CN106833934A - Detergent tablet containing enzyme and preparation method thereof - Google Patents
Detergent tablet containing enzyme and preparation method thereof Download PDFInfo
- Publication number
- CN106833934A CN106833934A CN201710028998.XA CN201710028998A CN106833934A CN 106833934 A CN106833934 A CN 106833934A CN 201710028998 A CN201710028998 A CN 201710028998A CN 106833934 A CN106833934 A CN 106833934A
- Authority
- CN
- China
- Prior art keywords
- surfactant
- detergent tablet
- enzyme
- acid
- containing enzyme
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- LBIYNOAMNIKVKF-FPLPWBNLSA-N palmitoleyl alcohol Chemical compound CCCCCC\C=C/CCCCCCCCO LBIYNOAMNIKVKF-FPLPWBNLSA-N 0.000 description 1
- LBIYNOAMNIKVKF-UHFFFAOYSA-N palmitoleyl alcohol Natural products CCCCCCC=CCCCCCCCCO LBIYNOAMNIKVKF-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 235000021118 plant-derived protein Nutrition 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention relates to a kind of detergent tablet containing enzyme and preparation method thereof.This contains enzyme detergent tablet by weight percentage, including the following raw material component：Enzyme 0.05~5%, porous adsorbent 0.5~20%, film forming agent 10~50%, surfactant 15~75%, auxiliary agent 0.1~60%, wherein, the porous adsorbent is the one kind in diatomite, aluminum oxide, montmorillonite.Detergent tablet containing enzyme of the invention, by each raw material components of reasonable disposition, and uses specific porous adsorbent to be processed with to enzyme, can effectively lift the conservation rate of the enzyme activity in detergent tablet preparation process.
Description
Technical field
The present invention relates to detergent composition, belong to daily use chemicals cleaning product technical field, more particularly to sheet containing enzyme is washed
Wash agent and preparation method thereof.
Background technology
In China, with the improvement of people's living standards, environmental consciousness also increasingly strengthens, detergent is also towards more environmentally-friendly
Concentrated type detergent direction develop, mainly have concentrated detergent powder and concentration liquid detergent (including laundry solidifying pearl) both direction.It is dense
Contracting washing powder and concentration liquid detergent there is a problem of being difficult quantitative, and washing powder also deposits alkaline stronger problem.For washing
Clothing coagulates pearl, although be easy to quantitative, but when washing a small amount of clothing, solidifying pearl cannot split for laundry, and use a solidifying pearl of laundry not
Exempt from waste occur.In addition, the solidifying pearl of laundry is higher to production equipment requirement, product is susceptible to seepage even fracture phenomena.Additionally,
The detergent of liquid also has that aviation is embargoed.Then, professional focuses on sight and is easy to quantitative and portable
Property more preferably on detergent tablet, detergent compositions engineer had attempted to develop detergent tablet in recent years.
Detergent is typically by compounding anion surfactant, nonionic surfactant and amphion surface-active
Agent is reaching excellent clean effect.But undeniable is that to rely solely on surfactant still difficult for some spots
With fully erased, some extra washing assisants are now needed to help wash.Enzyme refers to be extracted or by micro- from organic-biological
The class that bio secretion goes out has the material of catalysis activity, and, used as a kind of excellent washing assisant, a small amount of addition can be right for it
The effect of being obviously improved is played in decontamination, so adding it to the common wish that detergent tablet is professional.Enzyme is used as one
Plant protein, it is necessary to keep the stabilization of self-molecules present microstructure, could be played a role in washing process, and detergent tablet
High temperature is needed in preparation process so that by moisture evaporation, enzyme is extremely easy to be denatured and lose activity under the technique.At present, contain for preparation
The detergent tablet of enzyme remains unchanged and rarely has effective solution, and in the market is difficult to see the detergent tablet finished product containing enzyme, typically
Solid polypeptide formulation collocation detergent tablet is simply carried out into bundle sale.
Separately there are some technical schemes to be referred to and enzyme is added in detergent tablet to lift detergency, after its solution is
Phase sprays to detergent tablet.But do so, have following drawback：1st, it is higher to equipment requirement, it is difficult to popularize；2nd, spray
Device is spilt to easily cause leaking for enzyme and there is sensitization risk；3rd, enzyme solutions are sprayed easily to detergent tablet surface using flusher
Form is impacted, and enzyme can be gathered in the surface of detergent tablet, equally improves sensitization risk.
