CN103467890B - A kind of peelable protective film and composite formula thereof - Google Patents
A kind of peelable protective film and composite formula thereof Download PDFInfo
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Abstract
A kind of peelable protective film, there is splendid adhesive ability and there will not be stripping problem, be applicable to temporarily protect article purposes, especially the stripping strength of this protective membrane is between 35 ~ 100g/cm, can peel off easily and cull can not be left to by glue thing tearing off in process with article, it selects specific formula thing to make, the TI value of said composition is between 2.00 ~ 2.20, its composition comprises: vinyl chloride-vinyl acetate copolymer, height and lower molecular weight PVC emulsifying polymer powder, benzenetricarboxylic acid ester plasticizer, diisobutyrate plastic binder, without phenol calcium zinc stabilizer, smoked silica, aluminium hydroxide, barium sulfate and calcium carbonate.
Description
Technical field
The present invention relates to a kind of peelable protective film and composite formula thereof, can peel off easily after espespecially a kind of intermediate process and not stay peelable protective film and the composite formula thereof of cull.
Background technology
In the prior art; peelable protective film is a kind of film product having bonding and dust-proof scratch resistant function concurrently; through being usually used in the outward appearance temporarily protecting article; or in the middle work flow of electronic package or optical module or between the shelf lives in; for temporarily bonding and protect electronic package that is processed or that be stored or optical module (hereinafter referred to as by glue thing); complete or when formally using until middle work flow; easily protective membrane can be separated from being torn off by glue thing, and can not injure by glue thing.
But; peelable protective film of the prior art; a kind of acrylic copolymer protectiveness film that such as US Patent No. 6211282 publication discloses; when bonding or fit to by glue thing time; the problem of stripping is had under high-pressure washing; and; from being torn off the process of protective membrane by glue thing; the bonding composition of protective membrane often can form the glue-line (hereinafter referred to as cull) that not easily removes and be adhered to by the surface of glue thing; having causing needing wasting time and energy removes the defect of cull, therefore peelable protective film of the prior art is still improved space.
In addition; peelable protective film of the prior art; need in the fabrication process to use solvent and needs through crosslinked sclerosis; so that there is the environmental issue of solvent slop; especially peelable protective film is when after tearing off use; but can not recycling, need with waste disposal, do not have an environment protection meaning in fact.
Summary of the invention
For overcoming above-mentioned shortcoming; the invention provides a kind of peelable protective film; do not use solvent and crosslinked process of setting; by the combination of suitable resin and the collocation of different softening agent, have outside dimensional stabilizing, stable viscosity, bonding force appropriateness, water-repellancy and excellent heat stability, during use; also have concurrently and can peel off easily, do not break and do not stay the feature of cull; especially do not use solvent, circulation can be reclaimed and re-use, tool environment protection.
For the manufacture of the composition of peelable protective film of the present invention, use following special formulation composition, based on composition total weight, comprise
A) vinyl chloride-vinyl acetate copolymer, K value, between 69 ~ 71, accounts for 10 ~ 65wt%; Wherein, the content of vinyl acetate between to for plastic is 1.0 ~ 12.5%, is preferably 4.0 ~ 6.9%;
B) high molecular weight pvc emulsion polymerization powder, K value, between 77.5 ~ 81, accounts for 3 ~ 20wt%;
C) lower molecular weight PVC emulsifying polymer powder, K value, between 73.0 ~ 76.5, accounts for 3 ~ 20wt%;
D) benzenetricarboxylic acid ester plasticizer, accounts for 5 ~ 40wt%;
E) Fu acid mixed radix ester plasticizer and two kinds, diisobutyrate class softening agent used in combination, account for 1 ~ 20wt%;
F) without phenol calcium zinc stabilizer, 0.5 ~ 3wt% is accounted for;
G) smoked silica (Fumedsilica or title aerosil), accounts for 1 ~ 10wt%;
H) aluminium hydroxide, accounts for 0.1 ~ 10wt%;
I) barium sulfate, accounts for 0.1 ~ 20wt%;
J) calcium carbonate, accounts for 0.1 ~ 20wt%.
