CN105694322A - Water-soluble thin film with good water dissolving performance and small bag prepared from water-soluble thin film - Google Patents
Water-soluble thin film with good water dissolving performance and small bag prepared from water-soluble thin film Download PDFInfo
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- CN105694322A CN105694322A CN201610038696.6A CN201610038696A CN105694322A CN 105694322 A CN105694322 A CN 105694322A CN 201610038696 A CN201610038696 A CN 201610038696A CN 105694322 A CN105694322 A CN 105694322A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D31/00—Bags or like containers made of paper and having structural provision for thickness of contents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
- C08J2331/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention discloses a water-soluble thin film with a good water dissolving performance and a small bag prepared from the water-soluble thin film. The thin film is prepared from allyl acetate and a hydrolyzed derivative of a polymer of a second monomer; the thin film meets the following conditions: (a1) the hydrolyzing degree of the polymer is 90 percent to 99.5 percent; (a2) the viscosity of a water solution of the thin film with the mass percent of 4 percent is 10 centipoises to 25 centipoises; (a3) the thickness of the thin film is 70 microns to 85 microns; (a4) the second monomer is an acrylic monomer. The second monomer is selected from one of acrylic acid, methacrylic acid, acrylate or methacrylate. Before being subjected to ageing treatment, the single small bag prepared from the thin film is completely dissolved in one liter of water within 5 minutes; after being subjected to the ageing treatment, the single small bag prepared from the thin film is completely dissolved in one liter of water within 10 minutes, so that the water-soluble thin film has the very good water dissolving performance.
Description
Invention field
The present invention relates to water-soluble polymer。Specifically, the present invention relates to thin film prepared by water-soluble polymer and the pouch that thin film is made。
Background technology
In recent years, water-soluble polymer is widely used as preparing water-soluble film。The latter is used to prepare pouch。Pouch is a kind of suitable packaging material dosings for detergent。This kind of detergent is mainly fabric detergent compositions, Fabrid care composition, dish washing detergent compositions of automatic bowl agent etc.。Little packed type cleaning product is the facility that consumer provides accurate feeding, has reduced or remitted consumer and has weighed the trouble of detergent。Additionally, little packed type cleaning product also provides detergent to distribute for consumer, mix, the multiple facility such as topples over；Therefore suffer from the attention liking and washing industry of consumer。
For serviceability, one of consumer's problem comparing concern is that can pouch be completely dissolved in washing process。Owing to little packed type cleaning product is deposited in process, the temperature and humidity of environment can allow its solubility property produce change。Specifically, in the environment long-term storage of temperature more than 30 DEG C, pouch can cause that water soluble characteristic is decreased obviously。Thus the use sense affecting consumer is subject to。Therefore the bottleneck restricting the development of packed type Betengent product is become。
Patent US6657004B2 discloses containing oxyethylene group, carboxyl and sulfonic polyvinyl alcohol resin, has good cold water-soluble。Patent US20060559262 discloses the water-solubility membrane of polyvinyl alcohol, chitosan and alkali metal mixture。Patent document US7642226B discloses a kind of copolymer film and includes the vinylacetate of hydrolysis and the copolymer in itaconic acid, and this copolymer film has good cold water-soluble。The blend of a kind of PVOH polymer with good aqueous solubility disclosed in patent US8697624, this copolymer can make the pouch of multi-cavity。Patent US8276756B discloses the pouch that a kind of PVOH polymer is made, and pouch is placed 120 hours in an oven in temperature 38 DEG C and 45% relative humidity, still has good water solublity。Its aging condition is harsh not compared with actual climatic environment, and ageing time is too short, it is impossible to environment residing for more real phantom shoppers's use procedure and deposit the time limit。And its test condition is by the films test dissolution time of cutting certain size on aging rear pouch, and in reality is tested, find edge opposing surface area indissoluble more after aging of pouch, consumer's Actual laundering is easier to remain on medicated clothing, thus this test condition cannot react whole pouch aging after dissolving situation。
The process time that above-mentioned document carries out temperature and humidity for water-solubility membrane is comparatively short, it is impossible to environment residing for more real phantom shoppers's use procedure and deposit the time limit。Additionally, the dissolubility of pouch is tested the zone line mostly being at sack by above-mentioned document cuts a part, then test the solubility behavior of this part。Method of testing and the Actual laundering behavior of this solubility property have different。This is owing to, in testing in reality, the edge of pouch is relatively big due to thickness, is the most insoluble part in this pouch。After experience temperature and humidity processes, the solubility property of marginal portion declines and becomes apparent from。Therefore, in Actual laundering, the marginal portion of pouch is easier to remain on medicated clothing。
