CN101137550A - Process for the preparation of a package containing compacted composition and the package obtained with this process - Google Patents
Process for the preparation of a package containing compacted composition and the package obtained with this process Download PDFInfo
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- CN101137550A CN101137550A CNA2006800074916A CN200680007491A CN101137550A CN 101137550 A CN101137550 A CN 101137550A CN A2006800074916 A CNA2006800074916 A CN A2006800074916A CN 200680007491 A CN200680007491 A CN 200680007491A CN 101137550 A CN101137550 A CN 101137550A
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Abstract
A process for the preparation of a package containing a compacted particulate composition, comprises wrapping a compacted particulate composition with a first film and treating the wrapped compacted particulate composition at an elevated temperature to shrink the film such that it clings to said composition. The resulting packages maybe made using low compaction pressures and consequently may have low friability and be fast dissolving.
Description
Technical field
The present invention relates to be used to make the method for the water soluble package product that comprise the compacted granules composite.
Background technology
The compressing grains composition tablet that is used for dishwashing detergent machine or clothes washing machine is well-known.Such tablet adds when described machine brings into operation, and is fallen by full consumption when end of run.The example of described tablet has the dishwashing detergent tablet of selling such as with trade mark Finish, the water softening tablet of selling with trade mark Calgon, and with the cloth-washing detergent tablet of trade mark Persil sale.
These tablets are more crisp relatively, and are easily broken, break or cracked, and particularly when the customer falls it on the ground, perhaps when preserve in for example storehouse or supermarket, the package that described tablet is housed is during from overhead dropping.Pressure in the time of can being used for the tablet compression by raising improves its intensity, but this can hinder its dissolving in use, and this is undesirable.
When the such product of exploitation, often there be complicated influencing each other between each factor.Usually to take into account the hardness of tablet and relevant durability thereof, fragility, cracked or the difficulty and the dissolution time that peel off.When making the compacted granules composite, components selection also can be restricted; Use organic material usually can cause the product dissolving slowly too much, a large amount of crystallographic components then needs to add adhesives.In any case, usually all need to add at least a disintegrant, for example the water soluble salt of hydration (for example sodium acetate trihydrate), sweller (for example amorphous cellulose) or be used for water is introduced the wick feed agent (wicking agent) (for example microcrystalline cellulose) of solid.Use disintegrant/adhesives or other auxiliary agents in blocks all can increase the cost of tablet.
Most of tablets all are wrapped in before packing in the material, as blister pack (blister pack) or be rolled in the paillon foil of single pouches.Usually, because following any one or more former thereby need packing: (1) plays the effect of physical barriers, makes moist to prevent content; (2) physical protection content, the broken tablet in back can pollute primary package in case it breaks; (3) closure of using as anti-child.
The packing of tablet are known in this area.For example US 4,133, and 431 have disclosed a folded frangible tablet constrictor (shrink), and this constrictor wraps up with rigidity spacer and indicating member between every tablet group and folded end.US 4,928, and 813 have disclosed the capsule that contains the tablet part, at least a chlorine compound tablet is wherein arranged and be securely fixed in this tablet part shell on every side.Described shell has two holes at opposite end, and each elongated hole (extension) all partly extends from tablet, and has the conduit that is communicated with aperture, dissolves in speed in the water to reduce described chloride.
DE 10025187 has disclosed the tablet that is packaged in the paper tinsel bag, and this tablet is placed in the external packing that is formed by non-self-supporting packing.Described packing can be made by paper or the plastics foliation sheet (shrink fit foil) that for example contracts, and only need foil pouch is partly surrounded.DE 10254313 has disclosed has at least one seals the hole of opening with film molded Betengent product, and wherein said film surrounds described mechanograph with cover or obducent form.JP 2,004 155019 A have disclosed the hard vinyl chloride resin sheet, and it forms package sheet material through vacuum forming or extrusion forming.
DE 10245260 A1 have disclosed the manufacture method of the cleaning agent part that is close in the water soluble package.Described manufacture method comprises: 1) water-soluble basement membrane is placed on conveyer chain or the mould, 2) described part is placed on the described basement membrane 3) film is placed on the top, 4) adjust described film to enclose described part, and 5) described film is sealed, and cut where necessary.
Summary of the invention
We have found a kind of compacted granules method for compositions that is used to pack, and by described method, the ability of described composite opposing physical hazard obtains wonderful raising.Wherein a major advantage is, can allow that described compacted granules composite has wider physical property, as the hardness of reduction and the fragility of raising, therefore allows the component of wider scope to select and the production tolerance.Thereby have an opportunity to be provided at rapidly-soluble compacted granules composite in the water.
The invention provides the method that a kind of manufacturing comprises the package of compacted granules composite, described method comprises:
A. with first film parcel compacted granules composite;
B. the compacted granules composite that is wrapped in the Temperature Treatment that raises makes described film be close on the described composite so that described film shrinks.
Preferred steps a adopts streaming parcel (flow wrapping).
Found that method of the present invention provides the straightforward procedure of closely wrapping up the compacted granules composite.
Should be understood that, can classify as the compacted granules composite extruding with injection molding composite.
Surprisingly, described through parcel composite and be not easy to break or cracked, even when being packaged together in it in secondary package, also be like this.Therefore, described film not only plays the effect that the tablet that breaks is fitted together; And the generation that prevents to break, therefore make described tablet keep the integraty of its structure.Its effect is, can use the adhesives (using usually) of less amount and do not influence its integraty in the compacted granules composite; And/or can use lower squeeze pressure; And/or protected and/or kept by parcel, can use have moderate or even the compacted granules composite of relatively poor intrinsic engineering properties; And/or can prepare rapidly-soluble product.
Preferred described package is soluble in water.
