CN108148256A - It is a kind of can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve and preparation method thereof - Google Patents
It is a kind of can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve and preparation method thereof Download PDFInfo
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- CN108148256A CN108148256A CN201711409335.9A CN201711409335A CN108148256A CN 108148256 A CN108148256 A CN 108148256A CN 201711409335 A CN201711409335 A CN 201711409335A CN 108148256 A CN108148256 A CN 108148256A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention particularly discloses it is a kind of can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve and preparation method thereof, described sleeve pipe contains each component of following mass percent：Ethylene vinyl acetate copolymer elastomer 30% 50%, ethylene ethyl acrylate copolymer elastomer 15% 25%, high-efficiency compound fire-proof agent 25% 40%, laser additive 0.5 2%, color masterbatch 2% 4%, thermal oxidation stabilizer 0.5% 2%.The present invention prepare can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, with good laser printing performance, permanent identification performance, flame retardant property, shrinkage, mechanical performance can be applied to the permanent identification of the fields such as aerospace, military project, electronics, communication, high ferro, shipbuilding high performance cables.
Description
Technical field
The present invention relates to cable permanent identification heat-shrinkage material technical fields, and in particular, to one kind can laser printing
High fire-retardance flame-retardant heat shrinkable label sleeve and preparation method thereof.
Background technology
Heat-shrinkage material, also known as polymer shape memory material, memory material are that extraordinary linear high molecular material passes through spoke
According to becoming space network after crosslinking, the principle with " memory effect " after crosslinking and a kind of novel high polymer for manufacturing
Functional material.
Traditional identification sleeving is generally printed using thermal transfer, and needs to select dedicated carbon ribbon, but will for some
Harsh use environment is sought, such as touches various solvents, various petroleum products or repeatedly rubs back and forth, traditional printing
Effect does not reach requirement, and printable character is easy to fall off or is fallen by liquid corrosions such as solvents.For more demanding occasion, such as it is used to navigate
The permanent identification of the fields such as empty space flight, military project, electronics, communication, high ferro, shipbuilding high performance cables, traditional identification sleeving also reach
Less than requiring.
Therefore, it is badly in need of developing the heat that there is permanent printing to identify performance of a kind of character solvent resistant not easily to fall off, oil resistant
Shrink identification sleeving.
Invention content
For the above-mentioned deficiency of the prior art, the present invention provide it is a kind of can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve
And preparation method thereof.
To achieve these goals, the present invention is achieved by the following technical programs：
It is a kind of can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, each component containing following mass percent：Ethylene-
Vinyl acetate copolymer elastomer 35%-50%, ethylene-ethyl acrylate copolymer elastomer 15%-25%, high efficiency composition
Fire retardant 25%-40%, laser additive 0.5-2%, color masterbatch 2%-4%, thermal oxidation stabilizer 0.5%-2%.
Preferably, each component containing following mass percent：Vinyl-vinyl acetate copolymer elastomer 38%-
45%, ethylene-ethyl acrylate copolymer elastomer 20%-30%, high-efficiency compound fire-proof agent 30%-38%, laser additive
0.5-2%, color masterbatch 2.5%-3.5%, thermal oxidation stabilizer 0.5%-1.5%.
It is highly preferred that each component containing following mass percent：Vinyl-vinyl acetate copolymer elastomer 40%,
Ethylene-ethyl acrylate copolymer elastomer 20%, high-efficiency compound fire-proof agent 35%, laser additive 1%, color masterbatch 3%, hot oxygen
Change stabilizer 1%.
Preferably, the vinyl-vinyl acetate copolymer elastomer and ethylene-ethyl acrylate copolymer elastomer
Compound is as matrix；The MI ranging from 0.5-6g/10min of the vinyl-vinyl acetate copolymer elastomer；The second
The MI ranging from 1.0-5.0g/10min of alkene-ethyl acrylate copolymer elastomer.
