CN104293275A - Anti-ultraviolet high-temperature-resistant cooking adhesive as well as preparation method and application thereof - Google Patents
Anti-ultraviolet high-temperature-resistant cooking adhesive as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an anti-ultraviolet high-temperature-resistant cooking adhesive as well as a preparation method and application thereof. The anti-ultraviolet high-temperature-resistant cooking adhesive is suitable for cooking-resistant composite films and bags and comprises the following components in parts by weight: 28-42 parts of polyester polyol, 4-6 parts of isocyanate, 3-6 parts of titanium dioxide, 3-7 parts of silicon dioxide, 0.5-1 part of an organic silane coupling agent and 40-62 parts of ethyl acetate. The anti-ultraviolet high-temperature-resistant cooking adhesive as well as the preparation method and the application thereof have the benefits that the prepared cooking-resistant composite films and bags have anti-ultraviolet functions, so that the light shielding property and the barrier property are improved, and the shelf life of packaged food is longer; the production technology process is short, and the production cost is reduced by about 20 percent compared with that of a traditional high-temperature-resistant double-component polyurethane adhesive suitable for the cooking-resistant composite bags.
Description
Technical field
The present invention relates to the composite membrane of resistance to boiling, bag technique field, disclose a kind of uvioresistant high-temperature boiling resistant sizing agent and its preparation method and application especially.
Background technology
Along with China's expanding economy, the prosperity of tourism, golden week economy emergence, the demand of people to ready-to-eat is increasing.The ready-to-eat such as soft canned and high-temperature cooking food, not only numerous in variety, and also quantity required is huge.The food packaging items of large quantities of high barrier, high impact properties, thermophilic digestion resistance, resistance to medium arises at the historic moment, thus ensure that the fresh of ready-to-eat and nutrition, extends the quality guaranteed period of ready-to-eat, is the wrapping material of soft canned the best.
High-temperature retort bag is a kind of composite plastic film bag that can carry out heat treated, and it has the advantage of both Can container and the plastics bag of resistance to boiling water.Food can remain untouched in bag, through high temperature (generally at 120 ~ 135 DEG C) germicidal treatment, takes out just edible.The food of High Temperature Sterilization is as adopted Trend of High Obstructive Materials Ordnance Engineering College, and it is longer not only to deposit the quality guaranteed period at normal temperatures, and transport, and storage, sells all very convenient, be applicable to very much the consumers demand of modern society.
High-performance barrier film or high-barrier packaging are widely used in food service industry.Film class high-barrier packaging mainly comprises following a few class:
(1) PVA is coated with high-isolation film
It is through printing, being composited after the PVA that with the addition of nano-inorganic substance is coated polyethylene film that PVA is coated with high-isolation film, under the prerequisite that little amplitude raises the cost, solve the technical bottleneck of current three-layer polyethylene co-extrusion packaging film barrier property difference, PVA is coated with high-isolation film and has pushed market comprehensively to.
(2) PVDC (polyvinylidene dichloride)
PVDC resin Chang Zuowei matrix material or monomer material and coextruded film sheet, be use maximum Trend of High Obstructive Materials Ordnance Engineering Colleges, wherein PVDC coated film usage quantity is many especially.
(3) EVOH (ethylene/vinyl alcohol copolymer)
EVOH applies maximum high barrier material.
(4) nylon-type wrapping material
Nylon-type wrapping material used " nylon 6 " in the past always.
(5) inorganic oxide plating film
The so-called plating film that plating SiOx (silicon oxide) is obtained afterwards on the film of other base material is more and more subject to market and payes attention to, and except silicon oxide plated film, also has aluminum oxide evaporated film.
