CN108102257A - It is a kind of have can lettering feature PVC thermal contractive label films and preparation method thereof - Google Patents
It is a kind of have can lettering feature PVC thermal contractive label films and preparation method thereof Download PDFInfo
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- CN108102257A CN108102257A CN201810068673.9A CN201810068673A CN108102257A CN 108102257 A CN108102257 A CN 108102257A CN 201810068673 A CN201810068673 A CN 201810068673A CN 108102257 A CN108102257 A CN 108102257A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
Abstract
The invention discloses it is a kind of have can lettering feature PVC thermal contractive labels film and preparation method, on the basis of traditional PVC film manufacture craft, a certain amount of treated paper pulp is added in formula, to increase the hydrophily of film surface.Meanwhile go back emphasis and the lubricating system in formula is adjusted, lubricant quantity is significantly reduced, with there is smooth opening agent instead of the part external lubricant in common PVC thermal contractive label film formulation, increases the roughness on PVC film surface with this.So as on the basis of common PVC thermal contractive label film shrinking percentage and other main performances are kept, realize the purpose that can be directly write with pen above.
Description
Technical field
The present invention relates to PCV label technical field of membrane, and in particular to it is a kind of have can lettering feature PVC thermal contractive labels
Film and preparation method.
Background technology
Bottled drink and water because its distribution is convenient, carry, easy to use, hygienic fashion, it has also become a kind of all the fashion
Common consumer product, more as a kind of common drink occupation mode in group activity.Since bottled drink has certain capacity, base
It will not disposably finish off on this, generally to quote several times.The storage of the half bottle of water or beverage do not drunk, for personal or a small amount of
Crowd is not problem, but in the more group activity of number, these half bottle of drink is left concentratedly just very intractable into one
Problem.Since drink appearance is identical, these half bottle of beverage is left concentratedly when taking again, it is easy to mix up, be brought to drinking person tired
Puzzled and trouble.Sometimes due to can not distinguish, and be afraid of cross-infection, can only throw away, so as to cause to waste.It if can be outside bottle
It writes name or leaves mark, just can easily distinguish the user of drink, avoid mutually taking by mistake, pollute and awkward.
Thermal contractive label is mostly using the full mark mode of whole package bottle, and bottle is not by only bottom of bottle and the bottle of label package
Small parts area, these positions such as mouth are also inconvenient to write and check.Even if some PET bottles dress drink is using middle-size and small-size half mark mark
Label mode, bottle sheet have sufficient space and area that can write with it, equally very big with the difficulty for connecing writing straight in PET bottle.
In addition, in terms of MAT'L recycling angle, the pollution when writing will not cause to recycle on printed matter label, and if in bottle
It writes or is marked with pen on body, certain pollution problem will be brought to the recycling of bottle piece.
The content of the invention
The technical problem to be solved by the present invention is to the technical issues of existing thermal contractive label film dysgraphia.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：It is a kind of have can lettering feature PVC heat
The preparation method of shrink label film includes the component of following weight fraction：100 parts of polyvinyl chloride resin main material, heat stabilizer 1.5~
2.5 parts, 6~80 parts of plasticizer, 5-6 parts of toughener, 0.2~0.3 part of in-lubricant, 0.4~0.6 part of external lubricant, paper pulp 8~
10 parts, 0.05~0.08 part of preparing spherical SiO 2；Wherein paper pulp is by dry and coupling processing.
Further, dried paper pulp carries out coupling processing together with chitosan and amino silane, wherein dry paper pulp,
Chitosan, the mass ratio of amino silane three are：100：1.5~2.0：0.3~0.5.
Further, 1.5-2.5 parts of acrylate copolymer is further included in component.
Further, the thermostabilization is organotin mercaptide methyl tin 181, and plasticizer is dioctyl terephthalate, is increased
Tough dose is MBS, and in-lubricant is fatty alcohol complex ester, and external lubricant is oxidized polyethylene wax
Further, the D50 of the preparing spherical SiO 2 is 1.8 μm.
