTHF
4 parts of 10 parts of ether glycol, 8 parts of polyoxypropyleneglycol, 5 parts of polypropylene oxide triol and THF-PO copolymer and
6 parts of propylene oxide, the polyether polyol are to pass through average molecular weight made from sudden reaction by each raw material of above-mentioned parts by weight
For the polyether polyol of 2000-3000.
The mildewproof additive presses quality 1 by mould inhibitor and palm wax:1 is mixed to prepare, and the mould inhibitor is by following
Each raw material of parts by weight is mixed to prepare：10 parts of dodecyl-α-D glucosides, 8 parts of isothiazolinone, 4 parts of refined jasmine oil, two
1 part of methyl-silicone oil, 6 parts of ketoconazole, 9 parts of sodium benzoate, 1 part of sorbic acid, 12 parts of hydroxyethyl cellulose are mixed to prepare.
The isocyanates mixture is made by each raw material hybrid reaction of following parts by weight：Toluene di-isocyanate(TDI)
(TDI) 10 parts, 5 parts of methyl diphenylene diisocyanate (MDI), 5 parts of 1,5- naphthalene diisocyanates (NDI), to benzene diisocyanate
8 parts of 4 parts of ester (PPDI) and dimethyl diphenyl diisocyanate (TODI).
The hardening agent is made by each raw material hybrid reaction of following parts by weight：10 parts of Ludox, 12 parts of ethyl alcohol, silane are even
Join 4 parts of agent and 1, appropriate dilute sulfuric acid is added in 8 parts of 6- hexanediyl esters during reaction.The silane coupling agent by
Triple phenoxyl vinyl silanes are with aminoethyl amino propyl trimethoxy silane according to molar ratio 1.5:1 is mixed to prepare.
The foaming agent is by distilled water and easily foaming emulsifier according to mass ratio 10:1 mixing composition, wherein the easy hair
Bubble emulsifier is made by each raw material hybrid reaction of following parts by weight：10 parts of acrylate, 6 parts of atoleine, 6 parts of xanthans,
8 parts of 3 parts of lecithin, 4 parts of polyisobutene succinimide, 5 parts of Dehydrated Xylitol Monooleate and high hydroxyl value active constituent.
The filler selects villus fiber silk.
The antiseptic is metal nano antiseptic, by anatase titanium dioxide TiO2Powder adulterates trace silver composition, and silver and TiO2Powder
The doping weight ratio of body is 1.6:100, while silver and TiO2The grain size of powder is between 8-30nm.
The slipping agent is selected from zinc stearate.
The cross-linking catalyst has the following structure general formula：
Wherein R1And R2It is the independent alkyl containing 3 carbon atoms, Y is methyl；R3It is hydrogen；R4It is containing 18 carbon atoms
Alkyl, n is that 7, Z structures are as follows：
Embodiment 3
A kind of high-elastic Antibacterial polyurethane class powder puff, is made of the raw material hybrid reaction of following parts by weight：
The wherein described polyether polyol mixture is made by each raw material hybrid reaction of following parts by weight：Polytetrahydrofuran ether
3 parts of 10 parts of glycol, 6 parts of polyoxypropyleneglycol, 4 parts of polypropylene oxide triol and THF-PO copolymer and ring
5 parts of Ethylene Oxide.
The mildewproof additive presses quality 1 by mould inhibitor and palm wax:1 is mixed to prepare, and the mould inhibitor is by following heavy
Each raw material of amount part is mixed to prepare：9 parts of dodecyl-α-D glucosides, 7 parts of isothiazolinone, 3 parts of refined jasmine oil, dimethyl
0.8 part of silicone oil, 4 parts of ketoconazole, 8 parts of sodium benzoate, 0.8 part of sorbic acid, 11 parts of hydroxyethyl cellulose are mixed to prepare.
The isocyanates mixture is made by each raw material hybrid reaction of following parts by weight：Toluene di-isocyanate(TDI)
(TDI) 10 parts, 4 parts of methyl diphenylene diisocyanate (MDI), 4 parts of 1,5- naphthalene diisocyanates (NDI), to benzene diisocyanate
3 parts of ester (PPDI) and 6 parts by weight of dimethyl diphenyl diisocyanate (TODI).