Preferably, the high-efficiency compound fire-proof agent is the compound of decabromodiphenylethane, magnesium hydroxide and antimony oxide；
The compound proportion of decabromodiphenylethane, magnesium hydroxide and antimony oxide is mass percent 2:1:1；The decabromodiphenylethane
Grain size is less than 2 μm；The antimony oxide purity is more than 99.5%, and grain size is less than 1 μm；The magnesium hydroxide grain size is less than 1.5 μ
m；The high-efficiency compound fire-proof agent is modified using silane-modified or polymer overmold.
Preferably, the laser additive grain size is less than 2 μm, and applicable wavelengths are the laser printing system of 308-2200nm,
It is also applied for the CO that wavelength is 10600nm2Laser printing system.
Preferably, the thermal oxidation stabilizer is multiple using antioxidant 1010 and thio-2 acid 2 stearyl ester (DSDTP)
With into.
Preferably, the color masterbatch is the color masterbatch using ethylene-vinyl acetate copolymer or low density polyethylene (LDPE) as carrier.
It is above-described can laser printing application of the high fire-retardance flame-retardant heat shrinkable label sleeve in permanent identification product is prepared.
A kind of preparation method of above-mentioned high fire-retardance flame-retardant heat shrinkable label sleeve, includes the following steps：
S1. by vinyl-vinyl acetate copolymer elastomer, ethylene-ethyl acrylate copolymer elastomer, high efficiency composition
Fire retardant, laser additive, color masterbatch and thermal oxidation stabilizer compound be pre-mixed in proportion, and stir evenly；
S2. it is granulated by twin-screw mixer extruder blending extrusion, masterbatch passes through extrusion molding；Squeeze out the internal diameter of semi-finished product
0.5mm~30mm, wall thickness 0.4mm~1.0mm；
S3. cross-linking radiation；Cross-linking radiation dosage is 5Mrad~10Mrad；
S4. vacuum is continuously expanded；Product internal diameter 1.5mm~60mm, wall thickness 0.2mm~0.5mm after expansion；
S5. it flattens.
Pellet its performance indicator prepared by above-mentioned steps is as follows：Irradiate post-tensioning intensity >=10.4MPa, extension at break
Rate is >=200%；Oxygen index (OI) OI is >=29.
Compared with prior art, the present invention has the advantages that：
The present invention prepare can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, have good laser printing performance,
Permanent identification performance, flame retardant property, shrinkage, mechanical performance, can be applied to aerospace, military project, electronics, communication, high ferro,
The permanent identification of the fields such as shipbuilding high performance cables.
Description of the drawings
Fig. 1 is the structure diagram of the present invention.
Specific embodiment
The present invention is further elaborated with reference to specific embodiment, the embodiment is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.Test method used in following embodiments is routine unless otherwise specified
Method；Used material, reagent etc., unless otherwise specified, for the reagent and material commercially obtained.
Embodiment 1
It is a kind of can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, each component containing following mass percent, ethylene-
Vinyl acetate copolymer elastomer 30%-50%, ethylene-ethyl acrylate copolymer elastomer 15%-25%, high efficiency composition
Fire retardant 25%-40%, laser additive 0.5-2%, color masterbatch 2%-4%, thermal oxidation stabilizer 0.5%-2%.
It is above-mentioned can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve preparation method, include the following steps：
S1. by vinyl-vinyl acetate copolymer elastomer, ethylene-ethyl acrylate copolymer elastomer, high efficiency composition
Fire retardant, laser additive, color masterbatch and thermal oxidation stabilizer compound be pre-mixed in proportion, and stir evenly；
S2. it is granulated by twin-screw mixer extruder blending extrusion, masterbatch passes through extrusion molding；
S3. cross-linking radiation；
S4. vacuum is continuously expanded；
S5. it flattens.
As shown in Figure 1, part after including part before shrinking by casing prepared by above-mentioned preparation method and shrink.
Embodiment 2
By the formula and method of embodiment 1 prepare can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, use
Method is as follows：
By can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve laser printer types identify character, being sleeved on needs to mark
On the cable of knowledge, with the heating tools heat shrink such as heat gun or baking oven, heat shrink temperature is at 150 DEG C~200 DEG C or so, heating
It can shrink completely within 1~3 minute.Easy to operate, cladding appearance looks elegant is coated through the product pyrocondensation, it is clear lasting to identify, insulation
Barrier propterty is good, and flame retardant property is good.