At present, the pressure pad overwhelming majority in the world manufactures by dry type composite algorithm, and few in number also can go to manufacture by solvent-free composite algorithm or coextrusion composite algorithm.The quality of dry type compound than the height of solvent-free compound, also than coextrusion compound in the permutation and combination of material rationally and extensively, use also more relieved.Such as, patent CN103273724A discloses a kind of working method intercepting boiling type packing film, comprises the following steps: A, get the raw materials ready: get out binding agent and need the packing film base material of processing; B, gluing compound: adopt common glue application device to utilize gluing cable roll in glue application device or glue spreader binding agent on packing film substrate surface Jun Yun Tu, then by composite press roller, the basement membrane be coated with is formed composite membrane with another basement membrane pressure viscosity; C, slaking: in the curing chamber of composite membrane being inserted 40-60 degrees Celsius 72-168 hours; D, making finished product: the obstruct boiling type packing film composite membrane finished product obtained after slaking, intercept boiling type packing film volume film by above-mentioned obstruct boiling type packing film by cutting or obtaining after bag or intercept boiling type packing film sack.Patent CN103879125A discloses high temperature steaming composite membrane, the solvent-free complex method of bag and set composite thereof, and this complex method is to the first film pre-treatment, and to be contained on the first unwinding device and by Film laminated trend through guide roller; Compound is carried out through glue spreading apparatus oven dry and composite part; Second film to be contained on the second unwinding device and by Film laminated trend through guide roller; What regulate glue spreading apparatus enters glue amount, produces; Finally carry out rolling, slaking and cooling again.This set composite comprises rack-mounted first unwinding device, glue spreading apparatus, the second unwinding device, compound thermal drum, wrap-up and take off roll; And for glue spreading apparatus add sizing agent add glue bucket.
Usually, the manufacturing process of dry type compound comprises the steps:
First be selection.Which kind of which to go to determine to adopt base material, how to combine, with ink and tackiness agent according to the end-use of pressure pad.
Then, when concrete operations, follow the processing parameter of technique list, comprising concentration, the temperature of each heating zone of drying tunnel, the size of blast volume rim of the mouth exhaust air rate, the height of starting up speed of the line number of glue spreader and the site degree of depth, operation glue, also have unwinding tension, drying tunnel tension force, the control of winding tension, the surface temperature and composite pressure etc. of composite steel roll.
3rd, when concrete composition operation, after going to place 4h or 12h between some tackiness agent suppliers first will drop it off 50 ~ 55 DEG C slaking after requiring first time that two layers (PET/AL or OPA/AL) are multiple good, carry out the compound of second time third layer (PET/AL/CPP or PET/AL/OPA) again, compound well all will have this process each time, but also have many gluing punishment can at a dass two layers, three layers even four layers all multiple good after, the curing chamber being just put into 50 ~ 55 DEG C goes to allow its slaking.
4th is slaking.About the temperature of slaking and the time of slaking, general requirement keeps more than 48h at 50 ~ 55 DEG C, best 72h, but also some tackiness agent requires to put 15 ~ 7 days.
5th is detect bag.After mixture slaking is good, the compound fastness between first detection layers and residual solvent amount, after data reach requirement, just can take out bag of taking away.
The national standard that high-temperature retort bag adopts is GB10004-1998 " composite membrane of resistance to boiling, bag ", the material structure of product includes the transparent type of the transparent type of PET/CPP, PA/CPP bis-layers and the opaque type of PET/AL/CPP, PA/AL/CPP tri-layers and PET/PA/CPP tri-layers, also has this three major types of opaque type of PET/AL/PA/CPP tetra-layers.
High-temperature boiling resistant sizing agent technology is also constantly developed, and as patent CN1232851A discloses composite dry adhesive for high temperature steamed polyurethane bag, the component component by weight of its product is: glycol ether 13.64 ~ 18.6%; Sebacic acid 23.26 ~ 25.73%; 1,2-PD 2.06 ~ 2.94%; M-phthalic acid 6 ~ 5.43%; Diphenylmethanediisocyanate 3.86 ~ 5.74%; Vinyl acetic monomer 48.71 ~ 44.03%.Patent CN1629245A discloses a kind of boiling resistant polyurethane two component adhesive, and comprising mass percentage content is the host of 50-90% and the solidifying agent of 10-50%; Described host is made up of the polyester polyol of (A) hydroxyl value to be the polyester ether polylol of 10-30mgKOH/g and (B) hydroxyl value be 30-100mgKOH/g; Described solidifying agent is polyisocyanate prepolymers.Patent CN103666344A discloses the preparation method that a kind of high-temperature boiling resistant composite soft packaging film sticks with glue agent, first uses γ-aminopropyl triethoxysilane to Nano-meter SiO_2
2carry out surface graft modification; Add polyisocyanates and oligomer polyol, then add hydrophilic chain extender and be obtained by reacting base polyurethane prepolymer for use as; Use modified Nano SiO
2modifies to polyurethane prepolymer; Add hydroxy acryl acid ester end-blocking; Carry out neutralization dispersion after cooling, obtain modified aqueous polyurethane hybrid emulsions; Using dispersion as seed emulsion and macromolecule emulsifier, add fluorinated acrylate and initiator, prepare multiple modified aqueous polyurethane composite emulsion by seeded emulsion polymerization; Add thickening material and defoamer to this composite emulsion, obtain multiple modified aqueous polyurethane composite gel stick.But adopt with high barrier material such as Tu (boiling) film or pure aluminum foil etc., its starting material processing process is long, cost is high, according to the pressure pad of pure aluminum foil explained hereafter, can not adopt microwave-oven-heating.