In sum, industry needs to develop a kind of environment long-term storage that can experience temperature more than 30 DEG C in a hurry, still keeps the pouch of good water dissolution performance。
Summary of the invention
It is an object of the invention to provide a kind of thin film with good water dissolution performance, stability, prepared by the hydrolysis derivative that described thin film is the polymer of vinyl acetate and second comonomer。
It is a further object to provide and a kind of can prepare the pouch with good water dissolution performance further, it is closed cavity and can be used for containing liquid contents, after the environment long-term storage of temperature more than 30 DEG C, and the pouch good stability of maintenance and solubility property。
Technical scheme is as follows:
A kind of have good water dissolution performance, the thin film of stability and the pouch made thereof, and described thin film is the hydrolysis derivative of the polymer of vinyl acetate and second comonomer, and described thin film meets the following conditions；
A1) degree of hydrolysis of polymer is 90% to 99.5%；
A2) second comonomer is acrylic monomer；It is 2%-9% that second comonomer accounts for the molar percentage of water-soluble polymer；
A3) mass percent to be the solution viscosity of the thin film of 4% be 10 centipoises are to 25 centipoises；
A4) thickness of thin film is 70 microns to 85 microns。
Described acrylic monomer is selected from acrylic acid, methacrylic acid, acrylate, any one in methacrylate。
Described thin film can also contain plasticizer, and plasticizer mass percent in the film is 1% to 30%, selected from the mixture that glycerol, propylene glycol, trimethylolpropane are a kind of and multiple。
Described thin film can also contain water, and water mass percent in the film is 5% to 10%。
Described water-soluble film, it can be prepared according to following processing step:
The hydrolysis derivative of vinyl acetate and acrylic acid copolymer stirring and dissolving at 93 DEG C being formed slurry, is cooled to 85 DEG C, add the auxiliary agent such as glycerol, propylene glycol after ten h apart, on surface suitable again after mix homogeneously, curtain coating forms thin film。
The pouch that above-mentioned thin film is made is the closing cavity of tetragon, and cavity length is 2 centimetres to 8 centimetres, and wide is 1 centimetre to 6 centimetres, and the closed volume of cavity is 5 milliliters to 40 milliliters。The quality closing cavity is 0.2 gram to 1.5 grams。Pouch can be used for containing liquid contents, and the volume of content is 5 to 30 milliliters。
Described liquid contents is composition of detergent, comprises surfactant, washing assisant, solvent and their mixture。
Good water dissolution performance refers to: before the pouch experience burin-in process that described thin film is made, in 1 liter of water, be completely dissolved in 5 minutes；After pouch that thin film is made experience burin-in process in 1 liter of water, the time that is completely dissolved is less than 10 minutes。
Good stability refers to: after containing the pouch experience burin-in process of liquid contents, occurring without leakage, surface is tack-free。
Burin-in process refers to: the pouch made by thin film is put into when 25 DEG C and 35% relative humidity in high density polyethylene (HDPE) bag and sealed；High density polyethylene (HDPE) bag containing pouch is placed 4 weeks in the environment of 50 DEG C and 80% relative humidity, 8 weeks, 12 weeks。
By technique scheme, the present invention has the advantage that and provides the benefit that:
1, the present invention uses thin film prepared by specific water-soluble polymer to can be used for preparing the pouch with good water dissolution performance。
2, after pouch provided by the invention experience burin-in process, there is good water dissolution performance。
3, pouch provided by the invention can be used for containing liquid detergent composition, has good stability before and after experience burin-in process。
Detailed description of the invention
For a person skilled in the art, by reading the disclosure of the specification, inventive feature, beneficial effect and advantage will become clear from。
Except as otherwise noted, all percentage ratios, mark and ratio are all by the total weight of the present composition。Except as otherwise noted, being the content of active substance about all wt of ingredients listed, therefore they are likely to the solvent or the by-product that comprise not included in commercially available material。Term " weight percentage " available symbols " wt% " represents herein。
Except as otherwise noted, there is the environment at 25 DEG C in all preparations and test in this article。
Except as otherwise noted, " water " in this article, " aqueous solution ", " water " in " water solublity " and solubility property refers to tap water or is suitable for the domestic water of washing。
" include " herein, " comprising ", " containing ", " containing ", " having " or other variant be intended to non-enclosed including, do not distinguish between these terms。Term " comprises " and refers to and can add other step and composition not affecting final result。Term " comprise " also include term " by ... composition " and " substantially by ... form "。The compositions and methods of the invention/technique can comprise, consisting of be substantially made up of essential elements described herein and limit entry and arbitrary additional or optional composition described herein, component, step or limit entry。
