CN108752793A - A kind of preparation method of antifouling anti-scribble high-molecular decorative film - Google Patents
A kind of preparation method of antifouling anti-scribble high-molecular decorative film Download PDFInfo
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- CN108752793A CN108752793A CN201810612072.XA CN201810612072A CN108752793A CN 108752793 A CN108752793 A CN 108752793A CN 201810612072 A CN201810612072 A CN 201810612072A CN 108752793 A CN108752793 A CN 108752793A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- 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
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
- C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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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
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The preparation method for the antifouling anti-scribble high-molecular furniture decorative film based on fluorochemical that the present invention relates to a kind of, including PVC base layer and surface functional layer.Wherein surface functional layer is combined using fluorochemical with polyvinyl chloride, and fluorine-containing fat and siloxanes carry out crosslinking copolymerization under radical initiator effect, and production stage includes prepared by PVC base layer；The preparation of the anti-scribble functional membrane of surface soiling；Hot pressing is bonded.The antifouling anti-scribble high-molecular decorative film of gained contains the fluorine silicon structure side chain of large-size, and content is controllable, the surface property that can significantly improve high-molecular decorative film has the characteristics that hydrophobic oleophobic, low-surface-energy, can be used as antifouling, anti-scribble, antibacterial, automatically cleaning decorating film basis material.
Description
Technical field
It is the present invention relates to polyvinyl chloride functional technical field of macromolecules, more particularly to a kind of poly- based on fluorinated acrylate
The preparation method of vinyl chloride polymer compound film.
Background technology
PVC macromolecular film is one kind using polyvinyl chloride as raw material, and addition suitable adjuvants are combined by calendering
A kind of new decorative material, can with the compound preparation multipurpose ornament materials of base materials such as timber, plastics, metal, be widely used in furniture,
The fields such as household electrical appliances, building, traffic.
It is especially indoor in family in use, in more dirt heavy wool mist kitchens with the continuous expansion of polymeric membrane application field
Environment, such as closet surface decorating film, children's activity region etc., polymeric membrane not only play decoration function, and functionality is wanted
It asks higher and higher, more strict requirements is proposed for performances such as the resistance to soiling of decorating film, self-cleaning property, anti-scribbles.It is existing
Conventional polyvinyl chloride polymeric membrane, surface has certain hydrophobic property, water contact angle to can reach 95-105 ° by optimization, so
And it is also not enough to anti-pollution, anti-scribble, self-cleaning function.Thus, exploitation hydrophobic oleophobic has inorganic particle, greasy dirt
The high-molecular decorative film of the resistance to power of refusing has a very important significance and application value.
The higher atom of electronegativity is introduced on the molecular structure of polyvinyl chloride base material, or is added and is contained in formula designs
It is to increase its resistant, the effective means of automatical cleaning ability that special composition auxiliary agent, which improves its superficiality,.In Molecular Design and
In Design of Coatings Formulation, fluorine structure has been demonstrated, to increasing material water contact angle, to assign surface layer better hydrophobic oleophobic performance tool
There is good effect.Be blended by fluoropolymer and polyvinyl chloride merely, can make on physical method fluorine structure into
Enter into material system, however its dispersed, uniformity can not accurately control, and limit the further of the hydrophobic performance containing fluorine structure
Optimization is promoted.A kind of fluorinated acrylate modified PVC macromolecular composite membrane involved in the present invention, first by fluorine-containing
Ester is uniformly mixed with polyvinyl chloride and each analog assistant, and the free radical polymerization of heating initiation fluorinated acrylate, makes in calender line
Fluorine structure can be uniformly distributed in polymeric membrane.The fluorine structure of introducing can greatly improve polymeric membrane surface property, assign
Its resistant, anti-scribble characteristic are given, is had a very important significance and application value in functional macromolecule decoration technical field of membrane.
Invention content
The system for the antifouling anti-scribble high-molecular furniture decorative film based on fluorochemical that the object of the present invention is to provide a kind of
Preparation Method, including PVC base layer and surface functional layer.The surface functional layer is multiple with polyvinyl chloride using fluorochemical
It closes, fluorine-containing fat and siloxanes carry out crosslinking copolymerization under radical initiator effect, and the antifouling anti-scribble of gained is high
Molecule decorating film contains the fluorine silicon structure side chain of large-size, and content is controllable, can significantly improve high-molecular decorative film
Surface property has the characteristics that hydrophobic oleophobic, low-surface-energy.