Peelable protective film of the present invention, outside the bonding and dust-proof scratch resistant function of tool, also meets following conditional request, is applicable to making the peelable protective film for optical module:
1, the stripping strength of peelable protective film is between 35 ~ 100g/cm, during use, tearing off in process and can peel off easily, and the glue-line of peelable protective film can not leave cull to by glue thing;
2, the resistance to baking of peelable protective film tool, through 180 DEG C of bakings 10 minutes, and repetition same steps toasted 3 times continuously, and the glue-line of peelable protective film still has toughness, and surface drying good, inviscid problem;
3, peelable protective film tool excellent adhesion, be adhered to by glue thing time, through following wherein one or more test conditions, still possess the adhesive ability do not peeled off:
A) under temperature 45 C, frequency 46khz ultrasonic vibrating is carried out 5 minutes;
B) with 10kg/cm
2hydraulic pressure carries out high-pressure washing;
C) 60 DEG C of hot-water soaks 26 minutes are invaded;
D) the 3.17%NaOH basic solution immersing temperature 40 DEG C soaks 2 minutes; Or
E) the chloroazotic acid series acidic solution immersing temperature 46 DEG C soaks 2 minutes.
Embodiment
Peelable protective film of the present invention uses the composition (hereinafter referred to as peelable composition) of tool special formulation of the present invention to make through coating waste water at normal temperatures; Except there is viscosity stability, water-repellancy and thermostability, when bonding or fit to by glue thing, also have the characteristic of stripping strength between 35 ~ 100g/cm concurrently, and can peel off easily and not stay the feature of cull, especially do not use solvent, circulation can be reclaimed and re-use.
The peelable composition used, under 25 DEG C of room temperatures, the viscosity that VT-04 viscometer records is between 400 ~ 600ps, use the DVII+Pro type rotational viscosimeter test (hereinafter referred to as the test of use rotational viscosimeter) of BROOKFIELD company of the U.S., possesses the shake-change property index (ThixotropyIndex imposed a condition as under " 0.5rpm viscosity/2.5rpm viscosity ", be called for short TI value) physical property between 2.00 ~ 2.20, based on composition total weight, comprise following ingredients:
A) vinyl chloride-vinyl acetate copolymer, K value, between 69 ~ 71, accounts for 10 ~ 65wt%; Wherein, the content of vinyl acetate between to for plastic is 1.0 ~ 12.5%, is preferably 4.0 ~ 6.9%;
B) high molecular weight pvc emulsion polymerization powder, accounts for 3 ~ 20wt%; Its mean polymerisation degree (AverageDegreeofpolymerization, DP) between 1650 ~ 1850, K value (Fikentscher ' sConstant) between 77.5 ~ 81;
C) lower molecular weight PVC emulsifying polymer powder, accounts for 3 ~ 20wt%; Its mean polymerisation degree between 1350 ~ 1550, K value between 73.0 ~ 76.5;
D) benzenetricarboxylic acid ester plasticizer, accounts for 5 ~ 40wt%;
E) diisobutyrate class softening agent, accounts for 1 ~ 20wt%; And described diisobutyrate class softening agent is 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate (2,2,4-trimethyl-1,3-pentanedioldiisobutyrate, TXIB) softening agent, wherein, benzenetricarboxylic acid ester plasticizer and 2,2, the usage quantity ratio of 4-trimethylammonium-1,3-pentanediol diisobutyrate softening agent is 1.0 ~ 9.0, but best with 4.0 ~ 6.0;
F) without phenol calcium zinc stabilizer, 0.5 ~ 3wt% is accounted for;
G) smoked silica, accounts for 1 ~ 10wt%;
H) aluminium hydroxide, accounts for 0.1 ~ 10wt%;
I) barium sulfate, accounts for 0.1 ~ 20wt%;
J) calcium carbonate, accounts for 0.1 ~ 20wt%.
The present composition is many, containing solid, liquid raw material, feeding sequence can affect viscosity B coefficent, for control composition stable viscosity, and under not using solvent to adjust, first with plasticizer dissolves vinyl chloride-vinyl acetate copolymerization powder, lower molecular weight PVC emulsifying polymer powder, then high molecular weight pvc emulsion polymerization powder is dissolved, attention first can not drop into high molecular emulsion polymerization powder, in case viscosity hurriedly rises, stir after 40 minutes and leave standstill more than 2 hours, make copolymerization powder, the abundant swelling of emulsion polymerization powder, guarantee stable viscosity, smoked silica and aluminium hydroxide all significantly can improve viscosity, finally drop under low rate mixing, its manufacture method feeding sequence is as following:
(1) first benzenetricarboxylic acid ester plasticizer is dropped into mixing machine, then drop into diisobutyrate softening agent, then drop into one package stabilizer; Start paddle, low rate mixing also sequentially slowly drops into vinyl chloride-vinyl acetate copolymer, then drops into lower molecular weight PVC emulsifying polymer powder, finally drops into high molecular weight pvc emulsion polymerization powder, stirs after 40 minutes and leaves standstill more than 2 hours;
(2) start paddle and improve stirring velocity, sequentially dropping into barium sulfate, calcium carbonate;
(3) stir reduction of speed after 5 minutes to stir, finally drop into smoked silica and aluminium hydroxide;
(4) stir after 30 ± 5 minutes and measure viscosity, at 25 DEG C, viscosity is 400 ~ 600ps, churning time apparent viscosity and extend or shorten.