Water-soluble polymer
The water-soluble polymer that the present invention relates to is used to prepare water-soluble film。Such as this area, oneself knows, it is possible to extrude acquisition water-soluble film by polymeric material casting, blowing, extrusion or inflation。Preferably can prepare that the material of water-soluble film includes polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene oxide, acrylamide, acrylic acid, cellulose, cellulose ether, cellulose esters, cellulose amides, polyvinyl acetate, polycarboxylic acids and salt, polyamino acid or peptide, polyamide, polyacrylamide, maleic acid/acrylic acid copolymer, polysaccharide include starch and gelatin, natural gum such as xanthan gum and carrageenin and their mixture。It is highly preferred that comprise polyacrylate and water-soluble acrylic ester copolymer, methylcellulose, carboxymethyl cellulose, dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, maltodextrin, polymethacrylates and their mixture。Most preferably, polyvinyl alcohol, polyvinyl alcohol copolymer and their mixture are comprised。
Acetoxyl group ethylene unit and hydroxyl ethylene unit
During vinyl acetate polyisocyanate polyaddition, the construction unit of its generation is acetyl oxygen ethylene unit。Acetyl oxygen ethylene unit is in the presence of a base, it may occur that hydrolyze to form hydroxyl ethylene unit。The hydrolytic process of the polymer containing acetyl oxygen ethylene is as follows。
The alkali metal such as M:Na, K。
Polyvinyl alcohol
The hydrolyzate of the homopolymer of vinyl acetate is called polyvinyl alcohol。The construction unit of polyvinyl alcohol includes hydroxyl ethylene unit and acetyl oxygen ethylene unit。Polyvinyl alcohol is presently the most widely used water-soluble polymer, is used for making water-soluble film and pouch。
The hydrolysis derivative of the polymer of vinyl acetate and second comonomer
In the present invention, the monomer of water-soluble polymer is vinyl acetate and second comonomer。Second comonomer is acrylic monomer, selected from acrylic acid, the one of methacrylic acid or its mixture。
Containing acetoxyl group ethylene unit and second comonomer unit in the constitutional unit of vinyl acetate and second comonomer。For acrylic acid, it is carboxyl ethylene unit with second comonomer unit in the copolymer of the formation of ethyl acetate。
In the present invention, second comonomer molar percentage in the polymer is 2% to 9%。
The polymer of vinyl acetate and second comonomer is under alkali effect, and the hydrolysis of acetoxyl group ethylene unit produces hydroxyl ethylene unit；Its product is called the hydrolysis derivative of polymer。
Mole
Using the aggregation containing 6.02 × 1023 microgranules as a unit, being called mole, it indicates that the unit of amount of substance (symbol is n), and referred to as rubbing, unit symbol is mol。
Degree of hydrolysis
In the present invention, in polymer, hydroxyl ethylene unit accounting represents with degree of hydrolysis。Degree of hydrolysis is calculated as follows:
The method of testing of degree of hydrolysis has a detailed description in CNS " GB/T12010.2-2010 plastic polyethylene alcohol material (PVAL) part 2: performance measurement "。In " GB/T12010.2-2010 ", degree of hydrolysis is called alcoholysis degree, and both are meant that consistent。
The degree of hydrolysis method of testing of the present invention carries out according to " GB/T12010.2-2010 plastic polyethylene alcohol material (PVAL) part 2: performance measurement "。
The water-soluble polymer of the present invention is the hydrolysis derivative of the polymer of vinyl acetate and second comonomer, and degree of hydrolysis is 90% to 99.5%。
Water-soluble film
Water-soluble film involved in the present invention comprises water-soluble polymer, plasticizer, moisture。
Water-soluble polymer refers to the hydrolysis derivative of the polymer of vinyl acetate and second comonomer。
Plasticizer mass percent in the film is 1% to 30%, selected from the mixture that glycerol, propylene glycol, trimethylolpropane are a kind of and multiple。
Water mass percent in the film is 5% to 10%。
The thickness of water-soluble film
The inventors discovered that, the thickness of water-soluble film is relevant with the dissolubility of pouch。The thickness of the water-soluble film that the present invention relates to is 70 microns to 85 microns。
Water-soluble film thickness measuring uses the digital display calibrator of Zhong Huitian city, Beijing Science and Technology Ltd., specific experiment method is as follows: opening power, press " mm/in " key selection unit system (having " mm " character to occur during metric system), screw gauge rod, press " 0 " key and make numerical value zero setting。Thin film is sandwiched in the middle of two gauge rods by gauge rod of outwarding winding, and treats that thin film does not vertically drop, and gauge rod does not press to thin film, and reading now is the thickness of thin film。
The viscosity of water-soluble film
The inventors discovered that, at a certain temperature, the viscosity of the certain concentration aqueous solution of water-soluble film is relevant with the dissolubility of pouch。Specifically, specified temp refers to 20 DEG C；The solution of certain concentration refers to the aqueous solution of the water-soluble film that mass percent is 4%。
The present invention adopts BrookfieldLV type viscometer, No. 2 rotors。
