CN108299575A - A kind of high temperature resistant chlorinated polypropylene and preparation method thereof and application - Google Patents
A kind of high temperature resistant chlorinated polypropylene and preparation method thereof and application Download PDFInfo
- Publication number
- CN108299575A CN108299575A CN201810087698.3A CN201810087698A CN108299575A CN 108299575 A CN108299575 A CN 108299575A CN 201810087698 A CN201810087698 A CN 201810087698A CN 108299575 A CN108299575 A CN 108299575A
- Authority
- CN
- China
- Prior art keywords
- high temperature
- temperature resistant
- polypropylene
- chlorinated polypropylene
- petg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of high temperature resistant chlorinated polypropylene and preparation method thereof and application include following component by mass percentage：Polypropylene powder 95.06% ~ 95.88%, initiator 0.57% ~ 0.58%, suspending agent 0.38% ~ 0.38%, dispersant 1.43% ~ 1.44%, heat stabilizer 1.72% ~ 2.58%, heat stabilizer are made of terephthalic acid (TPA) lanthanum 0.76% ~ 1.15%, dibutyl tin laurate 0.96% ~ 1.43%.With special high temperature resistant chlorinated polypropylene, blending and modifying processing is carried out to middle layer materials PP materials, the adhesion strength on its surface is made to be significantly increased, generated good affinity with the faying face of PETG, reach the not stratified effect that co-extrusion is dissolved each other.To save the use of adhesive layer ionic resin, becomes real three-layer co-extruded production shrink label film new product, realize the purpose for directly processing PETG/PP/PETG thermal contractive label films with existing PETG thermal contractive labels film production line.
Description
Technical field
The invention belongs to plastic film processing technique fields, are related to a kind of preparation method of polyesters thermal contractive label film,
More particularly to the PETG/PP/PETG thermal contractive labels film improvement of heat stabilizer chlorinated polypropylene.
Background technology
Since thermal contractive label can assign the 360 ° of labels design of bottled drink and pure water, by be beautifully printed pattern and
Gorgeous color forms the packaging effect of stronger visual impact, highlights perfectly matched layers and attraction of the commodity on supermarket shelves, just
In brand differentiation design and the marketing.Therefore, become one of the primary label form of current bottled drink.
PETG thermal contractive label films are environment-protecting and non-poisonous, compared with PVC thermal contractive label films, possess higher shrinking percentage and mechanics
Thinner label film design scheme may be used in performance.Its transparency is good, and thickness uniformity is good, shrinkage curve, printing and storage
Arc manipulation part is suitable with PVC film, is the ideal environmentally friendly class product for substituting PVC thermal contractive label films.
PETG materials used in label film and PET bottle body material are all polyesters product, and proportion is close.It was recycling
Cheng Zhong can not carry out effectively separately processing by easy density separation.Though the two is same class material, property between the two
There can be notable difference, and PETG labels pass through printing treatment again, and a large amount of ink are attached on film surface.The not separated place of the two
Reason, it is similar with PVC shrink labels, PET bottle piece can equally be polluted.Such as, the Main way of PET bottle piece reuse is that processing is short
Fiber, PETG performances but cannot be satisfied the processing request of staple fiber.Therefore, the proportion for reducing PETG thermal contractive label films, makes it
There is apparent difference of specific gravity with bottle piece, be one of thermal contractive label membrane technology improvement direction.
In addition, due to meet set target requirement, thermal contractive label film needs have preferably deflection.But as set was marked
Journey is completed, and after thermal contractive label film is shunk, deflection and hardness meeting higher, this results in the handling property of thermal contractive label poor.
To improve the feel compliance of thermal contractive label, some new products in the industry, the heat for using PETG/PP/PETG MULTILAYER COMPOSITEs is received
Contracting label form membrane.Due to the introducing of PP, the compliance of thermal contractive label film is made to greatly improve, the feel after especially shrinking is soft
With it is very much, obtain good effect and public praise.Meanwhile the introducing of PP, so that the proportion of thermal contractive label film is greatly reduced, is convenient for
Label and bottle piece, are detached using easy difference of specific gravity method.
Since there are larger differences with PETG molecular structures by PP, polarity is also inconsistent, and two kinds of materials are incompatible, therefore,
There is adhesive layer between the PETG and PP of PETG/PP/PETG MULTILAYER COMPOSITE thermal contractive label films.In fact, commercialization
PETG/PP/PETG MULTILAYER COMPOSITE thermal contractive label films are made of five-layer co-squeezing.For the composite effect for reaching excellent, adhesive layer
The general firm or sarin plasma type resin using E.I.Du Pont Company's production.Though the thickness of the tunic is smaller, because of material price
Higher, film cost will but greatly improve.