In addition, the present invention also provides the preparation methods of the thermal contractive label film, specifically comprise the following steps
(1) processing is dried in paper pulp, coupling processing is carried out together with chitosan and amino silane after drying process, mixed
It closes uniform；
(2) polyvinyl chloride resin, heat stabilizer organotin, plasticizer terephthalic acid (TPA) two are added in high-speed mixer rotation process
Monooctyl ester；
(3) when high-speed mixer temperature is increased to 75-80 DEG C, toughener MBS, acrylate copolymer, interior profit are added
Lubrication prescription and by treated in step 1 paper pulp；
(4) when high-speed mixer temperature is increased to 95-100 DEG C, external lubricant oxidized polyethylene wax and spherical shape two are added
Silica；
(5) when high-speed mixer temperature is increased to 125 DEG C, mixture is put into cooling mixing machine and stirs cooling；
(6) cooling mixing machine temperature to less than 45 DEG C when discharge, obtain dry blend, it is spare；
(7) dry blend mixed is added in extruder plasticizing to squeeze out, is molded using blown-film die, secondary inflation；
Wherein each composition proportion is：100 parts of polyvinyl chloride resin main material, 1.5~2.5 parts of heat stabilizer organotin, plasticizer 6
~8 parts, 5-6 parts of toughener MBS, 0.2~0.3 part of in-lubricant, 0.4~0.6 part of external lubricant oxidized polyethylene wax, paper pulp 8
~10 parts, 0.05~0.08 part of preparing spherical SiO 2,1.5-2.5 parts of acrylate copolymer.
Further, when handling pulp dryer, using hot-air blowing drying mode, hot wind flow velocity is more than 5m/s, hot wind
Temperature is 105~115 DEG C or so, and air inlet need to be through dehumidification treatments.
Further, in paper pulp coupling processing, dry paper pulp, chitosan, the mass ratio of amino silane three are：100：
1.5~2.0：0.3~0.5, after being weighed according to proportioning, chitosan and amino silicane coupling agent are configured to 20~30% isopropyl
Alcoholic solution, it is uniform with high-speed mixer mixed at high speed then by the spray solution to dry paper pulp.
From above-mentioned technical proposal it can be seen that the present invention has the following advantages：Preparing spherical SiO 2 have the function of it is smooth, can
To play the lubricating function of external lubricant, and the roughness on PVC film surface can be increased, paper pulp can increase the table of the label film
Face hydrophily increases its tension, is unfolded so as to which pen oil be facilitated to be infiltrated on its surface.
Specific embodiment
The present invention is described in detail below in conjunction with specific embodiment, embodiment is only the preferred side of the present invention
Formula is not limitation of the invention.
Embodiment one：
Paper pulp is dried first and coupling processing；
Pulp dryer processing：Paper pulp uses hot-air blowing drying mode, hot wind flow velocity >=5m/s, hot blast temperature 105~115
DEG C or so, air inlet need to be through dehumidification treatments, 4 to 6 hours of drying time；
Coupling processing：Dry paper pulp is carried out even together with chitosan and amino silane (r- aminopropyltriethoxywerene werenes)
Connection processing.
Dry paper pulp, chitosan, the mass ratio of amino silane three are：100：1.5~2.0：0.3~0.5, according to proportioning
After weighing, chitosan and amino silicane coupling agent are configured to the aqueous isopropanol of 20~30% (being preferably 25%), then will
The spray solution is uniform with high-speed mixer mixed at high speed on dry paper pulp.
High-speed mixer and cooling mixing machine is recycled to be uniformly mixed material, the proportionate relationship of following material refers both to matter
Amount comparison, is as follows：
(1) 100 parts of polyvinyl chloride resins, 2 parts of heat stabilizer organotins, 6 parts of plasticizer pair are added in high-speed mixer rotation process
Thiol methyl tin 181 may be employed in dioctyl phthalate, organotin, and transparency is high, excellent heat resistance, has prominent inhibition
Tinctorial property early period when PVC product is processed.
(2) when high-speed mixer temperature is increased to 75-80 DEG C, 5 parts of MBS of toughener, 2 parts of acrylic ester copolymers are added
Object, 03 part of in-lubricant and 8 parts of the paper pulp crossed by above-mentioned drying and coupling processing；MBS- may be employed in toughener
736, acrylate copolymer can then select the ACR P551A of Mitsubishi Corporation of Japan, and in-lubricant uses RGH-4, RGH-4 with
The compatibility of PVC is good, can evenly spread between strand, so as to reduce the interior friction of strand, improves mobility；
PVC shows acid, contains acetylamino in chitosan molecule chain, shows alkalescence, and the two can combine very well.Meanwhile acetylamino is also
It can react with the hydroxyl in paper cellulose.There are two types of functional groups, i.e. amino and ethyoxyl for amino silane tool.Wherein three
A hydrolyzable groups (ethyoxyl), in the reaction first hydrolysis generation silanol, since silanol is unstable, easily with inorganic matter or metal
The hydroxy combining dehydration on surface, so as to combine with inorganic matter or metal.On amino band there are two active hydrogen can with it is various
Polymer reacts, and so as to be combined paper pulp and PVC by chemical bond, and paper pulp can then increase the parent of film surface
It is aqueous.