The water-soluble film that the present invention selects, at 20 DEG C, its mass percent be 4% solution viscosity be 10 centipoises to 25 centipoises。Pouch
The pouch that the present invention relates to is the closing cavity of the tetragon that water-soluble film manufactures。Cavity length 2 centimetres to 8 centimetres, wide 1 centimetre to 6 centimetres, the closed volume of cavity is 5 milliliters to 40 milliliters。
Close cavity and include at least one sealed compartments。Therefore, described pouch can include single compartment or multiple compartment。In the embodiment including multiple compartment, each compartment can comprise identical and/or different contents。
The burin-in process of pouch
The burin-in process that the present invention relates to refers to be put into when 25 DEG C and 35% relative humidity by the pouch containing liquid contents in high density polyethylene (HDPE) bag and seals；High density polyethylene (HDPE) bag containing pouch is placed a period of time in the environment of 50 DEG C and 80% relative humidity。
In the present invention, ageing time refers to the time that high density polyethylene (HDPE) bag containing pouch is placed in the environment of 50 DEG C and 80% relative humidity。
The solubility property of pouch
The solubility property that the present invention relates to refers to pouch dissolving situation in the water of 1 liter。1 pouch containing liquid contents is placed in beaker, pouch stir in beaker, dissolves a period of time after, stopping is stirred。At once by solution all in beaker and the residue sieved filter of yarn of 60 orders, the filtering residue situation sieved according to yarn in 5 minutes carries out solubility property grading。
In the present invention, pouch stirs in beaker, time of dissolving is called dissolution time。For the pouch without burin-in process, its dissolution time is 5 minutes。For experiencing the pouch of burin-in process, dissolution time is 10 minutes。
Solubility property grading is as shown in table 1。Solubility property adopts visual method to determine, grade 1 represents and is completely dissolved, and class 4 represents insoluble。
Table 1 solubility property evaluation and grade
The stability of pouch
After in the present invention, stability refers to the pouch experience burin-in process containing liquid contents, complete situation and touch impression to its surface are evaluated。Stability is evaluated and grade is as shown in table 2。
Table 2 stability evaluation and grade
| The complete situation in surface | Touch impression | Stability grade |
| Complete appearance, liquid contents does not leak | Surface is tack-free | Well |
| Complete appearance, liquid contents does not leak | Hands is glued on surface | Medium |
| Outward appearance is imperfect, and liquid contents leaks | Surface is tack-free | Poor |
| Outward appearance is imperfect, and liquid contents leaks | Hands is glued on surface | Difference |
Liquid contents
In the present invention, pouch can be used for containing liquid contents, and the volume of content is 5 to 30 milliliters。Liquid contents is composition of detergent, comprises surfactant, washing assisant, solvent, deionized water and their mixture。
In the present invention, surfactant is selected from anion surfactant, nonionic surfactant, a kind of and multiple mixture of amphoteric surfactant。The anionicsite of the anion surfactant in the present invention is selected from LABS root, fatty alcohol sulphuric acid root, fatty alcohol-polyoxyethylene ether sulfate radical, fatty acid radical。The cationic moiety of the anion surfactant in the present invention is selected from the alkali metal cation such as sodium, potassium and ammonia, monoethanolamine, diethanolamine, triethanolamine in conjunction with the ammonium root cation formed after proton。
Nonionic surfactant in the present invention is selected from fatty alcohol alkoxy compound。Fatty alcohol alkoxy compound is fatty alcohol and epoxyalkane product of ring-opening polymerisation under base catalyst effect, substantially mixture。Fatty alcohol includes the isomery alcohol of straight chain alcohol or side chain。Alkoxy grp includes ethoxy group and propoxyl group group。The preferred carbon number of fatty alcohol is the fatty alcohol of 8 to 18, preferred alcohol includes, but are not limited to capryl alcohol, decanol, 2-ethylhexanol, 3-propyl enanthol, lauryl alcohol, different three decanol, tridecyl alcohol, tetradecanol, hexadecanol, Palmitoleyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol, sub-oleyl alcohol, the one of linolenyl alcohol and mixture thereof。Average ethoxylation degree preferably 6 to 12。Preferred example is SHELL company NEODOL series linear primary alcohol ethoxylate product, DOW company ECOSURFEH series ethoxylation and the third oxidation 2-ethylhexanol product, BASF AG LutensolXL series ethoxylation and the third oxidation 3-propyl enanthol product and BASF AG LutensolXP series ethoxylation 3-propyl enanthol product。
In some embodiments, non-ionic surfactant mixture contains APG, has below general formula:
Wherein, n is 6 to 24, and p is 1.1 to 3。Preferred n is 8 to 16。Suitable APG is BASF AG Glucopon series alkyl polyglucoside product such as。
Non-ionic surfactant mixture can contain fatty acid alkyl alcohol amide, and the carbon number of fatty acid is 6 to 24, it is possible to is the fatty acid of straight chain, it is also possible to is the fatty acid of side chain, it is possible to is saturated fatty acid, it is also possible to is undersaturated fatty acid；Alkylol number is 0 to 2。Preferred fatty acid carbon number is a glycollic amide of 8 to 18, diglycollic amide, and isopropanol amide, suitable example is cocoanut oil diethan olamide。