Currently, PETG thermal contractive label film production lines are mostly 2 three-layer co-extruded configurations of extruder, be can not produce it is above-mentioned
Thermal contractive label film new product.Even if 3 extruders of some line configurations, can meet the primary condition of 5 layers of co-extrusion,
Extruder screw rod structure and extrusion capacity design also are difficult to meet the practical extrusion requirement of ionic resin.In addition, as carried out 5 layers altogether
Production is squeezed, the molding die or the distributor before die head of production line are also required to replace, to adapt to be turned from 3 layers of co-extrusion to 5 layers of co-extrusion
The demand of change.
Therefore, PETG/PP/PETG multilayer thermal contractive label films are processed with existing PETG thermal contractive labels film production line, had
Prodigious equipment aspect problem, it is difficult to smoothly change the line of production over.This, which is seriously constrained, possesses soft feel, is easy to detach place with bottle piece
Reason novel thermal contractive label film production and promote the use of.
To solve this technical problem, the prior art is improved compatible between two kinds of incompatible materials by using compatilizer
Property, by the way that the maleic anhydride of a certain amount of PP and PETG or glycidyl methacrylate graft object are mixed into middle layer PP
In material, the binding force at itself and PETG co-extrusions interface can be made to have certain promotion, but cannot thoroughly solve PP and PETG co-extrusion films
Lamination problem.When to find out its cause, compatilizer plays a role, not only needing certain additive amount, but also also needing to enough miscible
Between.In three-layer co-extruded film manufacturing process, compatilizer, which is only realized with middle layer PP, preferably to dissolve each other, and only exists with PETG melts
Ability intimate contact at distributor before die head or die head, and when contact, compatilizer is also wrapped among PP melts, can not be fine
Ground plays " bonding " function in time, keeps two layers of fusion integral.
Common chlorinated polypropylene adhesiveness is excellent, and good with PP compatibilities, fusing point is relatively low, is 100-120 DEG C, total with PP
Consolute easily precipitate into blends surface after melting, and is that tackifying assistant is preferably blended in PP/PETG, but chlorinated polypropylene decomposition temperature exists
180-190 DEG C, it is molding compared with high technology temperature that PETG/PP/PETG coextruded films can not be adapted to.
Still have much room for improvement.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of with PP compatibilities good, decomposition temperature is higher, is suitable for
PETG/PP/PETG coextruded films it is molding compared with high temperature resistant chlorinated polypropylene of high technology temperature and preparation method thereof and application.
Purpose to realize the present invention provides following technical scheme：A kind of high temperature resistant chlorinated polypropylene, it is characterised in that press
Mass percent meter includes following component：Polypropylene powder 95.06% ~ 95.88%, initiator 0.57% ~ 0.58%, suspending agent
0.38% ~ 0.38%, dispersant 1.43% ~ 1.44%, heat stabilizer 1.72% ~ 2.58%.
Preferably, initiator is benzoyl peroxide, cumyl peroxide, tert-butyl hydroperoxide, peroxidating two
Tertiary butyl is a kind of or combines.
Preferably, suspending agent is carboxymethyl cellulose, xanthans, polyvinyl alcohol is a kind of or combines.
Preferably, dispersant be neopelex, sodium cetanesulfonate, oleoyl oxygroup ethanesulfonic acid sodium one
Kind or combination.
Preferably, heat stabilizer is made of terephthalic acid (TPA) lanthanum and dibutyl tin laurate.Di lauric dibutyl
Tin is that have one of fatty acid salt machine tin stabilizer Representative Cultivars, is a kind of very outstanding dehydrochlorination inhibitor, there is preferable profit
Slip and processability, but have apparent initial coloration when exclusive use.Terephthalic acid (TPA) lanthanum is a kind of rare-earth stabilizer, transition gold
Belong to lanthanum ion La3+ to be easy that coordination occurs with Cl active in chlorinated polypropylene, reduces C-Cl bond polarities and β-H
Acidity, to hinder the formation of conjugated polyene；Additionally, due to the special electron structures of La3+, can be decomposed with chlorinated polypropylene
The HCl of release, which reacts, generates complex, reduces catalysis of the HCl to rearrangement reaction.Terephthalic acid (TPA) lanthanum has good
Initial stage and effect steady in a long-term, have synergistic effect with fatty acid salt organic tin stabilizer.
Two kinds of stabilizers are deep into chlorinated polypropylene strand, are synthesized by chemical bonded refractory by in-situ polymerization technology
One, more preferably can more effectively play heat stabilization.