It is of the present invention can the test method of high fire-retardance flame-retardant heat shrinkable label sleeve of laser printing include：SAE AMS-
DTL-23053、ASTM D2671、SAE AS81531、MIL-STD-202。
Embodiment 3
According to 1 preparation method of embodiment, be formulated using 3 kinds prepare different performance can the high fire-retardance heat of laser printing receive
Contracting identification sleeving, the formula of 3 kinds of casings are as shown in table 1.
Table 1
| Component | Formula 1 | Formula 2 | Formula 3 |
| Vinyl-vinyl acetate copolymer elastomer | 30% | 40% | 50% |
| Ethylene-ethyl acrylate copolymer elastomer | 23.5% | 20% | 18% |
| High-efficiency compound fire-proof agent | 40% | 35% | 27% |
| Laser additive | 2% | 1% | 0.5% |
| Color masterbatch | 4% | 3% | 2.5% |
| Thermal oxidation stabilizer | 0.5% | 1% | 2% |
According to the test method of embodiment 2, respectively to three kinds of formulas can laser printing high fire-retardance flame-retardant heat shrinkable label set
The properties of product of pipe are tested, and properties of product test result is as shown in table 2.
Table 2
The test result of summary analysis 2, show be formulated 1-3 can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve it is equal
With good tensile strength and elongation at break, there is the synthesis such as good heat resistance, high and low temperature resistance, thermal contraction performance
Performance, laser printing mark are had excellent performance, character solvent resistant, oil resistant, scratch-resistant, and with excellent flame retardant property, can be extensive
Applied to the permanent identification of the fields such as aerospace, military project, electronics, communication, high ferro, shipbuilding high performance cables, have wide
Market prospects and important application meaning.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of range is protected, although being explained in detail with reference to preferred embodiment to the present invention, those of ordinary skill in the art should
Work as understanding, technical scheme of the present invention can be modified or replaced equivalently, without departing from the reality of technical solution of the present invention
Matter and range.
Claims (10)
1. it is a kind of can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, which is characterized in that contain each of following mass percent
Component：Vinyl-vinyl acetate copolymer elastomer 30%-50%, ethylene-ethyl acrylate copolymer elastomer 15%-
25%, high-efficiency compound fire-proof agent 25%-40%, laser additive 0.5%-2%, color masterbatch 2%-4%, thermal oxidation stabilizer
0.5%-2%.
2. it is according to claim 1 can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, which is characterized in that containing following
The each component of mass percent：Vinyl-vinyl acetate copolymer elastomer 35%-45%, ethylene-ethyl acrylate copolymer
Elastomer 17%-23%, high-efficiency compound fire-proof agent 30%-38%, laser additive 0.8%-1.5%, color masterbatch 2.5%-
3.5%, thermal oxidation stabilizer 0.5%-1.5%.
3. it is according to claim 2 can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, which is characterized in that containing following
The each component of mass percent：Vinyl-vinyl acetate copolymer elastomer 40%, ethylene-ethyl acrylate copolymer elasticity
Body 20%, high-efficiency compound fire-proof agent 35%, laser additive 1%, color masterbatch 3%, thermal oxidation stabilizer 1%.
4. it is according to claim 1 can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, which is characterized in that the second
The compound of alkene-vinyl acetate copolymer elastomer and ethylene-ethyl acrylate copolymer elastomer is as matrix；The second
The MI ranging from 0.5-6g/10min of alkene-vinyl acetate copolymer elastomer；The ethylene-ethyl acrylate copolymer elasticity
The MI of body ranging from 1.0-5.0g/10min.
5. it is according to claim 1 can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, which is characterized in that it is described efficiently
Composite flame-retardant agent is the compound of decabromodiphenylethane, magnesium hydroxide and antimony oxide；Decabromodiphenylethane, magnesium hydroxide and
The compound proportion of antimony oxide is mass percent 2:1:1；The decabromodiphenylethane grain size is less than 2 μm；Three oxidation
Two antimony purity are more than 99.5%, and grain size is less than 1 μm；The magnesium hydroxide grain size is less than 1.5 μm；The high-efficiency compound fire-proof agent is adopted
It is modified with silane-modified or polymer overmold.