Described vinyl chloride-vinyl acetate copolymer (VinylChloride-VinylAcetatecopolymers) is jointly polymerized by vinylchlorid and vinyl acetate between to for plastic two kinds of monomers, and the content of vinyl acetate between to for plastic is higher, the bonding strength of vinyl chloride-vinyl acetate copolymer is then thereupon high, consider that film forming tack is good easily to peel off again, the content of vinyl acetate between to for plastic should be suitable, can not be higher or too low.Therefore, described vinyl chloride-vinyl acetate copolymer has the high tenacity of vinylchlorid and the strong viscosity of erosion resistance and vinyl acetate between to for plastic and plasticity-, coating waste water makes film dimensions good stability, can high-temperature baking resistant and hot-water soak, and obtained film, possess acidproof not only alkaline-resisting, moistureproof but also waterproof, nonflammable and not combustion-supporting characteristic.
Described high molecular weight pvc emulsion polymerization powder possesses low viscosity and low-temperature heat can the characteristic of gel, can make film by coating waste water at normal temperatures.And obtained film, possesses the characteristic of water tolerance and anti-electrostatic.
Described lower molecular weight PVC emulsifying polymer powder possesses proper viscosity, has good demoulding when making film.
In peelable protective film composition of the present invention, comprise vinyl chloride-vinyl acetate copolymer to arrange in pairs or groups together from the PVC emulsifying polymer powder of different mean polymerisation degree and use, under the condition not using solvent, choose appropriate vinyl chloride-vinyl acetate copolymer, again with the use of appropriate height, low-molecular-weight PVC emulsifying polymer powder, can obtain and possess the most suitable bonding strength, the peelable protective film of tension intensity and toughness, when as protective membrane use, have concurrently and can peel off easily, do not break and do not stay the feature of cull, simultaneously, the shake-change property index (TI value) that three mixes composition glue is the most stable, make a variation little favourable coating waste water.
Described benzenetricarboxylic acid ester plasticizer can be selected from benzenetricarboxylic acid trimethyl (Trimethyltrimellitate, TMTM), own ester (the Triethyltrimellitate of benzenetricarboxylic acid, TETM), own ester (the Trihexyltrimellitate of benzenetricarboxylic acid three, THTM), the different three monooctyl ester (Trisooctyltrimellitate of benzenetricarboxylic acid, or benzenetricarboxylic acid three monooctyl ester (Tri (2-ethylhexyl) trimellitate TIOTM), TOTM) wherein one is used alone or more than one mix and use, the lower tool low migration of high temperature 100 ~ 180 DEG C baking, can possess surface drying, and it is inviscid, and still possess excellent in toughness.
Described 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate (TXIB), is a kind of not containing the non-toxic, environmental friendly softening agent of phenyl ring, easily mixes with vinyl chloride-vinyl acetate copolymer, except can reducing the viscosity of peelable composition of the present invention, and the flow characteristics of peelable composition of the present invention can be promoted, make the stable viscosity of peelable composition of the present invention and be not easily mixed into bubble, being suitable for coating waste water most and obtaining film; And obtained finished film smooth in appearance, during use, not easily there is scratch in its surperficial tool anti-soil and antiwear property (or claiming scratch resistance).
In peelable composition of the present invention, comprise benzenetricarboxylic acid ester plasticizer to arrange in pairs or groups together with diisobutyrate softening agent and use, and do not use solvent, by the allotment of both different usage quantitys, wherein, benzenetricarboxylic acid ester plasticizer and 2,2, the usage quantity ratio of 4-trimethylammonium-1,3-pentanediol diisobutyrate softening agent is 1.0 ~ 9.0, but best with 4.0 ~ 6.0, can reach and its viscosity suitably be adjusted to described peelable composition and guarantees to possess viscosity stability, described peelable composition is not only contributed to be processed into film, and make obtained thin film for excellent flexibility, toughness and scratch resistant property, especially through 180 DEG C of bakings in 10 minutes 3 times, still possess toughness, its drying property is also good, when protective membrane first surface is 100 ~ 120 DEG C of prebake conditions after 3 minutes, when printing second, first surface and printing table inviscid, be more suitable for the purposes as peelable protective film, and in the process tearing off peelable protective film, can guarantee that peelable protective film can not be broken.
