CN101429405B - Raw material formula for automotive glass surface protective film and method of producing the same - Google Patents
Raw material formula for automotive glass surface protective film and method of producing the same Download PDFInfo
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- CN101429405B CN101429405B CN2008102202248A CN200810220224A CN101429405B CN 101429405 B CN101429405 B CN 101429405B CN 2008102202248 A CN2008102202248 A CN 2008102202248A CN 200810220224 A CN200810220224 A CN 200810220224A CN 101429405 B CN101429405 B CN 101429405B
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Abstract
The invention relates to a raw material formulation of a surface protective film for automobile glass and a preparation method thereof. The raw material formulation of the surface protective film for the automobile glass comprises the following components: polyfluortetraethylene, ethyl acrylate, a catalyst, an emulsifying agent and water, wherein the polyfluortetraethylene has an iodic active end group, the polymerization degree of the polyfluortetraethylene is 4 to 6, and the molecular weight of the polyfluortetraethylene is 200 to 600 thousand. The preparation method for the surface protective film for the automobile glass comprises the following steps: (1) weighing the raw materials according to a proportion; (2) making the polyfluortetraethylene and the water react for 2 to 4 hours at a temperature of between 120 and 140 DEG C in the presence of a catalyst; (3) and then adding the ethyl acrylate into the mixture to react for 1 to 2 hours at a temperature of between 110 and 118 DEG C; and (4) adding the emulsifying agent into the mixture to homogenize and emulsify the mixture to obtain the final product. The prepared surface protective film for the automobile glass has strong binding force with glass, can reduce surface tension and surface friction factor of the glass, and improve oil resistance and water resistance of the glass; and a coating is not easy to damage.
Description
Technical field
The invention belongs to chemical field, relate to composition of raw materials of automotive glass surface protective film and preparation method thereof.
Background technology
The Chinese automobile recoverable amount surpasses 3,000 ten thousand at present, annual simultaneously 18% the growth that keeps, and the development of automobile is progressively to privatization; Superior, the functionalization direction develops, but aspect the cleaning of vehicle glass; Also exist cleaning performance poor; Environmental pollution is big, and energy loss is big, problems such as VOC content height.
Vehicle glass plated film product is also released in the high-grade cosmetic products of part at home shop, and its basal component is a silicon-type, utilizes the low surface tension of silicone oil that glass is handled; But organosilicon and glass do not have bonding force loss through volatilization easily simultaneously; Persistence is poor, must successively repeat construction, makes troubles to the user; Surperficial boundary after simultaneously organic-silicon-modified can not possess oil-proofness water resisting property is only arranged about 30.In addition, the plain glass coating of the import fluorine of market sale also rests on basically and uses the organic solvent system dispersed polytetrafluoroethylresin; Be coated with construction then, this product has improved the shortcoming of organosilyl persistence difference when static test, but because tetrafluoroethylene C-F key has high bond energy; Sticking power for various grounds is all poor; The coating voidage of the big formation of intermolecular distance simultaneously is high, damage coating and lose modified effect easily when running into external force, and oil-proofness is bad.
Summary of the invention
The object of the present invention is to provide composition of raw materials of a kind of automotive glass surface protective film and preparation method thereof; Use the bonding force of prepared automotive glass surface protective film of this prescription and preparation method and glass strong; Can reduce the surface tension and the skin friction coefficient of glass; Improve the oil-proofness and the water resisting property of glass, and coating is difficult for impaired.
The present invention realizes through following technical scheme:
A kind of composition of raw materials of automotive glass surface protective film; Comprise following component: tetrafluoroethylene, ethyl propenoate, catalyzer, emulsifying agent, water; Wherein tetrafluoroethylene is the tetrafluoroethylene with iodine active end group, and its polymerization degree is 4～6, molecular weight is 20～600,000.
In the said composition of raw materials ratio of tetrafluoroethylene, water, ethyl propenoate be about 1: 1.7～3: 0.4～0.6.
Said ethyl propenoate is the active crylic acid ethyl ester that is closed the agent sealing, also comprises deblocking agent in the said composition of raw materials.