In addition, according to the present invention, can use the squeeze pressure of reduction to make rapidly-soluble compacted granules composite.For example, be less than 10 minutes at 40 ℃ under the standard testing stirring condition that the rapid-dissoved tablet of 20g constructed in accordance can be mentioned in aftermentioned embodiment, be preferably to be less than within 5 minutes and dissolve.Preferably can reach these dissolution velocities by all known agitating methods that in the test of use in dishwasher tablet dissolved, use.
As a kind of selection, but simplicity of explanation is as follows: in 1 liter round beaker, the 20g tablet is immersed in 40 ℃ of tap water of 800ml, then by grasping beaker and/or with immersing in the water but the hand-held tool that does not allow to contact described tablet stirs (can comprise vortex), the stirring that is produced is not for to make water spill the maximum stirring that beaker can reach.Under these conditions, tablet of the present invention preferably is being less than 10 minutes, more preferably is being less than dissolving within 5 minutes.
Usually, streaming comprises that the neighboring area of the film web of sealing encirclement object has the pipe of longitudinal seam with formation.The two ends of described pipe are sealed by the transverse seam packing by described product.In forming transverse seam, make the surperficial adjacent of described longitudinal seam and packaged product, and be usually located at the middle part at the back side of described package.
As an example, WO-A-92/16431 has disclosed tubulose pouch-packaged thing, and this packing material comprises the film web with composite structure.The relative neighboring area of described film forms the pipe with longitudinal seam through sealing.By two parallel transverse seams along object to be packaged with pipe sealing.Described longitudinal folding seam (flap seam) is arranged along the middle part of described packing material and flush.
When comparing with for example dip-coating or spraying, materials used film parcel compacted granules method for compositions is simple and economical.
Preferred employing known method with described film phonograph seal together.Under can employed in the method for the invention condition of molding, particularly under the situation of utilizing heating and/or pressurization, seal simply.Yet, also can use other packing technique.For example, can use heat seal or infrared, frequency of radio, ultrasonic, laser, solvent, adhesives, vibration, electromagnetism, hot gas, hot plate or insert and connect friction sealed, cold sealing or spin welding.Heat seal preferably.
The heat seal condition depends on employed machine and material.Usually, seal temperature is 100 ℃～180 ℃.Pressure is generally 100kPa～500kPa (1bar～5bar).Dwell time is generally 0.02 second～and 0.6 second.
Heat treatment step b preferably carries out in short hour range, to avoid that film and/or compacted granules composite are caused heat damage.Should be understood that this step time will depend on the thickness of employed film.Usually, described heat treatment step carried out 0.1 second～5 seconds, more preferably was 0.2 second～4 seconds, and more preferably 0.5 second～2 seconds, more preferably 1.0 seconds～2.0 seconds for example was about 1.5 seconds time.
Most preferably, in the zone of passing through through the composite transmission of parcel, carry out described heat treatment step.In the method, found that described heat treatment step can be configured for wrapping up the part of the manufacture method of compacted granules composite, wherein said method comprises other steps, as described the compacting of composite.Such method is carried out with the speed of 1500 independent compacted compositions particles of per minute on single operating line usually.Found that method of the present invention can advantageously carry out with described productive output.
Usually, described zone is included in described hot blast (for example being spray pattern) on the compacted granules composite of parcel.Multiply hot air jet stream is passed through on the composite of parcel described.For example, one air jet stream can spray to described composite from the top, and one air jet stream sprays to described composite from the below, and air jet stream can spray to a side or many sides of described composite.For make the multiply air jet stream spray to through the parcel described composite, preferred described composite is carried by described zone by tool hole conveyer.
Should be understood that the temperature of described air jet stream depends on described through the composite (particularly described composite to heat sensitive situation under) of parcel and the character of described film (employed material).Usually, described air is heated to 90 ℃～950 ℃, and more preferably 140 ℃～800 ℃, more preferably 180 ℃～650 ℃ temperature.
Should be understood that the temperature of described film can be lower than the temperature of described air jet stream.Most preferably, the temperature of described film is 80 ℃～220 ℃, more preferably 120 ℃～180 ℃.
Usually, described film has perforate, makes to discharge any captive air in heat process.Most preferably, described film (when being applied to described compacted granules composite) has a plurality of perforates.Preferred described perforate is distributed in the upper surface of described particulate composition.Usually adopt tapping and plugging machine to form described perforate.Described perforate preferred sizes (before described heat treatment step) is about 0.1mm～0.3mm.
Find that cooling step only is the optional nonessential step of step.
In described method, the thickness of described film is preferably 10 μ m～2000 μ m, especially 10 μ m～150 μ m, more particularly 15 μ m～80 μ m.These measurements were all carried out before heat treatment; After heat treatment, some film may have different thickness, especially around the corner.
It is desirable to, described film has water-soluble, and this term comprises water dispersible.Described package also be preferably have water-soluble.The product that water-solubility membrane makes method of the present invention can disperse in aqueous medium and need not and must untie.
Preferred described film comprises polymeric material.
The example of water-soluble polymer has PVOH, cellulose derivative such as HYDROXY PROPYL METHYLCELLULOSE (HPMC), gelatin, poly-(vinylpyrrolidone), poly-(acrylic acid) or its ester or poly-(maleic acid) or its ester.Also can use the copolymer of any of these poly-mer.
The example of preferred PVOH is the PVOH of esterification or etherificate.Alcoholysis or hydrolysis can partly or entirely take place in described PVOH.For example, it can have 40%～100%, is preferably 70%～92%, and more preferably about 88% or about 92% alcoholysis or hydrolysis take place.The degree of known hydrolysis can influence the temperature that PVOH begins to dissolve in water.88% hydrolysis is equivalent to PVOH and dissolves in cold (being room temperature) water, is dissolvable in water warm water and 92% hydrolysis is equivalent to PVOH.