The hardening agent is made by each raw material hybrid reaction of following parts by weight：10 parts of Ludox, 10 parts of ethyl alcohol, silane are even
Join 3 parts of agent and 1, appropriate dilute hydrochloric acid is added in 6 parts of 6- hexanediyl esters during reaction.The silane coupling agent by
Triple phenoxyl vinyl silanes are with γ-glycidyl ether oxygen propyl trimethoxy silicane according to molar ratio 1.5:1 is mixed to prepare.
The foaming agent is by distilled water and easily foaming emulsifier according to mass ratio 10:1 mixing composition, wherein the easy hair
Bubble emulsifier is made by each raw material hybrid reaction of following parts by weight：10 parts of acrylate, 5 parts of atoleine, 5 parts of xanthans,
7 parts of 2 parts of lecithin, 3 parts of polyisobutene succinimide, 4 parts of Dehydrated Xylitol Monooleate and high hydroxyl value active constituent.It is described
High hydroxyl value active constituent preferably by oleic acid and sorbierite, equimolar hybrid reaction is made under weakly alkaline environment, react in temperature
It is carried out under conditions of 200~250 DEG C of degree, 0.05~0.1MPa of negative pressure.
The filler selects villus fiber silk.
The antiseptic is modified active metal nano antiseptic, and the modified active metal nano antiseptic passes through isocyanide
The NCO group of acid esters carries out following modified-reaction to the surface-active hydroxyl of metal nano antiseptic under photo catalytic activation and obtains：
.In this way by using the pioneering this modified active metal nano antiseptic of the present invention so that this modified active
Metal nano antiseptic can be grafted to the end synthesized by the polyether polyol, isocyanates mixture by the method for grafting
Isocyanate based polyurethane performed polymer, the specific modified active metal nano antiseptic are grafted to poly- ammonia by grafting method
Fundamental reaction formula in ester prepolymer molecule chain is as follows：
The slipping agent is selected from oleamide.
The cross-linking catalyst has the following structure general formula：
Wherein R1And R2It is the independent alkyl containing 2 carbon atoms, preferably methyl, Y are methyl；R3It is hydrogen；R4Be containing
The alkyl of 12 carbon atoms, n are that 5, Z structures are as follows：
Finally provide polyurethanes powder puff made from various embodiments of the present invention and traditional latex powder puff and technical polyurethane
The performance comparison of powder puff, as shown in the table：
It can be seen that the polyurethanes powder puff for preparing of the present invention scaling-off, taste, environmental protection, feel, oil-control, antibiotic property, elasticity,
Cleaning, skin-friendly etc. have the protrusion effect different from traditional product, and moderate cost, replicability are good.
It the above is only and the preferred embodiment of the present invention is described, technical scheme of the present invention is not limited to
This, those skilled in the art on the basis of the design of the major technique of the present invention made by any known deformation belong to the present invention
Claimed technology scope, the specific protection domain of the present invention are subject to the record of claims.
Claims (12)
1. a kind of polyurethane material, which is characterized in that each raw material including following parts by weight：
2. a kind of high-elastic Antibacterial polyurethane class powder puff, which is characterized in that be made of each raw material of following parts by weight：
3. high-elastic Antibacterial polyurethane class powder puff according to claim 2, which is characterized in that by each original of following parts by weight
Material is made：
4. according to the high-elastic Antibacterial polyurethane class powder puff of claim 2-3 any one of them, which is characterized in that the polyethers is more
First alcohol mixture is mixed to prepare by each raw material of following parts by weight：
5. according to the high-elastic Antibacterial polyurethane class powder puff of claim 2-4 any one of them, which is characterized in that described mould proof to add
Add agent by mould inhibitor and palm wax in mass ratio 1:1 is mixed to prepare, and the mould inhibitor is mixed by each raw material of following parts by weight
It is made：
6. according to the high-elastic Antibacterial polyurethane class powder puff of claim 2-5 any one of them, which is characterized in that the isocyanic acid
Ester mixture is made by each raw material hybrid reaction of following parts by weight：
7. according to the high-elastic Antibacterial polyurethane class powder puff of claim 2-6 any one of them, which is characterized in that the hardening agent
It is made by each raw material hybrid reaction of following parts by weight：
The wherein described silane coupling agent is by any one of triethylvinylsilane silane, triple phenoxyl vinyl silanes and γ-ammonia
Propyl-triethoxysilicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, phenylaminomethyl trimethoxy silane, ammonia second
Any one of base aminopropyl trimethoxysilane and methacryloxypropyl trimethoxy silane are according to molar ratio 1.5:1
It is mixed to prepare.