Summary of the invention
The object of the present invention is to provide a kind of uvioresistant high-temperature boiling resistant sizing agent, can be applicable to the composite membrane of resistance to boiling, bag, it not only possesses resistance to elevated temperatures, also has anti-ultraviolet function, improves opacity and the barrier of high-temperature retort bag.
Another object of the present invention is to provide a kind of method preparing uvioresistant high-temperature boiling resistant sizing agent, and its technical process is short, and production cost is low.
Another object of the present invention is to provide the application of a kind of uvioresistant high-temperature boiling resistant sizing agent in the composite membrane of resistance to boiling, bag.
The invention provides a kind of uvioresistant high-temperature boiling resistant sizing agent, be applicable to the composite membrane of resistance to boiling, bag, comprise the component of following weight part: polyester polyol 28-42 weight part; Isocyanic ester 4-6 weight part; Titanium dioxide 3-6 weight part; Silicon-dioxide 3-7 weight part; Organo silane coupling agent 0.5-1 weight part; With vinyl acetic monomer 40-62 weight part.
Polyester polyol is matrix resin, and isocyanic ester makees solidifying agent, and being added with of mineral filler is beneficial to raising thermostability, barrier, opacity, and organo silane coupling agent can strengthen the coefficient of elasticity of glue.Wherein, the addition of mineral filler is not easily too much, otherwise can cause the degradation of stripping strength.The present invention adds appropriate silicon-dioxide on the basis of titanium dioxide has enhancement to stripping strength, to realize synergistic effect.
Preferably, described polyester polyol is selected from the polyester polyol that hydroxyl value is 20-90mgKOH/g, and its solid content is 65-72%, and viscosity is 3000-8000mPas; For 28-42 weight part, such as 28,29,30,31,32,33,34,35,36,37,38,39,40,41 or 42 weight parts, preferably, for 28-38 weight part, such as 28.5,29.5,30.5,31.5,32.5,33.5,34.5,36.5,37.5 weight parts, preferred further, be 28-32 weight part, but be also not limited thereto.
Polyester polyol, organism, normally by Dicarboxylic Acids (acid anhydrides or ester) and polyvalent alcohol (comprising glycol) condensation (or transesterify) or formed by lactone and polymerization.Diprotic acid has phthalic acid or phthalate anhydride or its ester, hexanodioic acid, halogeno-benzene dioctyl phthalate etc.Polyvalent alcohol has ethylene glycol, propylene glycol, glycol ether, TriMethylolPropane(TMP), tetramethylolmethane etc.The polyester polyol of different varieties is because kind is different or preparation technology is different, and character is also different, is hydroxyl value, acid number, moisture, viscosity, molecular weight, density and colourity etc. for several indexs that polyester polyol is important.The characteristic of polyester polyol and purposes: PAUR is because containing more ester group, amino isopolarity group in molecule, and cohesive strength and strong adhesion, have higher intensity, wear resistance.
Preferably, described isocyanic ester be selected from tolylene diisocyanate, di-isocyanate and two benzaldehyde methane cyanates one or more, its solid content is 75 ± 2%, viscosity 1000-3000mPas, for 4-6 weight part, such as 4,4.5,5,5.5,6 weight parts, preferably 4-5.5 weight part, preferably 4-5 weight part further, but be also not limited thereto.
Isocyanic ester is widely used in the fields such as rigid foam, RIM (resin injection is shaping) elastomerics, Polyurethane Thermoplastic Elastomer, coating, caking agent, spandex fiber and material of construction.In the present invention, be preferably in tolylene diisocyanate, di-isocyanate and two benzaldehyde methane cyanates one or more.
Preferably, described organo silane coupling agent is preferably γ-(2,3-glycidoxy) propyl trimethoxy silicane.Described organo silane coupling agent is 0.5-1 weight part, such as 0.5,0.6,0.7,0.8,0.9,1 weight part, further preferably 0.5-0.8 weight part.γ-(2,3-glycidoxy) propyl trimethoxy silicane, calls as silane coupling agent KH-560; Silane coupling A-187; 3-glycydoxy Trimethoxy silane; γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane; Silane coupling agent YDH-560; (3-oxiranyhnethoxy propyl group) Trimethoxy silane; Coupling agent 560; Coupling agent-560; γ-epoxypropyl-oxygen propyl-trimethoxysilane; 3-glycydoxy Trimethoxy silane.