(3) when high-speed mixer temperature is increased to 95-100 DEG C, add 0.5 especially lubricant oxidation polyethylene wax and
0.06 part of preparing spherical SiO 2；The external lubricants such as oxidized polyethylene wax can reduce polymer in molding process with shaping
The interface friction on processing equipment surface, it is single also to promote PVC surface smooth, its surface tension is reduced, causes pen oil effective
Infiltration expansion, it is therefore desirable to reduce its additive amount.Preparing spherical SiO 2 has the function of smooth, can play the lubrication of external lubricant
Function, and the roughness on PVC film surface can be increased, it is preferred to use D50 is the preparing spherical SiO 2 of 1.8um.
(4) when high-speed mixer temperature is increased to 125 DEG C or so, mixture is put into cooling mixing machine and stirs cooling；
(5) cooling mixing machine temperature to less than 45 DEG C when discharge, obtain dry blend, it is spare.
Material carries out blow molding after mixing again, and technological process is as follows：
Dry blend --- extruder plasticizing --- blown-film die shaping --- tubular film --- collapser --- biplate
Film --- infrared baking oven heating --- secondary inflation --- cooling and shaping --- collapser --- biplate film roll is bent --- point
Cut --- packaging --- inspection --- finished product；
Equipment：Single screw extrusion machine, screw diameter 65mm, screw slenderness ratio 29.5:1, compression ratio 2.8:1.
Blown film die port mould diameter 130mm, mouth mold gap 0.8mm, double air port vanes.
Extruder temperature：145-150 DEG C, 150-155 DEG C, 160-165 DEG C, 175-185 DEG C, 170-180 DEG C.Linkage section temperature
Degree：175-180℃.Mold temperature:180-190 DEG C, 190-200 DEG C.Baking oven heating temperature 78,81,85 DEG C.
The label film that thickness is 0.05mm is made into, is tested for the property, design parameter is as follows：
Its transverse tensile strength is 100.8MPa, longitudinal tensile strength 67.3MPa；Its transverse breakage elongation is
53.2MPa, longitudinal elongation at break rate 129.8MPa；Lateral shrinkage is 48.3%, and longitudinal contraction rate is 2.7%；Light transmittance
For 77.2%；Contact angle is 56.1 °；Dyne value is 44mN/m.
Embodiment two is substantially the same with the technical solution of embodiment one, and difference is the composition of component：
Wherein mass ratio of each component is：100 parts of polyvinyl chloride resin main material, 2 parts of heat stabilizer organotin, 8 parts of plasticizer, increasing
Tough dose of 6 parts of MBS, 0.2 part of in-lubricant, 0.5 part of external lubricant oxidized polyethylene wax, 10 parts of paper pulp, preparing spherical SiO 2 0.08
Part, 2 parts of acrylate copolymer.
The label film that thickness is 0.05mm is made into, is tested for the property, design parameter is as follows：
Its transverse tensile strength is 101.3MPa, longitudinal tensile strength 66.1MPa；Its transverse breakage elongation is
52.1MPa, longitudinal elongation at break rate 131.2MPa；Lateral shrinkage is 48.9%, and longitudinal contraction rate is 2.9%；Light transmittance
For 76.5%；Contact angle is 53.4 °；Dyne value is 46mN/m.
Comparative example one
PVC raw materials and auxiliary agent are weighed according to formula rate, charging in the following order is mixed with dry blend.
(1) 100 parts of polyvinyl chloride resins, 2 parts of 181,4.5 parts of thiol methyl tins are added in high-speed mixer rotation process to benzene two
Formic acid dioctyl ester；
(2) when high-speed mixer temperature is increased to 75-80 DEG C, add 4 parts of plasticizer MBS, 2 parts of acrylate copolymers,
0.7 part of in-lubricant；
(3) when high-speed mixer temperature is increased to 95-100 DEG C, external lubricant is added；
(4) when high-speed mixer temperature is increased to 120 DEG C or so, mixture is put into cooling mixing machine and stirs cooling；
(5) cooling mixing machine temperature to less than 45 DEG C when discharge, obtain dry blend, it is spare.
Material carries out blow molding after mixing again, and concrete technology is identical with embodiment two with embodiment one, herein not
It repeats again.