Zwitterionic surfactant in the present invention comprises betaine type amphoteric surfactant, Imidazoline Surfactants, amino acid type surfactant, amine oxide type surfactant；Include, but are not limited to: alkyl betaine, fatty acid amide glycine betaine, fattyamidopropyl betaine, 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, fatty acyl amido dimethylamine oxide etc.。
Solvent
In the present invention, the solvent of liquid contents is selected from glycerol, 1,2-PD, ethanol。
Washing assisant
The washing assisant of the liquid contents in the present invention is selected from the group of the compositions such as fluorescent whitening agent, enzyme preparation, anti redeposition agent。
Fluorescent whitening agent
The liquid contents that the present invention relates to preferably comprises fluorescent whitening agent。Fluorescent whitening agent application in detergent compositions is technology known in the art, and has much commercially available fluorescent whitening agent commodity。Fluorescent whitening agent exists with its alkali metal salt (mostly being sodium salt) form。Preferred fluorescent whitening agent including but not limited to: diphenylethyllene connects benzene compound。Suitable example is 4,4'-double; two (2-sodium sulfonate styryl) biphenyl, such as the product of BASF AG's CBS-X trade mark。Diamidogen stilbene two-sulfoacid compound。Suitable example is 4,4 '-bis-[(4-phenylamino 6-morpholino-1,3,5-, triazine-2-base)] amino stilbene-2,2 '-disulfonate。The group formed selected from following compound can be comprised: 2-(4-styryl-3-sulfo group phenyl)-2H-naphtho-[1,2-d] 1-Sodium-1,2,4-Triazole, 4,4 '-bis-{ [(4-phenylamino 6-(N-methyl-N-2-ethoxy) amino-1,3,5-, triazine-2-base)] amino stilbene-2,2 '-disulfonate, 4,4 '-bis-[(4-phenylamino 6-morpholino-1,3,5-, triazine-2-base)] amino } stilbene-2,2 '-disulfonate, 4,4 '-bis-(2-sulfostyryl) biphenyl disodiums。
Enzyme preparation
The liquid contents that the present invention relates to can comprise one or more of enzyme preparation, to provide clean-up performance, and fabric nursing and/or other beneficial effect。Described enzyme preparation is grouped selected from following enzyme: protease, α-amylase, cellulase, hemicellulase, phospholipase, esterase, lipase, peroxidase/oxidase, pectase, lyases, mannase, at, reductase, xylanase, amylopectase, tannase, pentosanase, 1,6-Anhydromaltose, arabinase, 1,4 beta-glucanase。Conventional enzyme preparation is protease, amylase, lipase, at and/or cellulase。
The liquid contents of the present invention can comprise enzyme stabilising system。Described enzyme stabilising system can be compatible with composition of detergent, can comprise calcium ion and other metal ions, boric acid, Borax, propylene glycol, glycerol, the one of polyhydric alcohol and mixture thereof。The weight of enzyme stabilising system and consumption are adjusted with the type of the form according to composition of detergent and composition and enzyme preparation。
Anti redeposition agent
The liquid contents that the present invention relates to comprises anti redeposition agent。Described anti redeposition agent includes, but are not limited to the component of following compound composition: polyacrylic acid and salt derivative thereof, cellulose derivative is carboxymethyl cellulose such as, ethylhydroxyethylcellulose, methylcellulose；The homopolymer of vinyl pyrrolidone and copolymer be straight linear polyethylene base ketopyrrolidine such as, the copolymer of vinyl pyrrolidone and vinyl acetate, the copolymer of vinyl pyrrolidone and vinyl imidazole。
Optional member
The liquid contents that the present invention relates to comprises additive optional as follows: preservative, coloring agent, essence。
In some embodiments, the liquid contents that the present invention relates to preferably comprises preservative, and suitable example is phenoxy group alcohol, sodium benzoate；Isothiazolone and derivant thereof such as Methylisothiazolinone, methylchloroisothiazandnone, the one of BIT or its mixture。
In some embodiments, the liquid contents that the present invention relates to contains coloring agent, and described coloring agent comprises dyestuff and pigment。Coloring agent can comprise all in cleaning product application coloring agent, suitable example such as acid red G, basic fuchsin, Methanil Yellow G, Acid Light Yellow G, alkalescence egg yolk, direct fast blue B2RL, indigo-blue etc.。
The liquid contents that the present invention relates to preferably comprises spice, and described spice comprises all fragrance components being applicable to cleaning product。The spice used of the present invention can be natural origin, it is also possible to is the goods of chemosynthesis, or the mixture of the two。Suitable example such as Fructus Citri Limoniae, Flos Rosae Rugosae, jasmine, lavandula angustifolia, Citrus are fragrant, QINGXIANG, the Radix Aucklandiae etc.。
The preparation method of pouch
In an embodiment, pouch is prepared according to following methods:
1) first bottom film being heated on heating roller, heating-up temperature is 30-50 DEG C。
2) utilizing vacuum to be sucked in suitable mould by bottom film, treat that thin film and mould fit, be filled in mould by liquid contents, addition can adjust according to mould size。
3) heat seal or moistening is adopted to seal surface film and bottom surface diaphragm seal。Preferably apply the water to upper layer film surface, then apply pressure to form sealing to sealing area。