The content of the invention
Based on this, it is necessary to provide that a kind of enzyme activity conservation rate is high, strong detergency, and dissolving rapidly sheet containing enzyme is washed
Agent.
A kind of detergent tablet containing enzyme, by weight percentage, including the following raw material component：
One kind in soil.
Wherein in one embodiment, the porous adsorbent is that average pore size is 10~150nm.
Wherein in one embodiment, the granularity of the porous adsorbent is 100 mesh~3000 mesh.
Wherein in one embodiment, the film forming agent is selected from polyvinyl alcohol or the copolymer containing polyvinyl alcohol block,
Its number-average molecular weight is 10000~200000.
Wherein in one embodiment, the monomer of the copolymer containing polyvinyl alcohol block is vinyl alcohol, and propylene
Acid, acrylic acid derivative, ethacrynic acid, α-chloroacrylic acid, α-itrile group acrylic acid, butenoic acid, atropic acid, sorbic acid, clothing
One kind in health acid, maleic acid, maleic acid derivatives, vinylpyrrolidone.
Wherein in one embodiment, the surfactant is selected from anion surfactant, non-ionic surface active
Agent, cationic surfactant, one kind of zwitterionic surfactant and its various mixtures.
Wherein in one embodiment, the surfactant is that anion surfactant and/or non-ionic surface are lived
Property agent；The anion surfactant is sulfonate surfactant, carboxylate surfactant, sulfate type surface
One or more in activating agent of mixture；The nonionic surfactant is selected from the aliphatic alcohol polyethenoxy of C12-C18
Condensation product, the coconut oil fat of ether, C12-C14 APGs, C12-C18 alcohol and ethylene oxide/propylene oxide block copolymer
One or more in sour diglycollic amide, coconut oil fatty acid monoethanolamide, C8-C20 branched-chain alcoho APEOs mixed
Compound.
Wherein in one embodiment, by weight percentage, including the following raw material component：
Wherein in one embodiment, the enzyme be selected from protease, amylase, carbohydrase, cellulase, laccase, lipase,
One kind in oxidizing ferment, peroxidase, pectate lyase, mannase.
Auxiliary agent of the present invention may be selected from polyalcohol, polymer, chelating agent, foam inhibitor, pigment, essence, preservative
One kind.
The present invention also provides the described preparation method containing enzyme detergent tablet, comprises the following steps：
Water is added in ingredients pot, after being heated to 60 DEG C~90 DEG C, the film forming agent, stirring and dissolving is added；Then then at
The surfactant, auxiliary agent are added in the ingredients pot, is stirred, obtain mixed liquor；
The enzyme is mixed with porous adsorbent, enzymatic mixture is obtained；
The temperature of the mixed liquor is down to less than 45 DEG C, the enzymatic mixture is added, stirring obtains slurry；
Pulling-on piece is carried out to the slurry, is obtained final product.
Compared with prior art, the invention has the advantages that：
(1) detergent tablet containing enzyme of the invention, by each raw material components of reasonable disposition, and using specific porous absorption
Agent is processed with to enzyme, can effectively lift the conservation rate of the enzyme activity in detergent tablet preparation process.
(2) detergency of detergent tablet containing enzyme of the invention is excellent and dissolving is rapid.
Specific embodiment
For a person skilled in the art, it is feature of the invention, beneficial by reading the disclosure of the specification
Effect and advantage will become obvious.
Except as otherwise noted, all percentages, fraction and ratio are calculated by the gross weight of the present composition.Remove
Non- otherwise indicated, all wt about ingredients listed gives the content of active material, thus they be not included in it is commercially available
The solvent or accessory substance that may be included in the material of acquisition.This paper terms " weight ratio " available symbols " % " are represented.
Except as otherwise noted, all of molecular weight is all the weight average molecular weight represented in units of dalton herein.
Herein " including ", "comprising", " containing ", " containing ", " having " or other variants be intended to it is non-enclosed including,
Do not distinguished between these terms.Term "comprising" refers to that can add other steps and composition for not influenceing final result.Term
"comprising" also includes term " Consists of " and "consisting essentially of ...".The compositions and methods of the invention/technique can include,
It is made from it and substantially by essential elements described herein and limit entry and described herein any additional or optional
Composition, component, step or limit entry composition.
Detergent tablet：
Detergent tablet refers to the water soluble flexible sheet-form product with washing dirt-removing functions.