Said catalyzer is a kind of in sodium hydroxide, the Pottasium Hydroxide or both mixtures; Said emulsifying agent is one or more the mixture in OP-10, acrylic amide propane sulfonic acid sodium (ammonium) salt, n-octyl sodium sulfate, sulfo-succinic acid double tridecyl ester sodium, the hydroxyethyl methacrylate propanesulfonic acid sodium; Said encapsulant is a kind of in terephthaldehyde's phenol, the Metol photo grade or both mixtures, and said deblocking agent is one or more the mixture in Potassium Persulphate, Potassium peroxide 85, the perfluor zincic acid.
A kind of preparation method of automotive glass surface protective film, its preparation process is following:
(1) take by weighing tetrafluoroethylene, ethyl propenoate, catalyzer, emulsifying agent, water, said tetrafluoroethylene is the tetrafluoroethylene with iodine active end group, and its polymerization degree is 4～6, molecular weight is 20～600,000;
(2) tetrafluoroethylene and water were reacted 2～4 hours down in 120～140 degrees centigrade under the condition that catalyzer exists;
(3) adding ethyl propenoate then reacted 1～2 hour down at 110～118 degrees centigrade;
(4) adding emulsifying agent carries out homogenizing emulsifying and makes the finished product.
In the above-mentioned steps (1) ratio of tetrafluoroethylene, water, ethyl propenoate be about 1: 1.7～3: 0.4～0.6.
Ethyl propenoate in the above-mentioned steps (3) is the active crylic acid ethyl ester that is closed the agent sealing, and itself and deblocking agent are added drop-wise in tetrafluoroethylene and the water simultaneously, at the uniform velocity stirs, and stirring velocity is 100r/min.Each component can fully be reacted, improve monomeric transformation efficiency, thereby improve performance of products.
Above-mentioned said catalyzer is a kind of in sodium hydroxide, the Pottasium Hydroxide or both mixtures.
Above-mentioned said emulsifying agent is one or more the mixture in OP-10, acrylic amide propane sulfonic acid sodium (ammonium) salt, n-octyl sodium sulfate, sulfo-succinic acid double tridecyl ester sodium, the hydroxyethyl methacrylate propanesulfonic acid sodium.
Above-mentioned said encapsulant is a kind of in terephthaldehyde's phenol, the Metol photo grade or both mixtures.Above-mentioned said deblocking agent is one or more the mixture in Potassium Persulphate, Potassium peroxide 85, the perfluor zincic acid.
The present invention compared with prior art has following advantage:
A) the present invention takes ethyl propenoate as modified monomer, and weather resisteant is good, snappiness, good hardness, and the transparency is high, with the strong adhesion of glass baseplate, does not influence the visible light transmissivity of vehicle glass simultaneously, can not cause glare phenomenon.
B) to adopt the monomer polymerization degree be 4～6 in the present invention, and molecular weight has reduced surface tension at 20～600,000 tetrafluoroethylene, strengthens oil-proofness and water resisting property, and coating is difficult for impaired.
C) the present invention adopts the tetrafluoroethylene with iodine active end group, not only has high reaction activity, and can carry out addition reaction, is convenient to introduce different groups, reaches the effect of comprehensively modifying.
D) the present invention adopts water to make solvent, and VOC content reduces greatly, does not contain poisonous hazardous solvent fully, has alleviated the pollution to environment, compliance with environmental protection requirements.
E) the present invention adopts water homogenizing emulsifying technology, has eliminated original employing acetone, the MIBK production technique as the reaction auxiliary, and VOC content reduces greatly, reduces environmental pollution, save energy, the minimizing injury to human body.
F) product of the present invention's preparation is used for the vehicle glass surface, has changed the surface tension and the frictional coefficient of vehicle glass, improves hydrophobic and lyophobic property, didirtresistance, the anti-company's of picking up property of vehicle glass, and then improves the sight line sharpness of vehicle glass.
G) product of the present invention's preparation can be painted on the vehicle glass surface, need not add washing composition or glass cleaner during glass cleaning, and only need simply wash with common water just can be clean, simple to operation.
H) material cost of the present invention's employing is lower, and product of the present invention is easy to carry, and is easy to use.