Can guarantee that it dissolves under required temperature by selecting suitable water-soluble polymer.Therefore, described film can be the film that can be dissolved in (20 ℃) in the cold water, but also can be to be insoluble to cold water and only to be dissolved in to have as 30 ℃, 40 ℃, 50 ℃ or even 60 ℃ warm water or the film in the hot water.
It is desirable to, described film mainly is made up of polymer composition, perhaps is made up of polymer composition.Can add proper additive, as plasticizer, lubricant and colorant.By making film have different colors, perhaps other films are painted by making the decolouring of a kind of film obtains attracting especially outward appearance.Also can add the component that can change described polymer property.Plasticizer dosage is generally 20 weight % at the most, for example 5 weight %～20 weight %, perhaps 10 weight %～20 weight %.The consumption of lubricant is generally 0.5 weight %～5 weight %.Therefore, based on the total amount of molding compounds, the consumption of described poly-mer is generally 75 weight %～94.5 weight %.Suitable manufacturing methods for example has water, pentaerythrite such as dipentaerythritol (depentaerythritol), sorbierite, sweet mellow wine, glycerine and such as diatomic alcohol such as glycerine, ethylene glycol and carbowax.Can be used as lubricant such as solids such as talcum, stearic acid, dolomol, silicon dioxide, zinc stearate or colloidal silicas.
Also can in described film, comprise one or more granular solids, to improve the dissolution velocity of described film.The dissolving of described solid in water is enough to accelerate the disintegration of described film, especially under the situation that produces gas.
The example of described solid have the bicarbonate of alkalies and alkaline earth (as sodium, potassium, magnesium and calcium) and carbonate and with the combining of acid.Suitable acid has and for example has carboxyl or sulfonic acidic materials or its salt.Its example has the free acid of cinnamic acid, tartaric acid, mandelic acid, fumaric acid, maleic acid, malic acid, palmitic acid, citric acid and naphthalenedisulfonic acid or their salt, for example alkali metal salt or alkali salt.
Described film can be a monofilm or as GB-A-2, disclosed laminated film in 244,258.Each layer in laminated film can be identical or different.But therefore described each self-contained identical poly-mer of layer or different poly-mers.
Can make described film by any method, for example by extruding and blow or making described film by casting.Described film can be unoriented, uniaxial orientation or biaxially oriented.If each layer in described film is directed, they have identical orientation usually, yet if desired, their oriented surface also can be different.
Utilize method of the present invention that the tablet of compacted granules composite is covered or is wrapped in the film.Described tablet can be the conventional tablet of known type.Though the applicant does not still desire to be subjected to the restriction of this theory, still think mutual action and/or outer membrane by outer layer copolymer film and tablet surface increases tablet to the compression of tablet intensity.
Form described compacted granules composite by the extruding particulate composition.If desired, described particle can be at the extruding precedent as handling by cohesion and/or granulation.Before extruding, described composite can have for example 100 μ m～2000 μ m, is preferably the mean grain size of 200 μ m～1200 μ m.
Described compacted granules composite can push under following squeeze pressure, for example for washing tablet, is 50kg/cm
2～1000kg/cm
2, be preferably 60kg/cm
2～300kg/cm
2, perhaps, be 50kg/cm for the dishwashing detergent tablet
2～1000kg/cm
2, 100kg/cm more preferably
2～700kg/cm
2For the tablet of the dishwashing detergent with good intrinsic engineering properties, described squeeze pressure is preferably 400kg/cm
2～1000kg/cm
2, 500kg/cm more preferably
2～700kg/cm
2For having relatively poor intrinsic engineering properties and/or the special tablet of dissolution properties rapidly, preferred range can be 150kg/cm
2～400kg/cm
2, 160kg/cm more preferably
2～350kg/cm
2, most preferably be 170kg/cm
2～300kg/cm
2These qualifications are meant the specified squeeze pressure that the concrete bead machine that is used to make described tablet is provided with.These regulations are meant that specified squeeze pressure should be within one or more above-mentioned scopes for any given press in using.
Suitable is, the described compacted granules composite part of described package, and the core that promptly is not wrapped has high fragility.Preferred described package is non-brittle.
The standard testing of test fragility is arranged, comprise the standard testing of being undertaken by embodiment.According to this aspect of the invention, the difference between " non-brittle " and " high fragility " so obviously-as after embodiment as shown in, so think and do not need further to define.
Preferably, partly the compacted granules composite than conventional is soft for the compacted granules composite of package of the present invention.The latter has the hardness number of 230N～260N usually.The compacted granules composite of preferred package of the present invention partly has the hardness number that is no more than 200N, is preferably and is no more than 150N.The compacted granules composite of preferred package of the present invention partly has 80N at least, is preferably the hardness number of 100N at least.For the purpose of these qualifications, can be by using ERWEKA tablet hardness tester THB30, hardness test is carried out in the tablet that the 20g with standard rectangular shape is not wrapped up at the Width test of breaking.In this tester, tablet is placed on the support that is the L type substantially, and leans against on its arm that protrudes upward.The circular piston of 8mm diameter advances and be pressed in the central area of respective side walls with 30mm/ minute speed, and is cracked up to tablet.
As a kind of selection, Ding Yi hardness can take it is such hardness as herein, they be necessary for be useful on the test dishwashing detergent and satisfy with the hardness test device/method of tablet.
The compacted granules composite part of preferred package of the present invention is not having to help keeping its shape under the situation of application of stress, but rapid disintegration when application of stress.Friction stress can easily cause it to peel off and be broken.Compression effort can be easily with its crushing.Yet, provide the water-soluble parcel of thermal contraction can avoid occurring these defectives, can operate neatly, and can utilize its rapidly-soluble major advantage.