Detergency ability and evaluation criterion：
Detergency ability refers to removal ability of the detergent tablet for spot.Using standard liquid detergent as control, by mark
The detergency test result of quasi- soiled cotton (JB01, JB02 and JB03) is evaluated.Mark is exceeded to three kinds of detergencies of standard soiled cloth
Quasi- liquid detergent, then it is assumed that with good detergency ability.
Solubility property and evaluation criterion：
Solubility property refers to the ability of detergent tablet rapid dispersing and dissolving in water.It is disintegrated in water with detergent tablet and is divided
The scattered time, disintegration scatter in 30s, thinks with good dissolubility energy as evaluation.
The mode of production containing enzyme detergent tablet：
The mode of production containing enzyme detergent tablet of the present invention is：The dispersion of each component water dissolves is configured to certain dense
The slurry of degree, is then made piece by slurry by way of roller drying pulling-on piece, and then is again cut piece.The temperature of pulling-on piece
At 80 to 90 DEG C, the pull-in time, pulling-on piece temperature influenceed very big to enzyme stability at 8 to 15 minutes.
Enzyme：
The optional enzyme for various fabric washing purposes, including for example remove protein-based, carbohydrate-based
Or triglycerides base spot, prevent free dyestuff from shifting, for fabric restoration.Suitable enzyme include protease, amylase,
Carbohydrase, cellulase, laccase, lipase, bleaching enzymes such as oxidizing ferment and peroxidase, pectate lyase, mannase
Or their mixture.Also other types of enzyme can be included.They are available from any suitable source, for example plant, animal, thin
Bacterium, fungi and yeast sources.However, their selection is arranged by many factors, pH value such as system, selected by surface live
Property agent, auxiliary agent factor, these factors directly influence enzyme high-temperature stability.In this respect, bacterium or fungal enzyme be it is preferred, such as
Bacterial amylase and protease, and fungal cellulase.
Suitable protease includes metalloproteinases and serine protease, such as subtilopeptidase A.Suitable egg
White enzyme includes those of animal sources, plant source or microbial source.In one aspect, such suitable protease can be microorganism
Source.Suitable protease includes the mutant of chemical modification or the above-mentioned suitable protease through genetic modification.In one aspect, close
Suitable protease can be serine protease, such as alkaline microbial protease or/and trypsase type protease.Amylase bag
Include, for example, the amylase (Novi's letter) described in the specification of BP GB1296839, RAPIDASE
(International Bio-Synthetics, Inc) and TERMAMYL (Novo Industries).
Can be used for cellulase of the invention includes bacterium or fungal cellulase.Preferably, they will be between 5 Hes
Optimal pH between 9.5.Suitable cellulase is the fungi fiber produced by Humicola insolens and humicola lanuginosa strain DSM 1800
Plain enzyme or belong to Aeromonas generation cellulase 212 fungi, and from sea mollusk
(DolabellaAuriculaSolander) cellulase that hepatopancrease is extracted.
The Suitable Fatty enzyme used for detergent includes those produced by pseudomonas group microorganism, such as it is false singly
Born of the same parents Pseudomonas stutzeri ATCC 19.154.The lipase can be with trade name Lipase P " Amano ", hereinafter referred to as
" Amano-P ", purchased from Amano Pharmaceutical Co.Ltd. (Nagoya, Japan).Other commercial fatty enzymes include
The lipase (lipases ex Chromobacterviscosum) that Amano-CES, Chromobacter viscosum are extracted, for example can be from
ToyoJozo Co. (Tagata, Japan) it is commercially available from Chromobacterviscosumvar.lipolyticum
Lipase obtained in NRRLB 3673；And from U.S.BiochemicalCorp., U.S.A. and Disoynth Co. (The
Netherlands Chromobacter viscosum lipase), and gladiolus pseudomonad extracts lipase T (lipases ex
Pseudomonas gladioli).Can from Novozyme it is commercially available from Humicola lanuginosa (Humicola
Lanuginose LIPOLASE enzymes) are to can be used for the preferred enzyme of the technical program.
Peroxidase is combined with oxygenatedchemicals source such as percarbonate, perborate, persulfate, hydrogen peroxide etc.
Use.It is used for " solution bleaching ", i.e. prevent the dyestuff or pigment that are removed from substrate during washing operation to be transferred to washing
Other substrates in solution.Peroxidase is it is known in the art, and including such as horseradish peroxidase, wooden
Plain enzyme and haloperoxidase.