Preferably, the terephthalic acid (TPA) lanthanum 0.76% ~ 1.15%, dibutyl tin laurate 0.96% ~ 1.43%.
Purpose to realize the present invention provides a kind of high temperature resistant chlorinated polypropylene preparation method, it is characterised in that including following
Step：
A. first by after polypropylene liquid nitrogen frozen 1-2 hours, attrition grinding is at polypropylene powdery;
B. polypropylene powder is added in the reaction kettle that 20 times of dosage water of polypropylene weight has been added, in whipping process, is added
0.57% ~ 0.58% initiator, 0.38% ~ 0.38% suspending agent and 1.43% ~ 1.44% dispersant, under stirring,
It is in suspended state to make polypropylene powder, is warming up to 80-85 DEG C；
C. start the chlorine for being passed through 1.2-1.5 times of polypropylene dosage, normal pressure chlorination reaction keeps the temperature 1-1.5 hours, uses compressed air
Chlorine is replaced away, synthesizing chlorinated polypropylene；
D. 0.76% ~ 1.15% terephthalic acid (TPA) lanthanum and 0.96% ~ 1.43% dibutyl tin laurate are added into reaction kettle,
Continue heat preservation 0.5 hour under stirring；
E. after reaction, stop heating, be cooled to room temperature, neutrality is neutralized to sodium hydroxide, after washing, drying, obtain
Powdery high temperature resistant chlorinated polypropylene.
Preferably, by powdery high temperature resistant chlorinated polypropylene extruding pelletization, high temperature resistant is made in 100-120 DEG C of prilling temperature
Chlorinated polypropylene particle.
Purpose to realize the present invention provides a kind of application of high temperature resistant chlorinated polypropylene, it is characterised in that is drawn for being cast
The preparation for stretching PETG/PP/PETG thermal contractive label films carries out blending and modifying processing for PP materials.
Advantageous effect of the present invention：The special high temperature resistant chlorinated polypropylene of the present invention（CPP）, middle layer materials PP materials are carried out
Blending and modifying processing, makes the adhesion strength on its surface be significantly increased, and generates good affinity with the faying face of PETG, reaches co-extrusion
The not stratified effect dissolved each other.To save the use of adhesive layer ionic resin, become real three-layer co-extruded production contraction mark
Film new product is signed, realizes the mesh for directly processing PETG/PP/PETG thermal contractive label films with existing PETG thermal contractive labels film production line
's.
Specific implementation mode
Embodiment 1：A kind of high temperature resistant chlorinated polypropylene includes following component by mass percentage：Polypropylene powder
95.06%, benzoyl peroxide 0.57%, carboxymethyl cellulose 0.38%, neopelex 1.43%, terephthalic acid (TPA) lanthanum
1.15%, dibutyl tin laurate 1.41%.
Its preparation includes the following steps：
First by after polypropylene liquid nitrogen frozen 1-2 hours, attrition grinding is at polypropylene powdery;
Polypropylene powder is added in the reaction kettle that 20 times of dosage water of polypropylene weight has been added, in whipping process, was added
Benzoyl Oxide 0.57%, carboxymethyl cellulose 0.38% and neopelex 1.43% make to gather under stirring
Propylene powder is in suspended state, is warming up to 80-85 DEG C；
Start the chlorine for being passed through 1.2-1.5 times of polypropylene dosage, normal pressure chlorination reaction keeps the temperature 1-1.5 hours, will with compressed air
Chlorine is replaced away, synthesizing chlorinated polypropylene；
Terephthalic acid (TPA) lanthanum 1.15% and dibutyl tin laurate 1.41% are added into reaction kettle, continue heat preservation 0.5 under stirring
Hour；
After reaction, stop heating, be cooled to room temperature, neutrality is neutralized to sodium hydroxide, after washing, drying, obtain powder
Shape high temperature resistant chlorinated polypropylene.
Finally by powdery high temperature resistant chlorinated polypropylene extruding pelletization, it is poly- that high temperature resistant chlorination is made in 100-120 DEG C of prilling temperature
Particulate propylene.
Embodiment 2：With reference to embodiment 1, specific preparation process is constant with step, and parameter is changed to：Polypropylene powder 95.55%,
Cumyl peroxide 0.58%, carboxymethyl cellulose 0.38%, sodium cetanesulfonate 1.44%, terephthalic acid (TPA) lanthanum 1.05%,
Dibutyl tin laurate 1.0%.