Described compacted compositions can adopt Any shape or form.It would be desirable tablet form.It for example can be the form of cuboid, cylinder or prism.It also can contain independent a kind of particulate composition or contain two kinds, three kinds even more kinds of composite.For example, described compacted granules composite can comprise two-layer, three layers or more multi-layered.
Described package can comprise more than one compacted granules composite.If described package comprises two or more composites, they can have very attracting outward appearance, and this is because described composite no matter be identical or different, can both remain on the fixed position that is relative to each other.Described composite can easily be distinguished, to emphasize their difference.For example, described composite can have different physical appearances, perhaps has different colors.
Described package can have any required shape.The appearance of described package is decided according to the shape of described packaged composite.For example, described package can be irregular or regular geometric configuration, as cube, cuboid, centrum, deltohedron or cylinder.Described cylinder can have any required cross-sectional plane, as circle, triangle or square cross section.
If described composite has two-phase or multiphase, each is single-phase not necessarily must be rule or identical.For example, if final composite is a rectangular shape, each single-phase can being of different sizes to be adapted to different amount of composition.
Described compacted granules composite also can for example comprise embolus, and this embolus can be contained in the recess of described compact.Described embolus also can exceed described compact and stand in this compact.For example, described compacted granules composite can be the form of tablet, is in particular the form of cuboid tablet, wherein comprises one deck, two-layer or more multi-layered and embolus, and described embolus for example is the form of the spheroid in mould.The example of such tablet can be enumerated the tablet of being sold with trade mark Finish by Reckitt Benckiser plc..
Every composite in mutually that can be contained in the composite in the described package or can be included in composite in the described package can be a fabric nursing with composite, surface nursing with composite or dishwashing detergent composite independently.Therefore, for example, they can be dishwashing detergent composite, water softening composite, laundry composition or cleanser compositions, or rinse aid.These composites are applicable to home-use cleaning robot.Described composite also can be disinfectant, antiseptic or antiseptic composition independently, or the formula that the refills composite used of trigger-type sprayer.These composites are especially packed for the total weight of 5g～40g usually with 5g～100g.For example, the weight of laundry composition can be 15g～40g, and the weight of dishwashing detergent usefulness composite can be 15g～40g for the weight of 5g～30g and water softening usefulness composite.
Described phase can have identical or different size and/or shape.Usually, each contains the component of different amounts mutually if desired, and described each phase can have 1: 1 to 20: 1, was preferably 1: 1 to 10: 1 volume ratio.
The upperlimit (not comprising any edge) that can have if desired, 10cm by the prepared package of method of the present invention.For example, a package can be grown and be 1cm～5cm, especially 3.5cm～4.5cm, the wide 1.5cm～3.5cm that can be, especially 2cm～3cm, and height can be 1cm～3cm, and especially 1.0cm～2.0cm for example is 1.8cm.
If the composite that exists is a kind of incessantly, can select described composite rightly according to the required purposes of described goods.
If described goods are used for clothes washing, main composite can comprise for example cleaning agent, and less important composite can comprise bleaching agent, stain remover, water softener, enzyme or fabric softening agent.The different time that described goods can be adapted in the clothes washing process discharges described composite.For example bleaching agent or fabric softening agent discharge when washing finishes usually, and water softener discharges when the washing beginning usually.Enzyme discharges in the time of can or finishing in the washing beginning.
If described goods are as fabric softening agent, main composite can comprise fabric softening agent, and less important composite can comprise enzyme, and described enzyme discharged before or after described fabric softening agent in rinse cycle.
If described article are used for dishwashing detergent, main composite can comprise washer solvent, and less important composite can comprise water softener, salt, enzyme, rinse aid, bleaching agent or bleach-activating.The different time that described goods can be adapted in the clothes washing process discharges described composite.For example, rinse aid, bleaching agent or bleach-activating discharge when washing finishes usually, and water softener, salt or enzyme discharge when the washing beginning usually.
The example of surface care composition has those composites that for example use for the surface is cleaned, handled or polishing etc. in the surperficial nursing field.There is for example family surface on suitable surface, as the surface of bench board and bath article such as tank, pond and toilet etc.
The component of every kind of composite depends on the purposes of described composite.Therefore, for example, described composite can contain inhibiter, as anionic surfactant, non-ionic surface active agent, cationic surfactant, ampholytic surface active agent or zwitterionic surfactant or their compound.
Examples of anionic surfactants has the sulfate of straight chain or branched-alkyl sulfate and alkyl poly-alkoxylation, is also referred to as alkyl ether sulfate.Such inhibiter can pass through C
8～C
20The sulfation of higher aliphatic and making.
The example of primary alkyl sulphates inhibiter is the inhibiter with following formula:
ROSO
3 -M
+
Wherein R is a straight chain C
8～C
20Alkyl, and M is a water-soluble cationic.Preferred R is C
10～C
16Alkyl for example is C
12～C
14Alkyl, M are alkalieses, as lithium, sodium or potassium.
Secondary alkyl sulfate surfactant has the inhibiter of sulphate moiety in molecule " skeleton ", for example, have the inhibiter of following formula:
CH
2(CH
2)
n(CHOSO
3 -M
+)(CH
2)
mCH
3
Wherein m and n are that the m+n sum is generally 6～20 more than 2 or 2 independently, for example are 9～15, and M is a water-soluble cationic, as lithium, sodium or potassium.
Particularly preferred secondary alkyl sulfate is (2, the 3) alkyl sulfate surfactant with following formula:
CH
2(CH
2)
x(CHOSO
3 -M
+) CH
3With
CH
2(CH
2)
x(CHOSO
3 -M
+)CH
2CH
3
They correspond respectively to 2-sulfate and 3-sulfate.In these formulas, x is more than 4, for example 6～20, be preferably 10～16.M is such as cations such as alkalieses, for example lithium, sodium or potassium.