Technical solution：
A kind of preparation method of antifouling anti-scribble high-molecular decorative film, it is characterised in that the antifouling anti-scribble polymeric membrane includes poly-
Vinyl chloride base base material and surface functional layer polymeric membrane, the surface functional layer polymeric membrane use fluorochemical and polychlorostyrene
Ethylene is combined, and fluorine-containing lipopolymer carries out crosslinking copolymerization, the polyvinyl chloride under radical initiator effect
Base's base material, surface functional layer polymeric membrane hot pressing are bonded to form antifouling anti-scribble high-molecular decorative film, and preparation method includes
Following steps：
1）Prepare polyvinyl chloride base material
1.1 dispensing
It uses Corvic for major ingredient, reinforcing agent, titanium dioxide, plasticizer, background color slurry and its dioctyl ester is added according to the ratio,
The weight proportion of its each component is as follows:
100 parts of Corvic
10 parts of reinforcing agent
30-35 parts of titanium dioxide
20-25 parts of dioctyl ester
Background color starches 1 ~ 2 part
1 ~ 2 part of other plasticizing adjuvants
1.2, it stirs
1.3, it is plasticized
1.4, Polish filtration
1.5, roll
1.6, sided corona treatment
1.7, cooling
2）Prepare surface functional layer polymeric membrane
2.1, dispensing
It uses Corvic for major ingredient, dioctyl ester, titanium dioxide, fluorinated acrylate and other plasticizings is added according to the ratio and help
The weight proportion of agent, each component is:
100 parts of Corvic
15-21 parts of dioctyl ester
25-28 parts of titanium dioxide
1-23 parts of fluorinated acrylate
1 ~ 2 part of other plasticizing adjuvants
0.5-1 parts of initiator
2.2, it stirs
2.3, copolymerization plasticizing is blended
2.4, Polish filtration
2.5, roll
2.6, sided corona treatment
2.7, cooling
3）Hot pressing is bonded
3.1, smooth to dry
3.2, opposite side
3.3, degasification
3.4, hot pressing is bonded
3.5, cooling and shaping
The fluorinated acrylate is the one or two of hexafluorobutyl acrylate and Hexafluorobutyl mathacrylate；
The initiator is one or two kinds of mixtures of benzoyl peroxide and cumyl peroxide.
Advantageous effect：
The antifouling anti-scribble high-molecular decorative film of one kind prepared by the present invention contains fluorine structure in polymer, and content is controllable, and solidification is handed over
After connection, polymeric membrane has low-surface-energy, hydrophobic oleophobic characteristic.
The preparation method of a kind of antifouling anti-scribble high-molecular decorative film according to the present invention, using polyvinyl chloride, fluorine-containing
Acrylate, dioctyl ester etc. are primary raw material, of low cost, simple for process, and existing process units and technique can be used directly；System
Standby reaction process is suitable for continuous industrial production without carrying out by-product separation.
Antifouling anti-scribble high-molecular decorative film prepared by the method for the present invention, has a wide range of application in furniture decoration material field
It is general.Gained decorating film water contact angle exceedes 25% up to 132 °, compared with the raising of common polyvinyl chloride polymeric membrane, has good hydrophobic
Oleophobic effects.
Specific implementation mode
Following embodiment the present invention is furture elucidated content, but be not used in and limit the scope of the invention.