Embodiment 3：With reference to embodiment 1, specific preparation process is constant with step, and parameter is changed to：Polypropylene powder 95.43%,
Tert-butyl hydroperoxide 0.57%, polyvinyl alcohol 0.38%, neopelex 1.43%, terephthalic acid (TPA) lanthanum 0.76%, two
Dibutyl tin laurate 1.43%.
Embodiment 4：With reference to embodiment 1, specific preparation process is constant with step, and parameter is changed to：Polypropylene powder 95.60%,
Di-t-butyl peroxide 0.58%, xanthans 0.38%, oleic acid oxygroup ethanesulfonic acid sodium 1.44%, terephthalic acid (TPA) lanthanum 0.98%, February
Dilaurylate 1.02%.
Embodiment 5：With reference to embodiment 1, specific preparation process is constant with step, and parameter is changed to：Polypropylene powder 95.48%,
Tert-butyl hydroperoxide 0.57%, carboxymethyl cellulose 0.38%, neopelex 1.44%, terephthalic acid (TPA) lanthanum
1.12%, dibutyl tin laurate 1.01%.
Embodiment 6：With reference to embodiment 1, specific preparation process is constant with step, and parameter is changed to：Polypropylene powder 95.41%,
Benzoyl peroxide 0.58%, carboxymethyl cellulose 0.38%, neopelex 1.44%, terephthalic acid (TPA) lanthanum 0.76%,
Dibutyl tin laurate 1.43%.
Claims (9)
1. a kind of high temperature resistant chlorinated polypropylene, it is characterised in that include following component by mass percentage：Polypropylene powder
95.06% ~ 95.88%, initiator 0.57% ~ 0.58%, suspending agent 0.38% ~ 0.38%, dispersant 1.43% ~ 1.44%, heat stabilizer
1.72%~2.58%。
2. high temperature resistant chlorinated polypropylene according to claim 1, it is characterised in that initiator is benzoyl peroxide, peroxide
Change diisopropylbenzene (DIPB), tert-butyl hydroperoxide, di-t-butyl peroxide one kind or combination.
3. high temperature resistant chlorinated polypropylene according to claim 1, it is characterised in that suspending agent is carboxymethyl cellulose, xanthan
Glue, polyvinyl alcohol are a kind of or combine.
4. high temperature resistant chlorinated polypropylene according to claim 1, it is characterised in that dispersant be neopelex,
Sodium cetanesulfonate, one kind of oleoyl oxygroup ethanesulfonic acid sodium or combination.
5. high temperature resistant chlorinated polypropylene according to claim 1, it is characterised in that heat stabilizer by terephthalic acid (TPA) lanthanum and
Dibutyl tin laurate forms.
6. high temperature resistant chlorinated polypropylene according to claim 5, it is characterised in that the terephthalic acid (TPA) lanthanum 0.76% ~
1.15%, dibutyl tin laurate 0.96% ~ 1.43%.
7. a kind of high temperature resistant chlorinated polypropylene preparation method as described in one of claim 1 ~ 6, it is characterised in that including following
Step：
First by after polypropylene liquid nitrogen frozen 1-2 hours, attrition grinding is at polypropylene powdery;
Polypropylene powder is added in the reaction kettle that 20 times of dosage water of polypropylene weight has been added, in whipping process, is added
0.57% ~ 0.58% initiator, 0.38% ~ 0.38% suspending agent and 1.43% ~ 1.44% dispersant, under stirring,
It is in suspended state to make polypropylene powder, is warming up to 80-85 DEG C；
Start the chlorine for being passed through 1.2-1.5 times of polypropylene dosage, normal pressure chlorination reaction keeps the temperature 1-1.5 hours, will with compressed air
Chlorine is replaced away, synthesizing chlorinated polypropylene；
0.76% ~ 1.15% terephthalic acid (TPA) lanthanum and 0.96% ~ 1.43% dibutyl tin laurate are added into reaction kettle, are stirred
Continue heat preservation 0.5 hour under mixing；
After reaction, stop heating, be cooled to room temperature, neutrality is neutralized to sodium hydroxide, after washing, drying, obtain powder
Shape high temperature resistant chlorinated polypropylene.
8. a kind of high temperature resistant chlorinated polypropylene preparation method according to claim 7, it is characterised in that by powdery high temperature resistant
High temperature resistant chlorinated polypropylene particle is made in chlorinated polypropylene extruding pelletization, 100-120 DEG C of prilling temperature.