Embodiment:
Ethyl propenoate modified Teflon automotive glass surface protective film preparation method of the present invention is following:
(1) takes by weighing tetrafluoroethylene, ethyl propenoate, catalyzer, emulsifying agent, water; Wherein tetrafluoroethylene is the tetrafluoroethylene with iodine active end group; Its polymerization degree is 4～6, molecular weight is 20～600,000, the ratio of tetrafluoroethylene, water, ethyl propenoate is about 1: 1.7～and 3: 0.4～0.6.
(2) tetrafluoroethylene and water were reacted 2～4 hours down in 120～140 degrees centigrade under the condition that catalyzer exists;
(3) adding ethyl propenoate then reacted 1～2 hour down at 110～118 degrees centigrade;
(4) adding emulsifying agent carries out homogenizing emulsifying and makes the finished product.
Ethyl propenoate in the said step (3) is the active crylic acid ethyl ester that is closed the agent sealing, and itself and deblocking agent are added drop-wise in tetrafluoroethylene and the water simultaneously, at the uniform velocity stirs, and stirring velocity is 100r/min.The said active crylic acid ethyl ester that is closed the agent sealing adopts the method for general synthesizing propylene acetoacetic ester to add encapsulant and makes.Said encapsulant is a kind of in terephthaldehyde's phenol, the Metol photo grade or both mixtures.
Table 1 is ethyl propenoate modified Teflon automotive glass surface protective film synthetic embodiment; Wherein each components contents is a mass percentage content, and the tetrafluoroethylene that wherein polymerization degree is 4～6, molecular weight is 20～600,000, have an iodine active end group adopts Daikin to produce.
Table 2 is by the ethyl propenoate modified Teflon automotive glass surface protective film performance of table 1 formulation and the plain coating performance contrast of B board fluorine.
Table 1
Table 2
Interpretation of result:
The present invention takes ethyl propenoate as modified monomer, and weather resisteant is good, snappiness, good hardness, and the transparency is high, with the strong adhesion of glass baseplate, does not influence the visible light transmissivity of vehicle glass simultaneously, can not cause glare phenomenon.
The size of tetrafluoroethylene monomer polymerization degree is determining final properties; The polymer surfaces tension force of macromolecule (more than 1,000,000) is little, and reactive behavior is low, and intermolecular distance is big; Be not easy to form filming of continuous densification, the polymer surfaces characteristic of small molecular weight (below 10,000) is not obvious.The tetrafluoroethylene that the present invention adopts, the monomer whose polymerization degree 4～6, molecular weight has reduced surface tension 20～600,000, strengthens oil-proofness and water resisting property.
The present invention adopts the tetrafluoroethylene with iodine active end group, not only has high reaction activity, and can carry out addition reaction, is convenient to introduce different groups, reaches the effect of comprehensively modifying.
The automotive glass surface protective film of the present invention's preparation is water white liquid, and solid content is 25-35%, and viscosity is 30-60s; Transmittance is 95-97%, and the frictional coefficient reduced rate is 65-75%, surface hardness＞H; Critical surfaces ability yc≤10 after the modification, the dynamic contact angle advancing angle of water＞30 degree, receding angle＜30 degree; Water droplet static contact angle＞100 degree, organic solvent-resistant scrubbing character＞100 time, wash resistant agent scrubbing character＞200; The washability of anti-heavy rain the 20 time, anti-persistence＞250 day of tanning by the sun.
Claims (6)
1. the preparation method of an automotive glass surface protective film is characterized in that: comprise the steps:
(1) takes by weighing tetrafluoroethylene, ethyl propenoate, catalyzer, emulsifying agent, water; Wherein tetrafluoroethylene is the tetrafluoroethylene with iodine active end group; Its polymerization degree is 4～6; Molecular weight is 20～600,000, and wherein the ratio of tetrafluoroethylene, water and ethyl propenoate is 1: 1.7～3: 0.4～0.6;
(2) tetrafluoroethylene and water were reacted 2～4 hours down in 120～140 degrees centigrade under the condition that catalyzer exists;
(3) adding ethyl propenoate then reacted 1～2 hour down at 110～118 degrees centigrade;
(4) adding emulsifying agent carries out homogenizing emulsifying and makes the finished product.