Embodiment
1）Prepare polyvinyl chloride base material
1.1 dispensing
It uses Corvic for major ingredient, reinforcing agent, titanium dioxide, plasticizer, background color slurry and its dioctyl ester is added according to the ratio,
The weight proportion of its each component is as follows:
100 parts of Corvic
10 parts of reinforcing agent
30 parts of titanium dioxide
20 parts of dioctyl ester
Background color starches 1 part
2 parts of other plasticizing adjuvants
1.2, it stirs
Now blender is added in Corvic by the formulation material weighed up according to the ratio, and dioctyl ester, titanium dioxide, reinforcing agent is added, adds
Heat is stirred evenly to 110 °C -130 °C
1.3, it is plasticized
The hot material being thoroughly mixed is conveyed into mixer and is heated to 170-190 °C, is plasticized in sealed states；
1.4, Polish filtration
The good material slitting shape of mill is conveyed into extruder, 140 °C -160 °C is heated to, is squeezed, stir pusher refining,
It pushes to die orifice through 120 mesh filter screens, " flake " and contaminant filter that will be plasticized, this process extruder, by what is be plasticized
Hot material is conveyed into two roller open mills and turn refining 15 minutes, further rapid to close plasticizing, two roll temperature cylinder temperature at 190-195 °C,
Screw speed is 85-95 revs/min；
1.5, roll
It will refine and filtered clinker be conveyed into five roll calendars into strips, calendering film forming is required according to thickness, width specifications,
Five roller heating roller temperatures are controlled at 180-185 °C, and wire velocity control is at 120-130 ms/min；
1.6, sided corona treatment
1.7, cooling
2）Prepare surface functional layer polymeric membrane
2.1, dispensing
It uses Corvic for major ingredient, dioctyl ester, titanium dioxide, fluorinated acrylate and other plasticizings is added according to the ratio and help
The weight proportion of agent, each component is:
100 parts of Corvic
20 parts of dioctyl ester
25 parts of titanium dioxide
20 parts of fluorinated acrylate
1 part of other plasticizing adjuvants
1 part of initiator
2.2, it stirs
Now blender is added in Corvic by the formulation material weighed up according to the ratio, and dioctyl ester, titanium dioxide, reinforcing agent is added, adds
Heat is stirred evenly to 110 °C -130 °C
2.3, copolymerization plasticizing is blended
The hot material being thoroughly mixed is conveyed into mixer and is heated to 170-190 °C, combined polymerization in sealed states is plasticized；
2.4, Polish filtration
The good material slitting shape of mill is conveyed into extruder, 140 °C -160 °C is heated to, is squeezed, stir pusher refining,
It pushes to die orifice through 120 mesh filter screens, " flake " and contaminant filter that will be plasticized, this process extruder, by what is be plasticized
Hot material is conveyed into two roller open mills and turn refining 15 minutes, further rapid to close plasticizing, two roll temperature cylinder temperature at 190-195 °C,
Screw speed is 85-95 revs/min；
2.5, roll
It will refine and filtered clinker be conveyed into five roll calendars into strips, calendering film forming is required according to thickness, width specifications,
Five roller heating roller temperatures are controlled at 180-185 °C, and wire velocity control is at 120-130 ms/min
2.6, sided corona treatment
2.7, cooling
3）Hot pressing is bonded
3.1, smooth to dry
Base material and functional film layer are made base material and functional film layer longitudinally smooth out whole nothing by hot pressing fitting through twill jockey pulley respectively first
Gauffer；
3.2, opposite side
To its base material and functional film layer both sides, two layers of portraitlandscape are adjusted in conjunction with jockey pulley；
3.3, degasification
It is folded through double roller rubber roller, the air put together between base material together and functional film layer first squeezes out to be bonded tightly again, is prevented
Bubble is only generated when thermal-adhering；
3.4, hot pressing fitting
Base material and functional film layer deaerated rear and fit closely together are heated to 160-170 °C through two-wheel hot-pressing roller, pressurization
0.4kg fits together two layers of base material and functional film layer fusion hot pressing in the initial plasticizing phase；
3.5, cooling and shaping
The composite membrane in hot pressing fitting jail is delivered to the cooling of five rollers through deflector roll, five rollers use spacer water cooling, water temperature to control at 15 °
C hereinafter, make material shaping after cooling.
Gained composite membrane water contact angle has good antifouling, resistance to scribble, self-cleaning performance up to up to 132 °.