Without further describing, it is believed that those skilled in the art use the above can use the present invention to greatest extent。The following examples purpose is in that to be further described and show specific embodiments within the scope of the present invention。Therefore, embodiment is it should be understood that be used only for showing in more detail the present invention, and the content not limited the present invention in any way。
In following example, except as otherwise noted, all of content is all weight percentage, and the content about ingredients listed is the content through the active substance converted。
The performance test of water-soluble film
The degree of hydrolysis test of water-soluble film, viscosity test and thickness measuring。These three test is called the performance test of water-soluble film。
Degree of hydrolysis testing procedure is as follows:
1) weigh 3 grams of water-soluble films, put in conical flask；Add 3 phenolphthalein solutions of 200 milliliters of hydrations, if display pink, then add 5 milliliters of 0.1 mol/L sulphuric acid；It is placed in dissolution equipment, heats and be completely dissolved to sample, open wide conical flask simultaneously, allow volatile organic matter overflow；
2) solution is cooled to room temperature, is titrated to pink with Standard Volumetric Solutions for Sodium Hydroxide；Accurately add the Standard Volumetric Solutions for Sodium Hydroxide of 0.5 mol/L of 25 milliliters, cover conical flask, shake up；At room temperature place more than 2 hours；
3) add the sulphuric acid of 25.00 milliliter of 0.5 mol/L, cover conical flask, shake up。
Viscosity test determination step is as follows: water-soluble film is made into the aqueous solution that mass percent is 4%, adopts BrookfieldLV type viscometer at 20 DEG C, and No. 2 rotors measure viscosity。
Thickness measuring step is as follows: using digital display calibrator, specific experiment method is as follows: opening power, presses " mm/in " key selection unit system (having " mm " character to occur during metric system), screws gauge rod, press " 0 " key and make numerical value zero setting。Thin film is sandwiched in the middle of two gauge rods by gauge rod of outwarding winding, and treats that thin film does not vertically drop, and gauge rod does not press to thin film, and reading now is the thickness of thin film。Test result is as shown in table 4 below。
Water-soluble film A-H is prepared according to table 3 formula:
The composition of table 3 water-soluble film A-H
Thin, water soluble membrane preparation method is as follows:
The hydrolysis derivative of vinyl acetate and acrylic acid copolymer stirring and dissolving at 93 DEG C being formed slurry, is cooled to 85 DEG C, add the auxiliary agent such as glycerol, propylene glycol after ten h apart, on surface suitable again after mix homogeneously, curtain coating forms thin film。
The performance test results of table 4 water-soluble film
The preparation of liquid contents
Liquid contents preparation method step is as follows:
1) in preparing tank, deionized water and solvent are added；
2) starting stirring, add following various surfactant, be warming up to 60 DEG C, stirring is to being completely dissolved；
3) withdrawing thermal source, in temperature lower than 45 DEG C, add fluorescent whitening agent, essence, pigment, preservative, stirring is to being completely dissolved。
Table 5 is the composition of liquid contents A and liquid contents B。
The composition of table 5 liquid contents
The preparation method embodiment of pouch
Pouch preparation method is as follows:
1) first bottom film being heated on heating roller, heating-up temperature is 45 DEG C；
2) utilize vacuum to be sucked in suitable mould by bottom film, treat that thin film and mould fit, 25 grams of liquid contents are filled in mould；
3) apply the water to upper layer film surface, then apply pressure to form sealing to sealing area。
Embodiment 1-4 and comparative example 1-4 it is prepared for, as shown in table 6 by this step。
The composition of table 6 embodiment 1-4 and comparative example 1-4 pouch
| Embodiment/comparative example | Name | Water-soluble film | Liquid contents |
| Embodiment 1 | Pouch A | Water-soluble film A | Liquid contents A |
| Embodiment 2 | Pouch B | Water-soluble film B | Liquid contents B |
| Embodiment 3 | Pouch C | Water-soluble film C | Liquid contents A |
| Embodiment 4 | Pouch D | Water-soluble film D | Liquid contents A |
| Comparative example 1 | Pouch E | Water-soluble film E | Liquid contents A |
| Comparative example 2 | Pouch F | Water-soluble film F | Liquid contents B |
| Comparative example 3 | Pouch G | Water-soluble film G | Liquid contents A |
| Comparative example 4 | Pouch H | Water-soluble film H | Liquid contents A |
The burin-in process of pouch
By embodiment 1-4 and the comparative example 1-4 pouch prepared at 25 DEG C, put into when 35% relative humidity humidity in high density polyethylene (HDPE) bag and seal；Take out after high density polyethylene (HDPE) bag containing pouch is placed a period of time in the environment of 50 DEG C and 80% relative humidity。Standing time is 4 weeks, 8 weeks, 12 weeks。
The solubility property test of pouch
To before experience burin-in process and the pouch prepared of embodiment 1-4 and comparative example 1-4 carry out solubility property test, step is as follows:
1) adding 1000 milliliters of water in the beaker of 1 liter, temperature controls at 20 DEG C ± 0.1 DEG C。Beaker is put into stirrer, opens magnetic agitation。Promoting mixing speed, until vortex occurs in the water surface, vortex distance water surface elevation is in beaker the 1/3 of liquid height。Keep mixing speed now。