6. it is according to claim 1 can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, which is characterized in that the laser
Additive grain size is less than 2 μm, and applicable wavelengths are the laser printing system of 308-2200nm, and it is 10600nm's to be also applied for wavelength
CO2Laser printing system.
7. it is according to claim 1 can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, which is characterized in that the hot oxygen
Change stabilizer to compound using antioxidant 1010 and thio-2 acid 2 stearyl ester.
8. it is according to claim 1 can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve, which is characterized in that the color masterbatch
It is the color masterbatch using ethylene-vinyl acetate copolymer or low density polyethylene (LDPE) as carrier.
9. a kind of claim 1-8 any one of them can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve preparation method,
It is characterized by comprising the following steps：
S1. by vinyl-vinyl acetate copolymer elastomer, ethylene-ethyl acrylate copolymer elastomer, high-efficiency compound fire-proof
Agent, laser additive, color masterbatch and thermal oxidation stabilizer compound be pre-mixed in proportion, and stir evenly；
S2. it is granulated by twin-screw mixer extruder blending extrusion, masterbatch passes through extrusion molding；Squeeze out the internal diameter of semi-finished product
0.5mm-30mm, wall thickness 0.4mm-1.0mm；
S3. cross-linking radiation；Cross-linking radiation dosage is 5Mrad-10Mrad；
S4. vacuum is continuously expanded；Product internal diameter 1.5mm-60mm, wall thickness 0.2mm-0.5mm after expansion；
S5. it flattens.
10. it is described in claim 1 can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve in permanent identification product is prepared
Using.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711409335.9A CN108148256A (en) | 2017-12-22 | 2017-12-22 | It is a kind of can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve and preparation method thereof |
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| CN201711409335.9A CN108148256A (en) | 2017-12-22 | 2017-12-22 | It is a kind of can laser printing high fire-retardance flame-retardant heat shrinkable label sleeve and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144077A (en) * | 2019-03-25 | 2019-08-20 | 大连联合高分子材料有限公司 | A kind of polyolefin flame-retardant heat shrinkable label sleeve and preparation method thereof |
| CN113929999A (en) * | 2021-09-27 | 2022-01-14 | 昶力管业(常州)有限公司 | Laser-engravable halogen-free flame-retardant identification sleeve and preparation method thereof |
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| JPH04122747A (en) * | 1990-09-14 | 1992-04-23 | Sumitomo Electric Ind Ltd | Flame-retardant resin composition and tube |
| CN1896128A (en) * | 2006-05-30 | 2007-01-17 | 广州凯恒科塑有限公司 | Fire-retarding thermal-shrinked indicated double pipe of radiant cross-linked and its preparation |
| CN102250405A (en) * | 2011-02-21 | 2011-11-23 | 长园集团股份有限公司 | 1E-grade K1-class halogen-free flame-retardant thermal shrinkage material for nuclear power plant and preparation method thereof |
| CN102276905A (en) * | 2010-06-13 | 2011-12-14 | 深圳市宏商材料科技股份有限公司 | Formulation of radiant cross-linked thermal-shrinked halogen-free fire-retardant identified casing product, and preparation method thereof |
| CN102741360A (en) * | 2010-01-14 | 2012-10-17 | 默克专利股份有限公司 | Laser additive |
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2017
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| JPH04122747A (en) * | 1990-09-14 | 1992-04-23 | Sumitomo Electric Ind Ltd | Flame-retardant resin composition and tube |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144077A (en) * | 2019-03-25 | 2019-08-20 | 大连联合高分子材料有限公司 | A kind of polyolefin flame-retardant heat shrinkable label sleeve and preparation method thereof |
| CN113929999A (en) * | 2021-09-27 | 2022-01-14 | 昶力管业(常州)有限公司 | Laser-engravable halogen-free flame-retardant identification sleeve and preparation method thereof |
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Application publication date: 20180612 |