Enzyme pretreating process：
Enzyme pretreating process is referred to and configures into before slurry enzyme preparation, in advance by enzyme preparation (usually solution) with
Porous adsorbent by batch mixer mix after be uniformly dispersed, until porous adsorbent enzyme preparation is adsorbed completely and particle between without bright
Aobvious adhesion is reunited.
Enzyme stability：
Part enzyme denaturation inactivation is had in the production process of detergent tablet high-temperature molding, the enzyme stability refers to that enzyme exists
The ability of its vigor is kept in detergent process.In the case of 85 DEG C of 10 minutes pull-in times, enzyme activity conservation rate exceedes
50%, then it is assumed that with good enzyme stability.
Enzyme activity conservation rate：
Energy value in the case of keeping activity completely with enzyme is 100%, and described enzyme activity conservation rate refers to detergent tablet
In contained enzyme actual energy value and theoretical energy value ratio.
Enzyme activity force test method：
After being reacted by specific substrate and enzyme, chromophore can be released colour developing, be with AAS
The depth of color can be determined, the curve ratio done with known standard enzyme relatively after, you can obtain the vigor of enzyme to be measured.
Porous adsorbent：
Porous adsorbent refers to that the hole by being mutually communicated constitutes the powdered solids with adsorptivity of network structure,
Selected from any one or more in diatomite, aluminum oxide, montmorillonite.Common enzyme molecule diameter is about 2~20nm, is adapted to this
The porous adsorbent aperture size of invention is 10~150nm, preferably 20~100nm.
It is 100 mesh~3000 mesh, preferably 300 mesh~700 mesh to be adapted to porous adsorbent granularity of the invention.
Enzyme and porous adsorbent are well mixed by batch mixer, and porous adsorbent quality is 4~10 times of enzyme, it is ensured that enzyme quilt
Fully absorption.
Film forming agent：
Film forming agent is the matrix of detergent tablet, each component of detergent tablet such as surfactant, auxiliary agent can be sticked
Close at one piece, make obtained piece that there is certain tensile strength.Examined based on film forming, dissolubility, technique, storage stability
Consider, the film forming agent is selected from polyvinyl alcohol or based on polyvinyl alcohol copolymer, its molecular weight is 10000~200000.It is described
Based on polyvinyl alcohol copolymer in addition to vinyl alcohol units also comprising arbitrarily be selected from acrylic monomers, acrylic acid derivative list
One or more in body, vinyl-pyrrolidone monomers, maleic acid monomer, maleic acid derivatives monomer.
Surfactant system：
Suitable surfactant system includes, but is not restricted to：Anion surfactant, non-ionic surface active
Agent, cationic surfactant, one kind of zwitterionic surfactant and its various mixtures.Preferred surfactant
Mixture of the system comprising anion surfactant and nonionic surfactant.
Anion surfactant：
Anion surfactant is selected from sulfonate surfactant, carboxylate surfactant, sulfate type table
One or more in the activating agent of face of mixture；It preferably is selected from alkylbenzenesulfonate, the alkyl sulfate of C8 to C18, C8 to C18
Ethoxylated fatty alcohol sulfate, the soap of C8 to C18, alpha-alkene sulfonate, fatty acid alkyl ester sulfonate, ethoxy
One kind or their mixture in base Fatty Alcohol Ether Carboxylate.
Alkyl sulfate is at normal temperatures generally pulverulent solids, is for the present invention the surface-active for preferably using
Agent, it is not easy to cause the greasy feel of detergent tablet, and make detergent tablet with more excellent feel.It is adapted to the present invention
Alkyl sulfate be the alkyl sulfate of C8 to C18, more preferably laurate sulfate.
In some embodiments, the mixture of anion surfactant preferably adds alkylbenzenesulfonate and its spreads out
It is biological improving the detergency to graininess dirt.The alkylbenzenesulfonate meets below formula：
Wherein R1It is alkyl that carbon number is 6 to 24, M+It is cation.R1Can be the alkyl, or side chain of straight chain
Alkyl；Can be the alkyl, or the alkyl containing one or more unsaturated double-bonds of saturation.Further preferred R1It is carbon
Number is 8 to 18 straight chained alkyl.
In some embodiments, the mixture of anion surfactant contains the aliphatic alcohol sulfate of ethoxylation.