The present invention also provides the method preparing above-mentioned uvioresistant high-temperature boiling resistant sizing agent, comprises the steps:
Step 1, configuration diluent: be added in vinyl acetic monomer by the titanium dioxide of selected weight part, silicon-dioxide, the obtained diluent that stirs is for subsequent use;
Step 2, matrix resin dissolves: polyester polyol stirring and dissolving in vinyl acetic monomer of selected weight part, and the diluent adding step 1 obtained stirs;
Step 3, the isocyanic ester of selected weight part adds in the mixed solution of step 2, stirs, obtained uvioresistant high-temperature boiling resistant sizing agent.
The invention provides the application of above-mentioned uvioresistant high-temperature boiling resistant sizing agent in the composite membrane of resistance to boiling, bag.
The invention provides a kind of composite membrane of resistance to boiling, bag, comprise high-isolation film and above-mentioned uvioresistant high-temperature boiling resistant sizing agent, described high-isolation film can be two-layer, such as: PA/PE or PA/RCPP, PET/PE or PET/RCPP; Also can be three layers, four layers, such as: PET/PA/PE, PET/PA/RCPP, etc.
The invention provides the preparation method of the above-mentioned composite membrane of resistance to boiling, bag, comprise the steps:
Step 1, gets the raw materials ready: prepare above-mentioned uvioresistant high-temperature boiling resistant sizing agent, selects suitable high-isolation film according to functional analysis,
Step 2, gluing compound: by glue application device, above-mentioned uvioresistant high-temperature boiling resistant sizing agent is evenly coated on high-isolation film, and carries out compound; Wherein, resin added controls at 3.5-5g/m
2;
Step 3, slaking: composite membrane inserts curing chamber slaking, the obtained composite membrane of resistance to boiling, bag; Wherein, curing temperature controls at 55-60 DEG C, and the curing time controls at 72-96 hour.
Beneficial effect of the present invention has:
1, the uvioresistant high-temperature boiling resistant sizing agent composite membrane of resistance to boiling of the present invention, bag have anti-ultraviolet function, and improve opacity and the barrier of high-temperature retort bag, the quality guaranteed period of its wrap food is longer.
2, the technological process of production of the uvioresistant high-temperature boiling resistant sizing agent composite membrane of resistance to boiling of the present invention, bag is short, and production cost sticks the agent laminated bag of resistance to boiling compared to traditional high temperature resistant two-component polyurethane adhesive can decline about 20%.
Embodiment
Can be well understood to the present invention further by specific embodiments of the invention given below and comparing embodiment, but they not limitation of the invention.The part do not described in detail in specific embodiment and comparing embodiment adopts prior art, known technology means and industry standard to obtain.
Except as otherwise noted, the percentage ratio adopted in the present invention is weight percentage.
embodiment 1
With reference to the recipe ingredient of table 1 and the processing parameter of table 2, prepare the composite membrane of resistance to boiling, bag as follows:
(1) uvioresistant high-temperature boiling resistant sizing agent is prepared:
Recipe ingredient in reference table 1 is got the raw materials ready: polyester polyol 28 weight part; Isocyanic ester 4 weight part; Titanium dioxide 3 weight part; Silicon-dioxide 7 weight part; Organo silane coupling agent 0.5 weight part; With vinyl acetic monomer 40 weight part.
Aforementioned body resin and solidifying agent all can purchased from Chinese Neweast Printing Ink Co., Ltd., Henkel Co., Ltd, the two component solvent polyurethane composite adhesive series of the producers such as Beijing Gao Meng type material limited-liability company, wherein, the physical parameter of main ingredient polyester polyol, isocyanic ester controls to refer to table 3.
The first step: titanium dioxide, silicon-dioxide add vinyl acetic monomer again and stirs for subsequent use;
Second step: polyester polyol (host) adds the diluent adding first step after vinyl acetic monomer stirs again, stirs and then adds isocyanic ester (solidifying agent), stir for subsequent use.