Alkoxylated alkyl group sulfate is the ethoxylated alkyl sulfates with following formula:
RO(C
2H
4O)
nSO
3 -M
+
Wherein R is C
8～C
20Alkyl is preferably C
10～C
18Alkyl for example is C
12～C
16Alkyl, n are more than 1, are 1～20 for example, are preferably 1～15, especially be preferably 1～6, and M are salt-forming cations, such as lithium, sodium, potassium, ammonium, alkylammonium or alkanol ammonium.Desirable especially clean fabric performance benefit when being used in combination, these cmpds and alkyl sulfate can be provided.
Described alkyl sulfate uses with the form that comprises the compound with different alkyl chain length and different extent of alkoxylation (if present) usually with alkyl ether sulfate.
Operable other anionic surfactants are aliphatic acid, for example C
8～C
18The salt of aliphatic acid especially is sodium salt or sylvite, and alkyl (C for example
8～C
18Alkyl) phenylsulfate.
The example of non-ionic surface active agent has fatty acid alkoxylates, such as fatty acid ethoxylates, especially has the alcoxylates of following formula:
R(C
2H
4O)
nOH
Wherein R is the C of straight chain or branching
8～C
16Alkyl is preferably C
9～C
15Alkyl for example is C
10～C
14Alkyl, and n is more than 1, for example is 1～16, is preferably 2～12, more preferably 3～10.
Described alkoxy fatty alcohols non-ionic surface active agent has 3～17 usually, and more preferably 6～15, most preferably be 10～15 hydrophilic-lipophilic balance value (HLB).
The example of alcohol ethoxylate is the aliphatic alcohol ethyl oxide that is made and contained 7 mole ethylene oxides of having an appointment by the alcohol with 12～15 carbon atoms.These materials carry out commercial distribution by Shell ChemicalCompany with trade mark Neodol 25-7 and Neodol 23-6.5.Other useful Neodol comprise Neodol 1-5, and described Neodol 1-5 is the ethoxylized fatty alcohol that on average has 11 carbon atoms and contain 5 mole ethylene oxides of having an appointment in its alkyl chain; Neodol 23-9, described Neodol 23-9 are the ethoxylation C with about 9 mole ethylene oxides
12～C
13Primary alconol; With Neodol 91-10, described Neodol 91-10 is the ethoxylation C with about 10 mole ethylene oxides
9～C
11Primary alconol.
Such pure b-oxide is also sold with trade mark Dobanol by Shell Chemical Company.Dobanol 91-5 is the ethoxylation C that on average has 5 mole ethylene oxides in every mole of fatty alcohol
9～C
11Fatty alcohol, and Dobanol 25-7 is the ethoxylation C that on average has 7 mole ethylene oxides in every mole of fatty alcohol
12～C
15Fatty alcohol.
The example of the ethoxylated alcohol nonionic surfactant that other are suitable comprises Tergitol 15-S-7 and Tergitol 15-S-9, and the two is can be by the linear secondary ethoxylate of Union Carbide Corporation acquisition.Tergitol 15-S-7 is the C that contains 7 mole ethylene oxides
11～C
15The ethoxylated product compound of linear secondary, and Tergitol 15-S-9 is the C that contains 9 mole ethylene oxides
11～C
15The ethoxylated product compound of linear secondary.
Other suitable alcohol ethoxylate non-ionic surface active agents have Neodol 45-11, and described Neodol 45-11 is the similar ethylene oxide condensation product with fatty alcohol of 14～15 carbon atoms, and wherein every mole ethylene oxide group number is about 11.Described product also can be obtained by Shell ChemicalCompany.
The non-ionic surface active agent that also has for example is C
10～C
18Alkyl poly glucoside is such as C
12～C
16Alkyl poly glucoside, especially polyglucoside.They are particularly useful when the high foaming property composite of needs.Inhibiter in addition also has polyhydroxy fatty acid amide, as C
10～C
18The ethylene oxide of N-(3-methoxy-propyl) glycamide (glycamide) and pluronic type-propylene oxide block polymer.
The example of cationic surfactant has the cationic surfactant of quaternary ammonium type.
Described composite particularly when using composite as clothes washing or dishwashing detergent, can also contain enzyme, as proteinase, lipase, amylase, cellulase and peroxidase independently.The all commercially available acquisition of these enzymes, and these enzymes are by for example Nova Industries A/S is with registered trade mark (RTM) Esperase, Alcalase and Savinase and International Biosynthetics, and Inc. sells with registered trade mark (RTM) Maxatase.It is desirable to, with 0.01 weight %～3 weight %, especially the amount with 0.01 weight %～2 weight % is present in the composite described enzyme independently, and is fashionable when adding as commercial formulation, these enzymes are also impure, and therefore described scale shows the amount of the pure enzyme that is equivalent to 0.005 weight %～0.5 weight %.
The composite that uses in dishwashing detergent comprises the soil release characteristics builder usually independently.The effect of described builder counteracting calcium or other ions, the water hardness.These examples of material for example have citrate, succinate, malonate, carboxymethyl succinate, carboxylate, polycarboxylate and the poly-acetyl group carboxylate that forms with alkalies or alkaline earth metal cation, or its corresponding free acid.Concrete example has oxo disuccinic acid, mellitic acid, benzene polycarboxylic acid, C
10～C
22The sodium of aliphatic acid and citric acid, potassium and lithium salts.Other examples have organic phosphate type chelant, as the chelant of selling with trade mark Dequest by Monsanto, and alkyl hydroxy phosphate.Optimization citric acid salt and C
12～C
18Fatty acid soaps.Builder in addition also has: phosphate, as sodium salt, sylvite or the ammonium salt of single phosphoric acid, two polyphosphoric acids or tripolyphosphate or oligomerization phosphoric acid; Zeolite; Amorphous or structurized silicate is as sodium, potassium or the ammonium salt of silicic acid.