2) 1 pouch containing liquid contents is placed in beaker, pouch stir in beaker, dissolves a period of time after, stopping is stirred。
3) at once by solution all in beaker and the residue sieved filter of yarn of 60 orders, the filtering residue situation sieved according to yarn in 5 minutes carries out solubility property grading。For the pouch without burin-in process, its dissolution time is 5 minutes。For experiencing the pouch of burin-in process, dissolution time is 10 minutes。
By table 7 below, solubility property is graded。Result is as shown in table 7。
The solubility property of table 7 pouch
| Embodiment/comparative example | Name | Before burin-in process | Aging 4 weeks | Aging 8 weeks | Aging 12 weeks |
| Embodiment 1 | Pouch A | It is completely dissolved | It is completely dissolved | It is completely dissolved | It is completely dissolved |
| Embodiment 2 | Pouch B | It is completely dissolved | It is completely dissolved | It is completely dissolved | It is completely dissolved |
| Embodiment 3 | Pouch C | It is completely dissolved | It is completely dissolved | It is completely dissolved | It is completely dissolved |
| Embodiment 4 | Pouch D | It is completely dissolved | It is completely dissolved | It is completely dissolved | It is completely dissolved |
| Comparative example 1 | Pouch E | It is completely dissolved | A small amount of dissolving | A small amount of dissolving | A small amount of dissolving |
| Comparative example 2 | Pouch F | A large amount of dissolvings | A small amount of dissolving | A small amount of dissolving | A small amount of dissolving |
| Comparative example 3 | Pouch G | A large amount of dissolvings | A large amount of dissolvings | A large amount of dissolvings | A small amount of dissolving |
| Comparative example 4 | Pouch H | A large amount of dissolvings | A large amount of dissolvings | A small amount of dissolving | A small amount of dissolving |
By table 7 data it is found that embodiment 1-4 all has the solubility property being better than comparative example 1-4 before and after burin-in process。
The stability test of pouch
To before experience burin-in process and the pouch prepared of embodiment 1-4 and comparative example 1-4 carry out stability test。Complete situation and touch impression to its surface are evaluated, and evaluation rule is as shown in table 8。Table 8 is the stability evaluation result of pouch。The stability of table 8 pouch
| Embodiment/comparative example | Name | Before burin-in process | Aging 4 weeks | Aging 8 weeks | Aging 12 weeks |
| Embodiment 1 | Pouch A | Well | Well | Well | Well |
| Embodiment 2 | Pouch B | Well | Well | Well | Well |
| Embodiment 3 | Pouch C | Well | Well | Well | Well |
| Embodiment 4 | Pouch D | Well | Well | Well | Well |
| Comparative example 1 | Pouch E | Well | Well | Well | Well |
| Comparative example 2 | Pouch F | Well | Well | Well | Well |
| Comparative example 3 | Pouch G | Well | Well | Well | Well |
| Comparative example 4 | Pouch H | Well | Medium | Poor | Difference |
As shown in table 8, embodiment 1-4 and comparative example 1,2,3 all have good stability before and after experience burin-in process。
Based on the above results, embodiment 1-4 all has the combination property being better than comparative example 1-4 before and after burin-in process。
Dimension disclosed herein and numerical value should not be construed as the strict restriction of described exact value。Unless otherwise indicated, each such dimension is intended to indicate that described value and the functionally equivalent scope around this value。Such as, the dimension being disclosed as " 40mm " is intended to indicate that " about 40mm "。
During the All Files quoted in summary of the invention is all incorporated herein with way of reference in relevant portion。Quoting of any file is not construed as admitting that it is prior art for the present invention。
Although having illustrate and described specific embodiments of the present invention, but it is obvious to those skilled in the art that can make when without departing substantially from spirit and scope of the present invention multiple other amendment and modification。These amendments and modification are all included within protection scope of the present invention。
Claims (10)
1. a water-soluble film with good water dissolution performance, it is characterised in that: described water-soluble film is the hydrolysis derivative of the polymer of vinyl acetate and second comonomer, and described water-soluble film meets the following conditions:
1) second comonomer is acrylic monomer, and it is 2%-9% that second comonomer accounts for the molar percentage of water-soluble polymer；
2) degree of hydrolysis of polymer is 90% to 99.5%；
3) mass percent to be the solution viscosity of the thin film of 4% be 10 centipoises are to 25 centipoises；
4) thickness of thin film is 70 microns to 85 microns。
2. water-soluble film as claimed in claim 1, it is characterised in that: described acrylic monomer is selected from acrylic acid, methacrylic acid, acrylate, any one in methacrylate。
3. water-soluble film as claimed in claim 1, it is characterised in that: it can also contain plasticizer or water, and described plasticizer mass percent in the film is 1% to 30%, one or more mixture in glycerol, propylene glycol, trimethylolpropane；Described water mass percent in the film is 5% to 10%。