(2) composite membrane of resistance to boiling, bag:
Prepare above-mentioned uvioresistant high-temperature boiling resistant sizing agent, select suitable high-isolation film according to functional analysis;
By glue application device, above-mentioned uvioresistant high-temperature boiling resistant sizing agent is evenly coated on high-isolation film, and carries out compound; Wherein, resin added controls at 3.5g/m2;
Composite membrane inserts curing chamber slaking, and curing temperature controls at 55 DEG C, and the curing time controls at 72 hours, the obtained composite membrane of resistance to boiling, bag.
Table 1 formula rate
Table 2 processing parameter
The physical parameter of table 3 main ingredient
embodiment 2
The implementation process of this embodiment is substantially the same manner as Example 1, and the adjustment of its recipe ingredient and processing parameter is see table 1 and table 2.
embodiment 3
The implementation process of this embodiment is substantially the same manner as Example 1, and the adjustment of its recipe ingredient and processing parameter is see table 1 and table 2.
embodiment 4
The implementation process of this embodiment is substantially the same manner as Example 1, and the adjustment of its recipe ingredient and processing parameter is see table 1 and table 2.
comparative example 1
The implementation process of this comparative example is substantially the same manner as Example 3, the adjustment of its recipe ingredient, component physical parameter and processing parameter is see table 1 and table 2, the proportion relation of main adjustment two kinds of filler components on formula, change mainly hydroxyl value, the viscosity etc. of the physical parameter of main ingredient, main resin added controling parameters in technique.
comparative example 2
The implementation process of this comparative example is substantially the same manner as Example 4, the adjustment of formula rate, component physical parameter and processing parameter refers to table 1, table 2, on formula, main adjustment filler is adjusted to the filler systems of single component, change mainly hydroxyl value, the viscosity etc. of the physical parameter of main ingredient, the controling parameters of main curing step in technique.
comparative example 3
The sizing agent formula of this comparative example adopts high temperature resistant two-component polyurethane adhesive conventional in prior art to stick agent, and such as referenced patent CN1629245A is prepared from.
Table 4 gives embodiment 1 to 4 and the obtained composite membrane of resistance to boiling, the bag the performance test results of comparative example 1 to 3.Wherein, stripping strength is the stripping strength before 121 DEG C of boilings, after boiling, adopts standard GB/T/T10004-2008 method to measure, and wherein stripping strength requirement is: for PET/PA material structure, stripping strength >=3.5N/15mm before boiling, the stripping strength >=2.8N/15mm after boiling; For PA/RCPP material structure, the stripping strength >=5N/15mm before boiling, the stripping strength >=4N/15mm after boiling.
Table 4 composite membrane of resistance to boiling, bag performance test
applied research
The laminated bag of resistance to boiling that prior art and the technology of the present invention obtain is applied to food product pack, and the high temperature resistant two-component polyurethane adhesive being about to commonly use sticks the agent laminated bag of resistance to boiling and carries out destructive test contrast with the uvioresistant high-temperature Resistance Adhesives laminated bag of resistance to boiling.Concrete:
Experiment Fruit variety sweet corn, reason has three: 1, has wide market, as long as outlet at present, domestic market potentiality are large.2, sweet corn is healthcare product, and does not add any additive in the course of processing, is the safety on practical significance, healthy products.3, this product is after High Temperature Sterilization, preserves nondiscoloration in a year, never degenerate under normal temperature.
Experiment condition: this product is after high temperature (121 DEG C) sterilization, and place in physical environment, through Exposure to Sunlight, wind and rain are beaten.
Experimental quantities: each 50.
Experimental result: as following table.
Adopt the uvioresistant high-temperature Resistance Adhesives laminated bag of resistance to boiling of the present invention, packing cost can decline about 20%.
Above disclosedly be only the preferred embodiments of the present invention, certainly can not limit the interest field of the present invention with this, therefore according to the equivalent variations that the present patent application the scope of the claims is done, still belong to the scope that the present invention is contained.
Claims (9)
1. a uvioresistant high-temperature boiling resistant sizing agent, is applicable to the composite membrane of resistance to boiling, bag, it is characterized in that: the component comprising following weight part: polyester polyol 28-42 weight part; Isocyanic ester 4-6 weight part; Titanium dioxide 3-6 weight part; Silicon-dioxide 3-7 weight part; Organo silane coupling agent 0.5-1 weight part; With vinyl acetic monomer 40-62 weight part.
2. uvioresistant high-temperature boiling resistant sizing agent according to claim 1, it is characterized in that: described polyester polyol is selected from the polyester polyol that hydroxyl value is 20-90mgKOH/g, its solid content is 65-72%, and viscosity is 3000-8000mPas.