Ethoxylated fatty alcohol sulfate is the derivative of ethoxylate fatty alcohol, with below formula：
Wherein R1It is alkyl that carbon number is 6 to 24；X is 0.5 to 30；Wherein M+It is cation.R1Can be the alkane of straight chain
The alkyl of base, or side chain；Can be the alkyl, or the alkane containing one or more unsaturated double-bonds of saturation
Base.It is preferred that R1It is straight chained alkyl that carbon number is 8 to 18.X represents average ethoxylation degree, is 0.5 to 30, and preferably 0.5 to 10,
More preferably 0.5 to 3.
In some embodiments, containing alpha-alkene sulfonate, with below formula：
Wherein a is 0 to 2, R1It is alkyl that carbon number is 6 to 24, preferably R1It is alkyl that carbon number is 8 to 18.The anion
Surfactant can also include one kind and various mixtures of alkyl sodium disulfonate or derivatives thereof, preferably alkyl diphenyl ether two
Sodium sulfonate, suitable example is disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate salt.Fatty acid alkyl esters sulfate can also be contained, preferably
Fatty acid methyl ester sulfate (MES), aliphatic acid carbon number preferably 8 to 18.Sulfosuccinate, preferably fat can also be included
Alcohol polyoxyethylene ether sulfosuccinic acid monoester disodium salt, fatty alcohol carbon number preferably 8 to 18, average ethoxylation degree is preferably
2.0。
In some embodiments, anion surfactant contains soap, and preferably carbon number is the fat of 8 to 18
Fat hydrochlorate.The alkyl segment of aliphatic acid can be straight chain, or side chain can be the alkyl of saturation, or contain
There is the alkyl of one or more unsaturated double-bonds.Soap can be single composition, or various aliphatic acid composition
Mixture.Suitable example is enuatrol, sodium laurate.The soap also includes ethoxylized fatty alcohol ether carboxylate,
The carbon number of fatty alcohol preferably 8 to 18, average ethoxylation degree is preferably 2.0 to 10.
Nonionic surfactant：
Nonionic surfactant is selected from AEO, C12-C14 APGs, the C12-C18 of C12-C18
Condensation product, cocoanut fatty acid diethanolamide, the coco-nut oil fatty acid list of alcohol and ethylene oxide/propylene oxide block copolymer
Any one in glycollic amide, C8-C20 branched-chain alcoho APEOs or more than two kinds.
In some embodiments, non-ionic surfactant mixture preferably comprises fatty alcohol alkoxy compound, described
Fatty alcohol alkoxy compound has below general formula：
Wherein, n is 6 to 24；X is that 0.5 to 30, y is 0 to 10.
Described fatty alcohol alkoxy compound is the ring-opening polymerisation under base catalyst effect of fatty alcohol and epoxyalkane
Product, substantially mixture.Fatty alcohol includes the isomery alcohol of straight chain alcohol or side chain.Alkoxy grp includes ethoxy group and the third oxygen
Group.The preferred carbon number of fatty alcohol is 8 to 18 fatty alcohol, and preferred alcohol includes but is not limited to hexanol, octanol, decyl alcohol, 2- second
Base alcohol, 3- propyl enanthols, laruyl alcohol, different three decyl alcohol, tridecanol, tetradecanol, hexadecanol, Palmitoleyl alcohol, stearyl alcohol,
One kind or its mixture in isooctadecanol, oleyl alcohol, sub- oleyl alcohol, linolenyl alcohol.Average ethoxylation degree x preferably 2 to 12.It is preferred that
Example is SHELL companies NEODOL series linear primary alcohol ethoxylate products, DOW companies ECOSURF EH series ethyoxyls
Change and the third oxidation 2-ethylhexanol product, BASF AG's Lutensol XL series ethoxylations and the third oxidation 3- propyl enanthols are produced
Product and BASF AG's Lutensol XP series ethoxylation 3- propyl enanthol products.
In some embodiments, non-ionic surfactant mixture preferably comprises APG, with following logical
Formula：
Wherein, n is that 6 to 24, p is 1.1 to 3, and preferably n is 8 to 16.Suitable APG such as BASF AG
Glucopon series APG products.
Non-ionic surfactant mixture can contain fatty acid alkoxylates, preferably be selected from ethoxylation C8 to C18
Fatty acid ester, average ethoxylation degree is 2 to 10.Ethoxylated sorbitan acid alcohol Arrcostab, alkyl carbon number can be contained
It is 6 to 18, average ethoxyquin degree is 4 to 20；Suitable example is Corda company's T ween series of products.