Other suitable builders are known poly-mer and copolymers with builder performance.For example, described material comprises the copolymer and the salt thereof of suitable polyacrylic acid, poly and poly propenoic acid maleic acid, as those products of being sold with trade mark Sokalan by BASF.
With respect to the total weight of described composite, described builder exists with the content of 90 weight % at the most ideally, and preferably with 0.01 weight %～90 weight %, more preferably the content with 0.01 weight %～75 weight % exists.More details of suitable component are at for example EP-A-694,059, EP-A-518,720 and WO 99/06522 in provide.
Described composite also comprises more than one other components alternatively.These components comprise conventional composition of detergent component, as other inhibiter, bleaching agent, bleach enhancers, builder, lather booster or foam inhibitor, antirust composition and corrosion inhibitor, organic solvent, cosolvent, phase stabiliser, emulsifying agent, anti fouling composition, soil suspender, soil releasing agent, bactericidal agent, pH conditioning agent or buffering agent, non-builder alkali source, chelant, clay (as montmorillonitic clay), enzyme stabilizers, the agent (anti-limescale agent) of anticalcium dirt, colorant, dyestuff, help hydrosolvent, dye transfer inhibitor, brightener and aromatic.If use, these selectable components can account for the 60 weight % at the most of the total weight of described composite, for example 1 weight %～50 weight %.
The composite that contains enzyme contains the material of the stability that can keep enzyme alternatively.These enzyme stabilizers comprise for example polyalcohol such as propylene glycol, boric acid or borax.Also can adopt the combination of these enzyme stabilizers.If use, described enzyme stabilizers accounts for the 0.01 weight %～2 weight % of described composite usually.
Described composite contains alternatively can be as the material of phase stabiliser and/or cosolvent.Its example has C
1～C
3Alcohol is as methyl alcohol, ethanol and propyl alcohol.Also can use C separately
1～C
3Alkanolamine, as monoethanolamine, diethanolamine (DEA) and triethanolamine, perhaps its with alcohol combination.Described phase stabiliser and/or cosolvent can for example account for the 0 weight %～1 weight % of described composite, are preferably 0.1 weight %～0.5 weight %.
Described composite contains alternatively can regulate or keep the component of the pH of composite at optimal level.Described pH can be 1～13 for example, and as 8～11, this depends on the character of described composite.For example dishwashing detergent has 8～11 pH ideally with composite, and laundry cleaning compositions has 7～9 pH ideally, and water softening has 7～9 pH ideally with composite.The example of pH conditioning agent has soda ash (Na
2CO
3) and citric acid.
Above-mentioned example can be used for tableware or fabric cleans.Particularly preferably be the dishwashing detergent preparation, it is applicable to the automatic tableware cleaning machine.Because their specific demand, so need the purpose made preparation, these preparations are described below.
The amount of each component can change in relative broad range, yet, preferred herein automatic tableware washing (has pH greater than 7 usually with cleanser compositions, more preferably 8～12, most preferably be 8～10.5 1% aqueous solution) be the composite that wherein has following component: 5%～90%, be preferably 5%～75% builder; 0.1%～40%, be preferably 0.5%～30% bleaching agent; 0.1%～15%, be preferably 0.2%～10% surfactant system; 0.0001%～1%, be preferably 0.001%～0.05% metallic bleaching catalyst; With 0.1%～40%, be preferably 0.1%～20% water-soluble silicate.The described embodiment of preparation fully also contains 0.1%～15% polymeric dispersant, 0.01%～10% chelant and 0.00001%～10% detergency enzymes usually, but also can further have additional or auxiliary component.There is restriction in the composition of detergent of particulate form as herein described to liquid water content usually, for example is less than 7% free water, to improve storage stability.
Useful non-ionic surface active agent comprises the inhibiter of 15% level that accounts for described composite at the most ideally in ADW of the present invention (automatic tableware washing) composite.Usually be preferably inhibiter with bleach stability.Non-ionic surface active agent is normally known, at the Encyclopedia of KirkOthmer of Chemical Technology, the 3rd edition, the 22nd volume, the 360th～379 page, in " Surfactants and Detersive Systems " more detailed description is arranged, be introduced into as a reference at this.
Preferably, described ADW composite contains at least a non-ionic surface active agent.One class non-ionic surface active agent is the non-ionic surface active agent that carries out the ethoxylation that prepared in reaction obtains by the monohydroxy alkanol with 6～20 carbon atoms or alkylphenol and ethylene oxide, the ethylene oxide of wherein every mol of alcohol or alkylphenol is preferably at least 12 moles, especially be preferably at least 16 moles, more preferably at least 20 moles.
Particularly preferred non-ionic surface active agent is the non-ionic surface active agent that is obtained by straight-chain fatty alcohol with 16～20 carbon atoms and ethylene oxide, wherein the ethylene oxide of every mol of alcohol is at least 12 moles, especially be preferably at least 16 moles, more preferably at least 20 moles.
According to one preferred embodiment, described non-ionic surface active agent contains propylene oxide (PO) unit extraly in molecule.Preferred described PO unit accounts for the 25 weight % at the most of the total molecular weight of described non-ionic surface active agent, is preferably 20 weight % at the most, more preferably 15 weight % at the most.Particularly preferred inhibiter is the monohydroxy alkanol or the alkylphenol of ethoxylation, wherein contains the polyox-yethylene-polyoxypropylene block copolymer unit extraly.The alcohol moiety of such inhibiter or alkylphenol partly constitute and surpass 30%, are preferably to surpass 50%, more preferably surpass the total molecular weight of 70% described non-ionic surface active agent.
Another kind of ionic surfactant pack is drawn together the reverse periodic copolymer (reverse block copolymer) of polyoxyethylene and polyoxypropylene and the polyoxyethylene that is caused by trimethylolpropane and the periodic copolymer of polyoxypropylene.