4. water-soluble film as claimed in claim 1, it is characterised in that: it can be prepared according to following processing step:
The hydrolysis derivative of vinyl acetate and acrylic acid copolymer stirring and dissolving at 93 DEG C being formed slurry, is cooled to 85 DEG C, add the auxiliary agent such as glycerol, propylene glycol after ten h apart, on surface suitable again after mix homogeneously, curtain coating forms thin film。
5. the pouch that the water-soluble film according to any one of claim 1-4 is made, it is characterized in that: described pouch is the closing cavity of the tetragon being made up of described water-soluble film, cavity length is 2 centimetres to 8 centimetres, wide is 1 centimetre to 6 centimetres, the closed volume of cavity is 5 milliliters to 40 milliliters, and cavity quality is 0.2 gram to 1.5 grams。
6. the pouch that water-soluble film as claimed in claim 5 is made, it is characterised in that: before single pouches experience burin-in process, in 1 liter of water, it is completely dissolved in 5 minutes；After single pouches experience burin-in process in 1 liter of water, it is completely dissolved in 10 minutes；Described burin-in process refers to that the pouch made by thin film is at 25 DEG C, puts in high density polyethylene (HDPE) bag and seal when 35% relative humidity；High density polyethylene (HDPE) bag containing pouch is placed 4 weeks in the environment of 50 DEG C and 80% relative humidity, 8 weeks, 12 weeks。
7. the pouch that water-soluble film as claimed in claim 6 is made, it is characterised in that: it can be used for containing liquid contents, and the volume of described liquid contents is 5 to 30 milliliters。
8. the pouch that water-soluble film as claimed in claim 7 is made, it is characterised in that: described liquid contents is composition of detergent, comprises surfactant, washing assisant, solvent, deionized water and their mixture；Described surfactant is selected from anion surfactant, nonionic surfactant, a kind of and multiple mixture of amphoteric surfactant；Described washing assisant is selected from the group of the compositions such as fluorescent whitening agent, enzyme preparation, anti redeposition agent；Described solvent is selected from glycerol, 1,2-PD, ethanol。
9. the pouch that water-soluble film as claimed in claim 8 is made, it is characterised in that: described nonionic surfactant is selected from fatty alcohol alkoxy compound；
Described zwitterionic surfactant comprises betaine type amphoteric surfactant, Imidazoline Surfactants, amino acid type surfactant, amine oxide type surfactant；Include, but are not limited to: alkyl betaine, fatty acid amide glycine betaine, fattyamidopropyl betaine, 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, fatty acyl amido dimethylamine oxide etc.；
Described fluorescent whitening agent including but not limited to: diphenylethyllene connects benzene compound；
Described enzyme preparation is grouped selected from following enzyme: protease, α-amylase, cellulase, hemicellulase, phospholipase, esterase, lipase, peroxidase/oxidase, pectase, lyases, mannase, at, reductase, xylanase, amylopectase, tannase, pentosanase, 1,6-Anhydromaltose, arabinase, 1,4 beta-glucanase；
It also comprises enzyme stabilising system, anti redeposition agent, optional additive: preservative, coloring agent, essence and coloring agent, spice etc.。
10. the pouch that water-soluble film as claimed in claim 8 is made, it is characterised in that: it can prepare according to following processing step:
1) first bottom film being heated on heating roller, heating-up temperature is 30-50 DEG C；
2) utilizing vacuum to be sucked in suitable mould by bottom film, treat that thin film and mould fit, be filled in mould by liquid contents, addition can adjust according to mould size；
3) heat seal or moistening is adopted to seal surface film and bottom surface diaphragm seal。Preferably apply the water to upper layer film surface, then apply pressure to form sealing to sealing area。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610038696.6A CN105694322A (en) | 2016-01-20 | 2016-01-20 | Water-soluble thin film with good water dissolving performance and small bag prepared from water-soluble thin film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610038696.6A CN105694322A (en) | 2016-01-20 | 2016-01-20 | Water-soluble thin film with good water dissolving performance and small bag prepared from water-soluble thin film |
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| CN105694322A true CN105694322A (en) | 2016-06-22 |
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| CN201610038696.6A Pending CN105694322A (en) | 2016-01-20 | 2016-01-20 | Water-soluble thin film with good water dissolving performance and small bag prepared from water-soluble thin film |
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| WO2018223357A1 (en) * | 2017-06-09 | 2018-12-13 | Dow Global Technologies Llc | Multilayer films and laminates containing slip agents |
| CN115926896A (en) * | 2022-11-02 | 2023-04-07 | 合创(广州)科技研究有限公司 | High viscosity water soluble unit dose detergent compositions and process for making same |
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Inventor after: Ma Yujie Inventor after: Sun Yiheng Inventor after: Huang Liang Inventor after: Chen Yue Inventor after: Wu Pingping Inventor after: Mai Kancheng Inventor after: Zhang Liping Inventor before: Ma Yujie Inventor before: Sun Yiheng Inventor before: Huang Liang Inventor before: Chen Yue Inventor before: Wu Pingping Inventor before: Zhang Liping |
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