Non-ionic surfactant mixture can contain fatty acid alkyl alcohol amide, and the carbon number of aliphatic acid is 6 to 24, can
Can be the aliphatic acid, or undersaturated fat of saturation to be the aliphatic acid of straight chain, or the aliphatic acid of side chain
Acid；Alkylol number is 0 to 2.Preferred fatty acid carbon number is 8 to 18 glycollic amide, diglycollic amide, isopropanol amide,
Suitable example is coconut acid diethanolamide (trade name 6501).
Non-ionic surfactant mixture can contain fatty acid methyl ester ethoxylate, and formula is as follows：
Wherein, n is 6 to 24；X is 2 to 20, and preferably n is that 8 to 18, x is 0.5 to 30.It is preferred that x is 4 to 10.Suitable example
It is LION companies MEE products.Non-ionic surfactant mixture can contain polyether surfactant.Live on polyether-type surface
Property agent be a kind of polymer, contain oxidation ethylene and/or oxidation trimethylene repeat unit nonionic surfactant, suitable example
Son such as BASF AG's Pluronic series of products.
Other surfactants：
Surfactant system of the present invention can contain other surfaces activating agent.Zwitterionic surfactant is selected
From amino acid type surfactant, amine oxide type surfactant, betaine type amphoteric surfactant, Imidazoline Surfactants
One or more mixture；Including but not limited to：Alkyl betaine, fatty acid amide glycine betaine, fatty amide propyl beet
Alkali, fatty amide propyl hydroxypropyl sulfonated betaine, including acetate alkyl sodium form imidazoline, fatty acid type imidazoline, sulfonic acid type
Imidazoline, alanine derivatives, glycine derivative, alkyl dimethyl amine oxide, the oxidation of fatty acyl amido propyl-dimethyl
Amine etc..Cationic surfactant includes quaternary ammonium salt surface active agent, heterocyclic surfactant, polymer-type cation form
Face activating agent.Including：Single long linear quaternary ammonium salt, double long linear quaternary ammonium salts, benzyl quaternary ammonium salt, hydroxyalkyl quaternary ammonium salt, fatty acid amide
Propyl group hydroxyalkyl quaternary ammonium salt, there are many quaternary ammoniums that vinyl pyrrolidone and unsaturated amides or unsaturated quaternary ammonium salt copolymerization obtain
Salt.
Auxiliary agent：
The addition of auxiliary agent is mainly used in outward appearance feel and clean result of the lifting containing enzyme detergent tablet.
Polyalcohol is the preferential raw material for adding of the invention, and it has plasticization for described detergent tablet, described
Polyalcohol include but is not limited to following compound group into group：Glycerine, propane diols, mannitol and sorbierite.
Polymer is the preferential raw material for adding of the invention, and it is formed by class relative molecular mass molecule aggregation very high
Compound, also referred to as macromolecule, macromolecular etc..Polymer is generally divided into natural polymer, synthesis macromolecule chemical combination
Thing and semi-synthetic macromolecular compound.Except the polymerization beyond the region of objective existence used as film forming agent, for the polymer of detergent tablet
Mainly have：Can improve the polymer of detergent tablet outward appearance feel, the polymer with decontamination synergistic effect with filling effect.
The polymer include but is not limited to following compound group into group：It is starch and its derivative, cellulose and its derivates, poly-
Ethylene glycol, polyacrylic acid and its derivative, polyacrylamide and its derivative, polyvinylpyrrolidone and its derivative.
Except mentioned component, detergent composition of the invention can also include chelating agent, foam inhibitor, pigment, essence, preservative
Etc. various common and conventional additives.These additives and associated method of use are all well known to those skilled in the art
, the selection of its specific type and consumption can be adjusted according to actual needs.
Preparation technology：
Described detergent tablet containing enzyme is obtained using following technique：
(1) process water is added in ingredients pot, 60 DEG C~90 DEG C are heated to, starts stirring, film forming agent dissolving stirring is equal
It is even；
(2) to surfactant, high temperature resistant auxiliary agent is added in ingredients pot, stir；
(3) it is uniformly dispersed after enzyme preparation is mixed with porous adsorbent by batch mixer, until porous adsorbent is by enzyme system
Agent adsorb completely and particle between without obvious adhesion reunite；
(4) start ingredients pot cooling program, cool the temperature to less than 45 DEG C, add the porous adsorbent that adsorbs enzyme preparation and
Stirred after other temperature-sensitive materials；
(5) slurry carries out pulling-on piece by pulling-on piece machine, and, at 80 to 90 DEG C, the pull-in time was at 8 to 15 minutes for the temperature of pulling-on piece；
(6) pulling-on piece is cut according to the shape, size for specifying.