Claims (3)
1. a kind of preparation method of antifouling anti-scribble high-molecular decorative film, it is characterised in that the antifouling anti-scribble polymeric membrane includes
PVC base layer base material and surface functional layer polymeric membrane, the surface functional layer polymeric membrane is using fluorochemical and gathers
Vinyl chloride is combined, and fluorine-containing lipopolymer carries out crosslinking copolymerization, the polychlorostyrene second under radical initiator effect
Alkenyl layer base material, surface functional layer polymeric membrane hot pressing are bonded to form antifouling anti-scribble high-molecular decorative film, preparation method packet
Include following steps：
1）Prepare polyvinyl chloride base material
1.1 dispensing
It uses Corvic for major ingredient, reinforcing agent, titanium dioxide, plasticizer, background color slurry and its dioctyl ester is added according to the ratio,
The weight proportion of its each component is as follows:
100 parts of Corvic
10 parts of reinforcing agent
30-35 parts of titanium dioxide
20-25 parts of dioctyl ester
Background color starches 1 ~ 2 part
1 ~ 2 part of other plasticizing adjuvants
1.2, it stirs
1.3, it is plasticized
1.4, Polish filtration
1.5, roll
1.6, sided corona treatment
1.7, cooling
2）Prepare surface functional layer polymeric membrane
2.1, dispensing
It uses Corvic for major ingredient, dioctyl ester, titanium dioxide, fluorinated acrylate and other plasticizings is added according to the ratio and help
The weight proportion of agent, each component is:
100 parts of Corvic
15-21 parts of dioctyl ester
25-28 parts of titanium dioxide
1-23 parts of fluorinated acrylate
1 ~ 2 part of other plasticizing adjuvants
0.5-1 parts of initiator
2.2, it stirs
2.3, copolymerization plasticizing is blended
2.4, Polish filtration
2.5, roll
2.6, sided corona treatment
2.7, cooling
3）Hot pressing is bonded
3.1, smooth to dry
3.2, opposite side
3.3, degasification
3.4, hot pressing is bonded
3.5, cooling and shaping.
2. a kind of preparation method of antifouling anti-scribble high-molecular decorative film as described in claim 1, it is characterised in that described fluorine-containing
Acrylate is the one or two of hexafluorobutyl acrylate and Hexafluorobutyl mathacrylate.
3. a kind of preparation method of antifouling anti-scribble high-molecular decorative film as described in claim 1, it is characterised in that the initiation
Agent is one or two kinds of mixtures of benzoyl peroxide and cumyl peroxide.
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| CN201810612072.XA CN108752793A (en) | 2018-06-14 | 2018-06-14 | A kind of preparation method of antifouling anti-scribble high-molecular decorative film |
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| CN201810612072.XA CN108752793A (en) | 2018-06-14 | 2018-06-14 | A kind of preparation method of antifouling anti-scribble high-molecular decorative film |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483696A (en) * | 2019-08-26 | 2019-11-22 | 江苏宝源高新电工有限公司 | A kind of super-hydrophobicity and self-cleaning PVC film material and preparation method thereof |
| WO2021227235A1 (en) * | 2020-05-14 | 2021-11-18 | 江苏海美新材料有限公司 | Embedded-type manufacturing method for high-strength pvc decorative film |
| TWI756101B (en) * | 2021-04-09 | 2022-02-21 | 厚生股份有限公司 | Antifouling film and manufacturing method thereof |
| CN114103339A (en) * | 2021-10-27 | 2022-03-01 | 南通百晟新材料科技有限责任公司 | Bending-resistant and impact-resistant steel plate water-based decorative film and preparation method thereof |
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| WO2015079442A1 (en) * | 2013-11-28 | 2015-06-04 | B. G. Negev Technologies And Applications Ltd | Fabrication and modification of polymer membranes using ink-jet printing |
| CN104844983A (en) * | 2015-05-29 | 2015-08-19 | 合肥得润电子器件有限公司 | Durable fluororubber modified PVC (polyvinyl chloride) cable material for automobile wire harnesses and preparation method thereof |
| CN104877228A (en) * | 2015-05-29 | 2015-09-02 | 合肥得润电子器件有限公司 | Anti-pollution and self-cleaning halogen-free flame retardant insulating material for household appliance and preparation method of anti-pollution and self-cleaning halogen-free flame retardant insulating material |
| CN105778341A (en) * | 2016-04-05 | 2016-07-20 | 江阴华东装饰材料有限公司 | Wall-like brick high-molecular hard wall decorative material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110483696A (en) * | 2019-08-26 | 2019-11-22 | 江苏宝源高新电工有限公司 | A kind of super-hydrophobicity and self-cleaning PVC film material and preparation method thereof |
| WO2021227235A1 (en) * | 2020-05-14 | 2021-11-18 | 江苏海美新材料有限公司 | Embedded-type manufacturing method for high-strength pvc decorative film |
| TWI756101B (en) * | 2021-04-09 | 2022-02-21 | 厚生股份有限公司 | Antifouling film and manufacturing method thereof |
| CN114103339A (en) * | 2021-10-27 | 2022-03-01 | 南通百晟新材料科技有限责任公司 | Bending-resistant and impact-resistant steel plate water-based decorative film and preparation method thereof |
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