2. the preparation method of automotive glass surface protective film according to claim 1; It is characterized in that: ethyl propenoate is the active crylic acid ethyl ester that is closed the agent sealing in the said step (3); Itself and deblocking agent are added drop-wise in tetrafluoroethylene and the water simultaneously; At the uniform velocity stir, stirring velocity is 100r/min.
3. the preparation method of a kind of automotive glass surface protective film according to claim 1; It is characterized in that: described catalyzer is a kind of in sodium hydroxide, the Pottasium Hydroxide or both mixtures, and described emulsifying agent is one or more the mixture in OP-10, acrylic amide propane sulfonic acid sodium salt, acrylic amide propane sulfonic acid ammonium salt, n-octyl sodium sulfate, sulfo-succinic acid double tridecyl ester sodium, the hydroxyethyl methacrylate propanesulfonic acid sodium.
4. the preparation method of a kind of automotive glass surface protective film according to claim 2 is characterized in that: described encapsulant is a kind of in terephthaldehyde's phenol, the Metol photo grade or both mixtures.
5. the preparation method of a kind of automotive glass surface protective film according to claim 2 is characterized in that: described deblocking agent is one or more the mixture in Potassium Persulphate, Potassium peroxide 85, the perfluor zincic acid.
6. a kind of automotive glass surface protective film that preparation method according to claim 1 obtains.
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| CN2008102202248A CN101429405B (en) | 2008-12-16 | 2008-12-16 | Raw material formula for automotive glass surface protective film and method of producing the same |
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| CN2008102202248A CN101429405B (en) | 2008-12-16 | 2008-12-16 | Raw material formula for automotive glass surface protective film and method of producing the same |
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| CN101429405B true CN101429405B (en) | 2012-05-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016083862A1 (en) | 2014-11-28 | 2016-06-02 | Corning Incorporated | Methods for producing shaped glass articles |
| CN106085171B (en) * | 2016-05-31 | 2018-08-07 | 天津市一玛防护材料有限公司 | Polytetrafluoroethylmodified modified high solid automobile varnish of a kind of normal temperature cure and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1310190A (en) * | 2000-02-15 | 2001-08-29 | 旭硝子株式会社 | Block polymer and its producing process, and the same polymer electrolytic fuel cell |
| US6369178B1 (en) * | 1998-12-23 | 2002-04-09 | Alliedsignal Inc. | Poly (chlorotrifluoroethylene/vinylidenefluoride/vinylester) copolymers with excellent long-term ultraviolet light resistance |
| CN1304437C (en) * | 2005-04-01 | 2007-03-14 | 东南大学 | Method for preparing stable latex of copolymer containing fluorinated acrylic ester |
| WO2007117493A2 (en) * | 2006-04-05 | 2007-10-18 | University Of Massachusetts | Graft copolymers and related methods of preparation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6369178B1 (en) * | 1998-12-23 | 2002-04-09 | Alliedsignal Inc. | Poly (chlorotrifluoroethylene/vinylidenefluoride/vinylester) copolymers with excellent long-term ultraviolet light resistance |
| CN1310190A (en) * | 2000-02-15 | 2001-08-29 | 旭硝子株式会社 | Block polymer and its producing process, and the same polymer electrolytic fuel cell |
| CN1304437C (en) * | 2005-04-01 | 2007-03-14 | 东南大学 | Method for preparing stable latex of copolymer containing fluorinated acrylic ester |
| WO2007117493A2 (en) * | 2006-04-05 | 2007-10-18 | University Of Massachusetts | Graft copolymers and related methods of preparation |
Non-Patent Citations (1)
| Title |
|---|
| Seong-Mu Jol et al.New AB or ABA type block copolymers: atom transfer radical polymerization (ATRP) of methyl methacrylate using iodine-terminated PVDFs as (macro)initiators.《Polymer Bulletin》.2002,第44卷(第1期),1-8. * |
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Denomination of invention: The invention relates to a raw material formula of automobile glass surface protective film and a preparation method thereof Effective date of registration: 20211228 Granted publication date: 20120523 Pledgee: Guangzhou Conghua Branch of China Construction Bank Co.,Ltd. Pledgor: GUANGZHOU BOTNY CHEMICAL Co.,Ltd. Registration number: Y2021440000404 |