Further is made to enzyme-containing detergent sheet-like composition of the invention and preparation method thereof below in conjunction with specific embodiment
Detailed description.
Embodiment
Embodiment 1~5 is the technology used in the present invention, by using specific porous adsorbent, it is ensured that enzyme is in film-making
During stabilization.
The comparative example of table 1 and embodiment detergent tablet containing enzyme are formulated
Note：Ratio described in table is calculated value, and the moisture in piece is not considered.
Comparative example 1~4 is using following technique manufacture detergent tablet：
(1) toward water is added in ingredients pot, stirring is opened, heats the water to 90 DEG C, add polyvinyl alcohol, stirring is to dissolving；
(2) sodium alkyl benzene sulfonate, NaLS, 6501, glycerine, sodium citrate, shallow lake are sequentially added by the proportioning of table 1
Powder；
(3) agitated kettle cooling system is opened, less than 45 DEG C are cooled the temperature to；
(4) enzyme preparation, essence are added, is stirred；
(5) slurry is dried into pulling-on piece by pulling-on piece machine at 85 DEG C, is cut.
Embodiment 1~5 is using following technique manufacture detergent tablet：
(1) toward water is added in ingredients pot, stirring is opened, heats the water to 90 DEG C, add polyvinyl alcohol, stirring is to dissolving；
(2) sodium alkyl benzene sulfonate, NaLS, 6501, glycerine, sodium citrate, shallow lake are sequentially added by the proportioning of table 1
Powder, dispersed with stirring is uniform；
(3) agitated kettle cooling system is opened, less than 45 DEG C are cooled the temperature to；
(4) it is uniformly dispersed after enzyme preparation is mixed with porous adsorbent by batch mixer, until porous adsorbent is by enzyme system
Agent solution adsorb completely and particle between without obvious adhesion reunite；
(5) porous adsorbent, the essence of adsorptive enzyme are added, is stirred；
(6) slurry is dried into pulling-on piece by pulling-on piece machine at 85 DEG C, is cut.
Above-mentioned comparative example 1-4 and embodiment 1-5 final products compare：
The present invention by use specific porous adsorbent, it is ensured that enzyme under high-temperature technology prepared by detergent tablet according to
It is old to keep configuration stably without losing activity, with enzyme preparation vitality retaining percentege higher.The following is comparative example and embodiment
Sample contrast.
Enzyme activity is determined using the full-automatic differentiation assays instrument of Thermo Fisher Arena Scientific 20XT.
Enzyme theory energy value is 100% with sample, and measured value contrast is as shown in the table.
The comparative example of table 2 is contrasted with the enzyme activity conservation rate of embodiment sample
From the above it can be seen that porous adsorbent is not added with comparative example 1~4, and after high temperature dries film-making, portion big absolutely
Enzyme is divided to have been out activity；Comparing embodiment 1~5 and comparative example 1~4, in detergent tablet containing enzyme of the invention, enzyme activity is tried hard to keep
Holdup is greatly improved.
Dissolution time is determined in accordance with the following methods：Laundry sheet is cut into the square plate of 3 × 3cm, standing is gently inserted
Water (diameter>The container of 25cm) in, record laundry sheet is disintegrated the scattered time.
The comparative example of table 3 is contrasted with the dissolution time of embodiment sample
By contrast, it is seen that, had using the embodiment dissolution velocity of the technical program and accordingly lifted, embodiment 3,
4 and 5 in the water for standing, can spread out in 20s.
The comparative example of table 4 is contrasted (ratio of whiteness difference before and after soiled cotton washing) with the detergency of embodiment sample
| JB01 | JB02 | JB03 | |
| Standard liquid detergent | 1.00 | 1.00 | 1.00 |
| Comparative example 4 | 1.06 | 0.98 | 1.03 |
| Embodiment 4 | 1.18 | 2.96 | 1.25 |
| Comparative example 5 | 1.12 | 2.19 | 1.13 |
| Embodiment 5 | 1.19 | 3.21 | 1.18 |
With reference to liquid detergent standard《Dress material liquid detergent standard QB/T 1224-2012》, using standard liquid detergent as
Control, standard liquid detergent wash concentration be 0.2%, detergent tablet wash concentration be 0.07%, carry out standard soiled cloth (JB01,
JB02 and JB03) detergency test, as a result as shown in table 4.