The label film that thickness is 0.05mm is made into, is tested for the property, design parameter is as follows：
Its transverse tensile strength is 98.7MPa, longitudinal tensile strength 63.4MPa；Its transverse breakage elongation is
60.7MPa, longitudinal elongation at break rate 150.3MPa；Lateral shrinkage is 50.2%, and longitudinal contraction rate is 2.1%；Light transmittance
For 88.1%；Contact angle is 88.7 °；Dyne value is 38mN/m.
To sum up, its contact angle of PVC thermal contractive labels film is at 55 ° or so made of proportioning and technique using the present invention, parent
Aqueous good, for dyne value 45 or so, surface tension can be adapted for water-color paintbrush or ball pen used in everyday.
Claims (8)
1. it is a kind of have can lettering feature PVC thermal contractive label films preparation method, it is characterised in that including following weight point
Several components：100 parts of polyvinyl chloride resin main material, 1.5~2.5 parts of heat stabilizer, 6~80 parts of plasticizer, 5-6 parts of toughener, interior profit
0.2~0.3 part of lubrication prescription, 0.4~0.6 part of external lubricant, 8~10 parts of paper pulp, 0.05~0.08 part of preparing spherical SiO 2；
Wherein paper pulp is by dry and coupling processing.
2. it is according to claim 1 have can lettering feature PVC thermal contractive label films, it is characterised in that：It is dried
Paper pulp carries out coupling processing together with chitosan and amino silane, wherein dry paper pulp, chitosan, the quality of amino silane three
Than for：100：1.5~2.0：0.3~0.5.
3. it is according to claim 2 have can lettering feature PVC thermal contractive label films, it is characterised in that：In component also
Include 1.5-2.5 parts of acrylate copolymer.
4. it is according to claim 1 have can lettering feature PVC thermal contractive label films, it is characterised in that：The heat is steady
It is set to organotin mercaptide methyl tin 181, plasticizer is dioctyl terephthalate, and toughener MBS, in-lubricant is fatty alcohol
Complex ester, external lubricant are oxidized polyethylene wax.
5. it is according to claim 1 have can lettering feature PVC thermal contractive label films, it is characterised in that：The spherical shape
The D50 of silica is 1.8 μm.
6. it is a kind of have can lettering feature PVC thermal contractive label membrane preparation methods, it is characterised in that include the following steps：
(1) processing is dried in paper pulp, coupling processing is carried out together with chitosan and amino silane after drying process, mixing is equal
It is even；
(2) polyvinyl chloride resin, heat stabilizer organotin, plasticizer dioctyl terephthalate are added in high-speed mixer rotation process；
(3) when high-speed mixer temperature is increased to 75-80 DEG C, toughener MBS, acrylate copolymer, in-lubricant are added
And by treated in step 1 paper pulp；
(4) when high-speed mixer temperature is increased to 95-100 DEG C, external lubricant oxidized polyethylene wax and spherical titanium dioxide are added
Silicon；
(5) when high-speed mixer temperature is increased to 125 DEG C, mixture is put into cooling mixing machine and stirs cooling；
(6) cooling mixing machine temperature to less than 45 DEG C when discharge, obtain dry blend, it is spare；
(7) dry blend mixed is added in extruder plasticizing to squeeze out, is molded using blown-film die, secondary inflation；
Wherein each composition proportion is：100 parts of polyvinyl chloride resin main material, 1.5~2.5 parts of heat stabilizer organotin, plasticizer 6~8
Part, 5-6 parts of toughener MBS, 0.2~0.3 part of in-lubricant, 0.4~0.6 part of external lubricant oxidized polyethylene wax, paper pulp 8~
10 parts, 0.05~0.08 part of preparing spherical SiO 2,1.5-2.5 parts of acrylate copolymer.
7. it is according to claim 6 have can lettering feature PVC thermal contractive label membrane preparation methods, it is characterised in that：
When handling pulp dryer, using hot-air blowing drying mode, hot wind flow velocity is more than 5m/s, and hot blast temperature is 105~115 DEG C of left sides
The right side, air inlet need to be through dehumidification treatments.
8. it is according to claim 7 have can lettering feature PVC thermal contractive label membrane preparation methods, it is characterised in that：
In paper pulp coupling processing, dry paper pulp, chitosan, the mass ratio of amino silane three are：100：1.5~2.0：0.3~
0.5, after being weighed according to proportioning, chitosan and amino silicane coupling agent are configured to 20~30% aqueous isopropanol, then will
The spray solution is uniform with high-speed mixer mixed at high speed on dry paper pulp.
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Cited By (1)
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| CN114316479A (en) * | 2022-02-23 | 2022-04-12 | 宜兴市光辉包装材料有限公司 | Environment-friendly tracing type PVC heat-shrinkable label film and preparation method thereof |
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