Another kind of preferred nonionic can be explained by following formula:
R
1O[CH
2CH(CH
3)O]
x[CH
2CH
2O]
Y[CH
2CH(OH)R
2]
R wherein
1Expression has aliphatic alkyl or its compound of the straight or branched of 4～18 carbon atoms, R
2Expression has straight or branched aliphatic alkyl or its compound of 2～26 carbon atoms, and x is the value between 0.5～1.5, and y is the value more than 15.
Another kind of preferred nonionic is the non-ionic surface active agent of poly-alkoxylation with endcapped of following formula:
R
1O[CH
2CH(R
3)O]
x[CH
2]
kCH(OH)[CH
2]
jOR
2
R wherein
1And R
2Expression have 1～30 carbon atom straight or branched, saturated or undersaturated aliphatics or aromatic hydrocarbyl, R
3Expression hydrogen atom or methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 2-butyl or 2-methyl-2-butyl, x is the value between 1～30, k and j are the values between 1～12, are preferably the value between 1～5.When the value of described x greater than 2 the time, each R in following formula
3Can be different.R
1And R
2Be preferably straight or branched with 6～22 carbon atoms, saturated or undersaturated aliphatics or aromatic hydrocarbyl, wherein particularly preferably be group with 8～18 carbon atoms.For R
3Group particularly preferably is H, methyl or ethyl.Particularly preferred x value is included between 1～20, more preferably between 6～15.
As mentioned above, x greater than 2 situation under, each R in described formula
3Can be different.For example, when x=3, described R
3Group can selectedly be used for making up ethylene oxide (R
3=H) or propylene oxide (R
3=methyl) unit, it for example can be used in following each simple in-order: (PO) (EO) (EO), (EO) (PO) (EO) (EO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO) of (EO), (PO) of (PO), (EO) of (EO), (EO).The x value is 3 only to be an example, can select bigger value, obtains (EO) or (PO) the more changeableization number of unit thus.
Particularly preferred poly-alkoxylation alcohol with endcapped of following formula is the molecule with following skeleton symbol that wherein obtains when k=1 and j=1:
R
1O[CH
2CH(R
3)O]
xCH
2CH(OH)CH
2OR
2
In the ADW preparation, the preferred especially compound that uses different non-ionic surface active agents, for example pure and mild compound that contains the alcohol alcoxylates of hydroxyl of alkoxylate.
If desired, described package itself also can be packaged in the outer layer container (for example water-insoluble container), removes described water-insoluble container before using described water soluble package product.
In use, one or more packages are added simply make outer dissolving in the entry.Therefore, they can join in dishwashing detergent machine or the clothes washing machine in a usual manner, particularly in dishwashing detergent machine compartment or turning barrel.Also they can be added in a certain amount of water, for example in a certain amount of water in bucket or trigger-type sprayer.
A second aspect of the present invention provides above-mentioned package, and described package has the heat shrink films of the compacted granules composite that surrounds article washing (being preferably dishwashing detergent) usefulness.
A third aspect of the present invention provides above-mentioned package, and described package has the heat shrink films of the lightly compacting particulate composition that surrounds article washing (being preferably dishwashing detergent) usefulness.
A fourth aspect of the present invention provides a kind of package, and described package comprises the compacted granules composite that is wrapped in the water-soluble lapping, and described compacted granules composite is at 150kg/cm
2～400kg/cm
2Compaction pressure under carry out compacting.
A fifth aspect of the present invention provides a kind of package, and described package comprises the compacted granules composite that is wrapped in the water-soluble lapping, and described package is non-brittle, but described compacting microparticle compositions itself has high fragility.
A sixth aspect of the present invention provides a kind of package, and described package comprises the compacting microparticle compositions with the hardness that is no more than 200N, and described hardness is measured along the width of the cuboid compacted granules composite of 37mm * 27mm * 14mm of 20g." along width " is meant that described squeeze pressure is applied on that side that is of a size of 37mm * 14mm.
Preferred described second, third, the package of the either side of the 4th, the 5th or the 6th aspect is that method by first aspect makes.
Preferred package of the present invention satisfies in second aspect and the condition of either side in aspect the 3rd, the 4th, the 5th or the 6th or many aspects defined; Perhaps satisfy the preferred product of the either side of the present invention that this paper provides or other qualifications of method.
The specific embodiment mode
Embodiment
To further describe the present invention by the mode of embodiment now.In this embodiment of the invention, the PVOH film streaming that 28 μ m are thick is wrapped on the compressing grains tablet that dishwashing detergent uses and carries out thermal contraction, and the compressing grains tablet that described dishwashing detergent is used comprises inhibiter, builder, enzyme and auxiliary reagent; All typical A DW raws MAT'L.In the rotary tablet machine of standard, use 230kg/cm
2Squeeze pressure tablet is pushed.
By with accordingly through increase the weight of the extruding (700kg/cm
2Squeeze pressure) do not wrap up that tablet compares and to parcel and do not estimate through hardness, fragility and the dissolution time of the gained tablet of parcel.
Described the results are shown in the following table 1.