By contrast it is seen that, comparative example 4 is compared using the embodiment 4 and 5 of the technology of the present invention, three kinds of standard soiled cloths
Detergency has lifting, and the detergency lifting of especially albumen soiled cotton JB02 is obvious.Embodiment 4 and the comparison with standard of embodiment 5 are done washing
Liquid, also fully meets the standard of detergency, with excellent detergency.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of detergent tablet containing enzyme, it is characterised in that by weight percentage, including the following raw material component：
One or more in soil.
2. detergent tablet containing enzyme according to claim 1, it is characterised in that the porous adsorbent is for average pore size
10~150nm.
3. detergent tablet containing enzyme according to claim 2, it is characterised in that the granularity of the porous adsorbent is 100
Mesh~3000 mesh.
4. detergent tablet containing enzyme according to claim 1, it is characterised in that the film forming agent be selected from polyvinyl alcohol or
Copolymer containing polyvinyl alcohol block, its number-average molecular weight is 10000~200000.
5. detergent compositions in tablet form containing enzyme according to claim 4, it is characterised in that described containing polyvinyl alcohol block
The monomer of copolymer be vinyl alcohol, and acrylic acid, acrylic acid derivative, ethacrynic acid, α-chloroacrylic acid, α-itrile group acrylic acid,
One kind in butenoic acid, atropic acid, sorbic acid, itaconic acid, maleic acid, maleic acid derivatives, vinylpyrrolidone.
6. detergent tablet containing enzyme according to claim 1, it is characterised in that the surfactant is selected from anion table
Face activating agent, nonionic surfactant, cationic surfactant, one kind of zwitterionic surfactant and its various
Mixture.
7. detergent tablet containing enzyme according to claim 6, it is characterised in that the surfactant is anionic surface
Activating agent and/or nonionic surfactant；The anion surfactant is sulfonate surfactant, carboxylic acid type
One or more in surfactant, sulfated surfactant of mixture；The nonionic surfactant is selected from
The AEO of C12-C18, C12-C14 APGs, C12-C18 alcohol and ethylene oxide/propylene oxide block are common
The condensation product of polymers, cocoanut fatty acid diethanolamide, coconut oil fatty acid monoethanolamide, C8-C20 branched-chain alcoho polyoxy second
One or more in alkene ether of mixture.
8. the detergent tablet containing enzyme according to claim any one of 1-7, it is characterised in that by weight percentage, bag
Include the following raw material component：
9. the detergent tablet containing enzyme according to claim any one of 1-7, it is characterised in that the enzyme be selected from protease,
In amylase, carbohydrase, cellulase, laccase, lipase, oxidizing ferment, peroxidase, pectate lyase, mannase
One kind.
10. the preparation method containing enzyme detergent tablet described in any one of claim 1-9, it is characterised in that including following step
Suddenly：
Water is added in ingredients pot, after being heated to 60 DEG C~90 DEG C, the film forming agent, stirring and dissolving is added；Then then at described
The surfactant, auxiliary agent are added in ingredients pot, is stirred, obtain mixed liquor；
The enzyme is mixed with porous adsorbent, enzymatic mixture is obtained；
The temperature of the mixed liquor is down to less than 45 DEG C, the enzymatic mixture is added, stirring obtains slurry；
Pulling-on piece is carried out to the slurry, is obtained final product.
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| CN108130214A (en) * | 2017-12-08 | 2018-06-08 | 武汉奥克特种化学有限公司 | A kind of functional form cleaning surfactant and preparation method thereof |
| CN109055948A (en) * | 2018-09-20 | 2018-12-21 | 王建东 | A kind of water base wax removing agent in steel and iron parts surface |
| CN112314640A (en) * | 2020-08-03 | 2021-02-05 | 吴丹 | Compound disinfectant with high adsorption performance |
| CN113604294A (en) * | 2021-09-16 | 2021-11-05 | 廊坊佰美生物科技有限公司 | Commercial laundry detergent and preparation method thereof |
| CN115651770A (en) * | 2022-11-02 | 2023-01-31 | 浙江华诺化工有限公司 | A kind of powdery foaming cleanser containing catalase and preparation method thereof |
| CN119776085A (en) * | 2024-12-31 | 2025-04-08 | 佛山市魔晶科技发展有限公司 | Clean water laundry tablet and preparation method thereof |
| CN120866005A (en) * | 2025-07-05 | 2025-10-31 | 广州洁生日化有限公司 | Long-acting enzyme-stabilized washing composition and preparation method thereof |
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