8. according to the high-elastic Antibacterial polyurethane class powder puff of claim 2-7 any one of them, which is characterized in that the foaming agent
By distilled water and easily foaming emulsifier according to mass ratio 10:1 mixing composition, the easy foaming emulsifier is by each of following parts by weight
Raw material hybrid reaction is made：
Wherein described high hydroxyl value active constituent equimolar hybrid reaction 3~7 hours under weakly alkaline environment by oleic acid and sorbierite
It is made, reaction condition is 200~250 DEG C of temperature, 0.05~0.1MPa of negative pressure.
9. according to the high-elastic Antibacterial polyurethane class powder puff of claim 2-8 any one of them, which is characterized in that the antiseptic
For metal nano antiseptic, by silver powder and anatase titanium dioxide TiO2Powder is 1-1.6 according to weight ratio:100 doping compositions, and the silver
Powder and anatase titanium dioxide TiO2The grain size of powder is between 8-30nm；The slipping agent is selected from erucyl amide, stearmide, zinc stearate
Or one kind in oleamide；The filler selects villus fiber silk.
10. according to the high-elastic Antibacterial polyurethane class powder puff of claim 2-9 any one of them, which is characterized in that the antibacterial
Agent is modified active metal nano antiseptic, the NCO group pair that the modified active metal nano antiseptic passes through isocyanates
The following modified-reaction of surface-active hydroxyl progress of metal nano antiseptic obtains under photo catalytic activation：
；The modified active metal nano antiseptic is grafted to by grafting method by polyether polyol composition, foam and isocyanide
In the polyurethane prepolymer strand of acid esters performed polymer synthesis, graft reaction is as follows：
11. according to the high-elastic Antibacterial polyurethane class powder puff of claim 2-10 any one of them, which is characterized in that the catalysis
Crosslinking agent has the following structure general formula：
Wherein R1And R2It is the independent alkyl containing 1-3 carbon atom, Y is methyl, and the structural formula of Z is as follows：
Wherein R3It is hydrogen, R4It is the alkyl containing 1 to 18 carbon atom, n is the integer of the 1-7 including endpoint.
12. a kind of preparation method of the high-elastic Antibacterial polyurethane class powder puff of claim 2-11 any one of them, feature exist
In including the following steps：
Step 1 prepares each material component according to above-mentioned setting weight part；
Step 2, the preparation of polyether polyol composition, foam：By the polyether polyol mixture, wollastonite in powder, mould proof add
Add agent, filler, slipping agent and foaming agent by setting weight part successively input to the first reaction kettle, is stirred at 30-40 DEG C
1.5 hours, speed of agitator was that 60-120 turns/min, and polyether polyol composition, foam is made after the completion of stirring；
Step 3, the preparation of Isocyanate prepolymers body：The isocyanates mixture, antiseptic and hardening agent are pressed into setting weight
In part input to the second reaction kettle, it is 80-120 turns/min to open and stir and control speed of agitator, is gradually warming up to 70-80 DEG C,
And insulated and stirred 2 hours at this temperature, then the cross-linking catalyst is put by setting weight part to warm 2 hours
The second reaction kettle in, continue stir and keep the temperature 2 hours at 70-80 DEG C, measure nco value, reach theoretical value later start to drop
Temperature is to 40 DEG C hereinafter, Isocyanate prepolymers body is made；
Step 4 puts into Isocyanate prepolymers body made from polyether polyol composition, foam made from step 2, step 3
Into third reaction kettle, it is that 2000-2500 turns/min to open and stir and control speed of agitator, finally directly pours into powder puff mold,
High-elastic Antibacterial polyurethane class powder puff is made.
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| CN110128812A (en) * | 2019-05-15 | 2019-08-16 | 雅丽日化实业(惠州)有限公司 | A kind of powder puff with can temperature become sponge and its manufacture craft |
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| CN110522157A (en) * | 2019-09-18 | 2019-12-03 | 广州市达戈彩美容科技有限公司 | It is a kind of using flowers and plants powder as powder puff of filler and preparation method thereof |
| CN111303613A (en) * | 2020-03-06 | 2020-06-19 | 广州琪彩化妆工具有限公司 | Cellular large-pore polyurethane sponge and processing method thereof |
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