9. a kind of application of high temperature resistant chlorinated polypropylene as described in one of claim 1 ~ 6, it is characterised in that drawn for being cast
The preparation for stretching PETG/PP/PETG thermal contractive label films carries out blending and modifying processing for PP materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810087698.3A CN108299575A (en) | 2018-01-30 | 2018-01-30 | A kind of high temperature resistant chlorinated polypropylene and preparation method thereof and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810087698.3A CN108299575A (en) | 2018-01-30 | 2018-01-30 | A kind of high temperature resistant chlorinated polypropylene and preparation method thereof and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108299575A true CN108299575A (en) | 2018-07-20 |
Family
ID=62866827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810087698.3A Pending CN108299575A (en) | 2018-01-30 | 2018-01-30 | A kind of high temperature resistant chlorinated polypropylene and preparation method thereof and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108299575A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0369023A1 (en) * | 1988-04-06 | 1990-05-23 | Toyo Seikan Kaisha, Ltd. | Container equipped with label and production method thereof |
| CN1283607A (en) * | 2000-07-17 | 2001-02-14 | 彭世杰 | Rare-earth phenyldiformate, and its preparing process and application |
| CN1961007A (en) * | 2004-05-31 | 2007-05-09 | 日本制纸化学株式会社 | Chlorinated propylene random copolymer and compositions containing the same |
| CN101304876A (en) * | 2005-11-15 | 2008-11-12 | 陶氏环球技术公司 | Oriented multi-layer shrink labels |
| CN102504059A (en) * | 2011-10-26 | 2012-06-20 | 上海氯碱化工股份有限公司 | Aqueous-phase suspension chlorination method for producing chlorinated polypropylene |
-
2018
- 2018-01-30 CN CN201810087698.3A patent/CN108299575A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0369023A1 (en) * | 1988-04-06 | 1990-05-23 | Toyo Seikan Kaisha, Ltd. | Container equipped with label and production method thereof |
| CN1283607A (en) * | 2000-07-17 | 2001-02-14 | 彭世杰 | Rare-earth phenyldiformate, and its preparing process and application |
| CN1961007A (en) * | 2004-05-31 | 2007-05-09 | 日本制纸化学株式会社 | Chlorinated propylene random copolymer and compositions containing the same |
| CN101304876A (en) * | 2005-11-15 | 2008-11-12 | 陶氏环球技术公司 | Oriented multi-layer shrink labels |
| CN102504059A (en) * | 2011-10-26 | 2012-06-20 | 上海氯碱化工股份有限公司 | Aqueous-phase suspension chlorination method for producing chlorinated polypropylene |
Non-Patent Citations (1)
| Title |
|---|
| 许长清: "《合成树脂及塑料手册》", 30 November 1991, 化学工业出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108297511A (en) | One kind is for casting and stretching thermal contractive label film and preparation method thereof | |
| TW212771B (en) | ||
| US6616998B2 (en) | Polyester packaging films producing a peelable seal | |
| WO1998003334A1 (en) | Gas-barrier composite film | |
| NL2019329B1 (en) | Multilayer laminate film assembly and standing pouch | |
| CN102020056B (en) | Multilayer coextruded liquid packaging film capable of reducing leakage rate | |
| WO1992005941A1 (en) | Process for producing laminate film | |
| WO2021103519A1 (en) | High-barrier biodegradable stand-up pouch and preparation method therefor | |
| JPH03176142A (en) | Multi-layer barrier structure for packaging and manufacture therefor | |
| CN102079418A (en) | Multi-layer co-extruded paper-like liquid packaging film | |
| CN1537138A (en) | Synthetic paper skins and methods of their manufacture | |
| TW445281B (en) | Multilayered moldings and polyphenylene sulfide compositions | |
| JP6350276B2 (en) | Biaxially oriented polyamide resin film | |
| JPH11106592A (en) | Resin composition and its laminate | |
| CN105416797B (en) | A kind of biodegradable express packaging bag and its preparation technology | |
| CN108102194A (en) | A kind of PE film packing materials and preparation method thereof | |
| CN102963094B (en) | A kind of polyamide/polypropylene composite materials medical package film | |
| WO2006019092A1 (en) | Stretched polyamide film | |
| CN108299575A (en) | A kind of high temperature resistant chlorinated polypropylene and preparation method thereof and application | |
| CN102471546A (en) | Polymeric composition, method for producing non-stretched film, non-stretched film, heat-sealing material, and packaging material | |
| JP2002155135A (en) | Adhesive polymer composition and its manufacturing method | |
| JPH0459353A (en) | Laminate wrapping film | |
| CN202986265U (en) | Antibacterial barrier five-layer co-extruded composite film | |
| CN110105642A (en) | A kind of high-impact ABS/PVC luggage handle alloy material and preparation method thereof | |
| JP2004001252A (en) | Stretched laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180720 |