3. uvioresistant high-temperature boiling resistant sizing agent according to claim 1, is characterized in that: described isocyanic ester is selected from the isocyanic ester that solid content is 75 ± 2%, viscosity 1000-3000mPas.
4. uvioresistant high-temperature boiling resistant sizing agent according to claim 1, is characterized in that: described organo silane coupling agent is γ-(2,3-glycidoxy) propyl trimethoxy silicane.
5. prepare a method for uvioresistant high-temperature boiling resistant sizing agent according to any one of claim 1 to 4, it is characterized in that: comprise the following steps:
Step 1, configuration diluent: be added in vinyl acetic monomer by the titanium dioxide of selected weight part, silicon-dioxide, the obtained diluent that stirs is for subsequent use;
Step 2, matrix resin dissolves: polyester polyol stirring and dissolving in vinyl acetic monomer of selected weight part, and the diluent adding step 1 obtained stirs;
Step 3, the isocyanic ester of selected weight part adds in the mixed solution of step 2, stirs, obtained uvioresistant high-temperature boiling resistant sizing agent.
6. the application of uvioresistant high-temperature boiling resistant sizing agent in the composite membrane of resistance to boiling, bag that prepare of uvioresistant high-temperature boiling resistant sizing agent according to any one of claim 1 to 4 or method according to claim 5.
7. the composite membrane of resistance to boiling, a bag, comprise high-isolation film and uvioresistant high-temperature boiling resistant sizing agent according to any one of claim 1 to 4, described high-isolation film is PA/PE, PA/RCPP, PET/PE, PET/RCPP, PET/PA/PE, PET/PA/RCPP.
8. prepare a method for the composite membrane of resistance to boiling according to claim 8, bag, it is characterized in that: comprise the steps:
Step 1, gets the raw materials ready: prepare uvioresistant high-temperature boiling resistant sizing agent according to any one of claim 1 to 4, selects suitable high-isolation film according to functional analysis;
Step 2, gluing compound: by glue application device, above-mentioned uvioresistant high-temperature boiling resistant sizing agent is evenly coated on high-isolation film, and carries out compound; Wherein, resin added controls at 3.5-5g/m
2;
Step 3, slaking: composite membrane inserts curing chamber slaking, the obtained composite membrane of resistance to boiling, bag; Wherein, curing temperature controls at 55-60 DEG C, and the curing time controls at 72-96 hour.
9. the composite membrane of resistance to boiling according to claim 7, bag or method according to claim 8 prepare the composite membrane of resistance to boiling, the application of bag in food product pack.
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| CN201410624526.7A CN104293275B (en) | 2014-11-06 | 2014-11-06 | Uvioresistant digestion resistant adhesive and its preparation method and application |
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| CN201410624526.7A CN104293275B (en) | 2014-11-06 | 2014-11-06 | Uvioresistant digestion resistant adhesive and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105082708A (en) * | 2015-08-10 | 2015-11-25 | 漳州市芳远印务有限公司 | Manufacturing method for compound packaging film resistant to high-temperature steaming and boiling |
| CN106905904A (en) * | 2015-12-22 | 2017-06-30 | 北京奥托米特电子有限公司 | Digestion resistant adhesive and preparation method thereof |
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| CN103660437A (en) * | 2013-12-05 | 2014-03-26 | 广东挚信彩印有限公司 | Nanometer impermeable boiling bag, and nano-binder and making method thereof |
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- 2014-11-06 CN CN201410624526.7A patent/CN104293275B/en active Active
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| CN103660437A (en) * | 2013-12-05 | 2014-03-26 | 广东挚信彩印有限公司 | Nanometer impermeable boiling bag, and nano-binder and making method thereof |
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| 陈晓东等: "耐蒸煮软包装用聚氨酯胶黏剂的研制", 《化学与黏合》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105082708A (en) * | 2015-08-10 | 2015-11-25 | 漳州市芳远印务有限公司 | Manufacturing method for compound packaging film resistant to high-temperature steaming and boiling |
| CN106905904A (en) * | 2015-12-22 | 2017-06-30 | 北京奥托米特电子有限公司 | Digestion resistant adhesive and preparation method thereof |
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| C06 | Publication | ||
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Inventor after: Cai Liangguo Inventor after: Hong Chaojin Inventor after: Zhang Heping Inventor after: Cai Yuanwen Inventor before: Cai Liangguo Inventor before: Cai Xu Inventor before: Su Meilan Inventor before: Cai Yuanwen |
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