Described is not containing nonyl phenol (NonylPhenol), not containing dihydroxyphenyl propane (Bis-Phenol-A), not containing the stablizer of phenol (Phenol) three kinds of solvents without phenol calcium zinc stabilizer, its objective is that processing procedure does not contain phenol solvent and improves the resistance toheat of peelable composition of the present invention.
The purposes of described smoked silica, being use as adjusting adhesive, for adjusting the viscosity of peelable composition of the present invention, preventing vertical stream from also can prevent stopping composition from precipitating.The structure of described smoked silica, be preferably particle diameter between 5 ~ 50nm, surface-area is between 50 ~ 600m
2/ g.
For preventing viscosity drastic change in time, coordinate smoked silica to use aluminium hydroxide to adjust and stickyly has thickening effectiveness, aluminium hydroxide has both sexes characteristic simultaneously, can with acid-respons again can with alkali reaction, playing the function of acid-and base-resisting, is also feature of the present invention.Smoked silica consumption is 2 ~ 6 times of aluminium hydroxide is good, and the variate TI (ThixotripicIndex) that shakes of this two things consumption adjustable control composition is good 2.00 ~ 2.20.
In addition, the diisobutyrate class softening agent in peelable composition of the present invention, is a kind of nonionogenic tenside, both had lipophilic group, have hydrophilic radical again.And described aluminium hydroxide has both sexes, can with acid-respons again can with alkali reaction.Therefore, in peelable composition of the present invention, described aluminium hydroxide is arranged in pairs or groups together with described diisobutyrate softening agent and uses, can promote that described nonionogenic tenside forms micelle, and strengthen the surface tension of tensio-active agent thus, make peelable composition of the present invention reach the effect of thickening.
The purposes of described barium sulfate, for improving the performance of peelable composition of the present invention, comprise and improve electric insulating quality, resistance to heat distorsion, resistance to opticity and thermostability, reduce linear expansivity and shrinking percentage, increase thermal conductivity, improve glue-line stability, increase thermotolerance and physical strength, change the mobility of gluey peelable composition or regulate the viscosity etc. of peelable composition.The structure of barium sulfate of the present invention, is preferably median size between 1 ~ 50nm, for improving wear resistance, the acid resistance of peelable protective film.
The structure of described calcium carbonate; be preferably median size between 30 ~ 100nm; for improving the toughness of peelable composition of the present invention, and the shrinking percentage of peelable protective film obtained by reducing, the surface flatness of promoting described peelable protective film and scratch resistance characteristic.Especially when peelable composition of the present invention uses nanometer calcene as weighting agent, then peelable composition of the present invention possesses better thermostability and dispersiveness, is more suitable for making the peelable protective film for optical module.
Do not using under solvent, peelable composition of the present invention, possess TI value (under the 0.5rpm viscosity/2.5rpm viscosities) physical property between 2.00 ~ 2.20, shake-change property is little, stable viscosity, the most applicable coating waste water.And in the process of coating waste water, peelable composition of the present invention, the anti-fluidity that hangs down of tool, there will not be vertical flow phenomenon.
And the peelable protective film that peelable composition according to the present invention obtains with coating waste water, can meet following conditional request:
1. the stripping strength of peelable protective film is between 35 ~ 100g/cm, is preferably between 45 ~ 80g/cm, tearing off in process and can peel off easily, and the glue-line of peelable protective film can not leaves cull to by glue thing;
2. the resistance to baking of peelable protective film tool, through 180 DEG C of bakings 10 minutes, and repetition same steps toasted 3 times continuously, and the glue-line of peelable protective film still has toughness;
3. peelable protective film tool excellent adhesion, be adhered to by glue thing time, after following test condition, still do not have stripping problem:
Under temperature 45 C condition, carry out frequency 46khz ultrasonic vibrating 5 minutes, at pressure 10kg/cm
2carry out high-pressure washing under condition, invade 60 DEG C of hot-water soaks 26 minutes, immerse (3.17%NaOH) basic solution of temperature 40 DEG C soak 2 minutes, (chloroazotic acid series) acidic solution of immersing temperature 46 DEG C soaks 2 minutes.
Below enumerate embodiment and comparative example to illustrate peelable composition of the present invention and be applicable to make a kind of peelable protective film.The peelable composition that embodiment and comparative example use and obtained peelable protective film, test its physical property and characteristic according to following appraisal procedure.
1. Nian Du ︰
Under temperature 25 DEG C of conditions, the VT-04F type viscometer of Japanese RION company is used to test the viscosity of peelable composition.