Table 1
| Tablet | Hardness N | Dissolution time minute | Tablet weight g before the fragility test | Tablet weight g after the fragility test | Fragility % % | |
| Bao Guo hard (contrast) soft (contrast) not | Aviation value | 250 244 | 10.75 12.00 | 21.08 21.17 | 19.93 19.77 | 5.46 6.61 |
| 247 | 11.38 | 21.13 | 19.85 | 6.04 | ||
| Aviation value | 136 133 | 3.00 3.25 | 21.12 20.89 | 4.87 5.76 | 76.94 72.43 | |
| 134.5 | 3.13 | 21.01 | 5.32 | 74.69 | ||
| Hard (the present invention) soft (the present invention) through parcel | Aviation value | 235 248 | 10.92 12.00 | 21.43 21.48 | 21.39 21.47 | 0.19 0.05 |
| 241.5 | 11.46 | 21.46 | 21.43 | 0.12 | ||
| Aviation value | 145 135 | 2.83 3.00 | 21.27 21.31 | 21.26 21.30 | 0.05 0.05 | |
| 140 | 2.92 | 21.29 | 21.28 | 0.05 | ||
ERWEKA tablet hardness tester THB 30 is used in described hardness test.Use ERWEKA tablet hardness tester THB 30, along the width of the tablet of the 20g that is of a size of 37mm * 27mm * 14mm with standard rectangular shape to the test of breaking of this tablet.Use described tester, tablet is placed on the support that is the L type substantially, and lean against on its arm that protrudes upward.The circular piston of 8mm diameter advances and is pressed in the central area of respective side walls (promptly being of a size of that side of 37mm * 14mm) with 30mm/ minute speed, up to tablet rupture.
Disintegration tester ERWEKA 2T 54 is used in the disintegration test, knocks operation 68 times with per minute.Use 1 liter glass beaker, wherein fill 40 ℃ of tap water of 800ml.Beaker is placed in the water-bath to keep its temperature.Tablet is placed in the three joint baskets (3-segment basket).Described basket is placed in the water, opens tester, it produce to be stirred and pick up counting with stopwatch.When becoming empty, basket records the time.
Use Vankel fragility tester (Vankel Friabilator, model No.45-2100) and accuracy rate are that the analytical balance of 0.01g carries out the fragility test.Tablet is placed in the drum (drum) of described fragility tester, 30 circulations are set.Again tablet is weighed at each halt point.Percent loss is calculated as follows:
Can see that the tablet that forms of the low squeeze pressure extruding of Bao Guo usefulness does not have fine solubility matter but engineering properties is general.They have soft and high fragility; They are easy to release particles and have even (when for example operating) also broken easily trend under applying low stress.These defectives are significantly improved by the thermal contraction parcel, and excellent simultaneously dissolution properties is not affected yet.
Claims (17)
1. a manufacturing comprises the method for the package of compacted granules composite, and described method comprises:
A. with first film parcel compacted granules composite;
B. through the described compacted granules composite of parcel described film is shunk in the Temperature Treatment that raises, make described film be close on the described composite.
2. the method for claim 1, wherein described step a comprises that using described first film that described compacted granules composite is carried out streaming wraps up.
3. method as claimed in claim 1 or 2, wherein, described heat treatment step b carried out 0.1 second～5 seconds, more preferably was 0.2 second～4 seconds, and more preferably 0.5 second～2 seconds, and then be preferably 1.0 seconds～2.0 seconds, for example be about 1.5 seconds time.
4. each described method in the claim as described above, wherein, described heat treatment step b uses the windstream of the temperature with rising to carry out.
5. method as claimed in claim 4, wherein, described air is heated to 90 ℃～950 ℃, more preferably is 140 ℃～800 ℃, more preferably 180 ℃～650 ℃ temperature.
6. each described method in the claim as described above, wherein, in described step b, the temperature of described film is 80 ℃～220 ℃, more preferably 120 ℃～180 ℃.
7. each described method in the claim as described above, wherein, described film has perforate, thereby any captive air can be discharged in described heating steps.
8. each described method in the claim as described above, wherein, the thickness of described film is 10 μ m～2000 μ m.
9. each described method in the claim as described above, wherein, described film is water miscible.
10. method as claimed in claim 9, wherein, described film comprises PVOH.
11. each described method in the claim as described above, wherein, described compacted granules composite is a fabric nursing with composite, surface nursing with composite or dishwashing detergent composite.
12. a package, this package comprise the thermal contraction water-solubility membrane of the compacted granules composite that surrounds article washing usefulness.
13. a package, this package comprise the thermal contraction water-solubility membrane of the lightly compacting particulate composition that surrounds article washing usefulness.
14. a package, this package comprise the compacted granules composite that is wrapped in the water-soluble lapping, described compacted granules composite is at 150kg/cm
2～400kg/cm
2Squeeze pressure under carry out compacting.
15. a package, this package comprise the compacted granules composite that is wrapped in the water-soluble lapping, described package is non-brittle, but described compacted granules composite itself has high fragility.
16. a package, this package comprise the compacted granules composite that is wrapped in the water-soluble lapping, described package can dissolve in water fast; Described quick dissolving is meant that under the condition that water stirs, the package of 20g is being less than dissolving in 10 minutes in 40 ℃ water, preferably is being less than dissolving in 5 minutes.
17. a package, this package comprise the compacted granules composite that is wrapped in the water-soluble lapping, the hardness of described compacted granules composite is no more than 200N.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0504919A GB0504919D0 (en) | 2005-03-10 | 2005-03-10 | Improvements in or relating to compositions |
| GB0504919.2 | 2005-03-10 | ||
| GB0522556.0 | 2005-11-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101137550A true CN101137550A (en) | 2008-03-05 |
Family
ID=34452111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800074916A Pending CN101137550A (en) | 2005-03-10 | 2006-03-10 | Process for the preparation of a package containing compacted composition and the package obtained with this process |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN101137550A (en) |
| GB (1) | GB0504919D0 (en) |
| ZA (1) | ZA200707546B (en) |
-
2005
- 2005-03-10 GB GB0504919A patent/GB0504919D0/en not_active Ceased
-
2006
- 2006-03-10 CN CNA2006800074916A patent/CN101137550A/en active Pending
-
2007
- 2007-08-30 ZA ZA200707546A patent/ZA200707546B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB0504919D0 (en) | 2005-04-13 |
| ZA200707546B (en) | 2010-10-27 |
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Application publication date: 20080305 |