2. shake-change property index (or claims TI value) ︰
Under temperature 25 DEG C of conditions, the DVII+Pro type rotational viscosimeter of BROOKFIELD company of the U.S. is used to test the TI value of peelable composition.
Ce amount Fang Fa ︰ is under 2.5rpm rotating speed, and after making the stable viscosity of peelable composition, wait for about 3 minutes, surveying its viscosity is V1; Under 0.5rpm rotating speed, after making the stable viscosity of peelable composition, same wait about 3 minutes, surveying its viscosity is V
2.Wherein, TI value=10V
2/ V
1.
3. Dinging Xing of viscosity Wen ︰
Under temperature 25 DEG C of conditions, peelable composition is statically placed in dust free chamber after 24hr, uses the DVII+Pro type rotational viscosimeter of BROOKFIELD company of the U.S. to test the viscosity of peelable composition.
4. the anti-fluidity that hangs down:
Gluey peelable composition after coating, without the flow phenomenon that hangs down.
5. Gan Zao ︰
Under temperature 100 ~ 120 DEG C of conditions; by the first surface of peelable protective film surface prebake conditions after 3 minutes; peelable protective film be placed on printing table and print its second surface, then the first surface surface of peelable protective film need meet with printing table inviscid.
6. Nai baking Xing ︰
Under temperature 180 DEG C of conditions, after peelable protective film being toasted 10 minutes, then repeat baking 3 times, the glue-line of peelable protective film still has toughness.
7. divesting Xing ︰
After peelable protective film and 3M adhesive tape (tape) being fitted, divested by 3M adhesive tape, 3M adhesive tape need not have cull to occur.
8. attachment Xing ︰
Coated by composition by glue thing, after 150 DEG C × 2 minutes film forming, peelable protective film is attached to by glue thing, then with the adhesive ability of following 5 kinds of methods test peelable protective film.After test, more whether visual observations peelable protective film can be peeled off with by glue thing, does not occur stripping problem, represents peelable protective film and has splendid adhesive ability:
A. ultrasonic vibrating:
Under temperature 45 C condition, with frequency 46kHz ultrasound to attachment peelable protective film shaken 5 minutes by glue thing.
B. water jets under high pressure is impacted:
With pressure 10kg/cm
2water column rinsed by the peelable protective film of glue thing being attached to.
C. hot-water soak:
Under water temperature 60 DEG C of conditions, by attachment peelable protective film soaked 26 minutes by glue thing.
D. alkali resistance:
Temperature 40 DEG C and in sodium hydroxid (NaOH) solvent of concentration 3.17%, attachment peelable protective film soaked 2 minutes by glue thing.
E. acid resistance:
In the chloroazotic acid range of solvents of temperature 46 DEG C, by attachment peelable protective film soaked 2 minutes by glue thing.
9. stripping strength:
Get the peelable protective film of width 1 centimeter, from its fit peeled off by glue thing time, measure the stripping strength in its 180 degree of directions.
The stripping strength of peelable protective film is under the condition of 35 ~ 100g/cm, and peelable protective film there will not be cull tearing off in process.
[embodiment 1-6]:
According to the formula (numeral is weight part) of table 1, be modulated into the peelable composition of embodiment 1-6 respectively, then measure its physical property respectively, comprise viscosity, TI value, viscosity stability and the anti-fluidity that hangs down, measuring result is as shown in table 2.
Modulated peelable composition is made peelable protective film respectively with coating waste water, then measures its characteristic respectively, comprise resistance to baking, divesting property, tack and stripping strength, measuring result is as shown in table 3.
[comparative example 1-4]:
According to the formula (numeral is weight part) of table 1, be modulated into the peelable composition of comparative example 1-4 respectively, then measure its physical property respectively, comprise viscosity, TI value, viscosity stability and the anti-fluidity that hangs down, measuring result is as shown in table 2.
Modulated peelable composition is made peelable protective film respectively with coating waste water, then measures its characteristic respectively, comprise resistance to baking, divesting property, tack and stripping strength, measuring result is as shown in table 3.
Table 1 embodiment and comparative example formula
Note 1: vinyl chloride-vinyl acetate copolymer comprises 5.0 ﹪ vinyl acetate between to for plastics (VinylAcetate), and its K value is 70;
Note 2: vinyl chloride-vinyl acetate copolymer comprises 13.0 ﹪ vinyl acetate between to for plastics (VinylAcetate), and its K value is 50
Note 3: the model PR1069PVC emulsifying powder product that Taiwan plastics industry limited-liability company manufactures, its K value is 77.5 ~ 81;
Note 4: the model PR415PVC emulsifying powder product product that Taiwan plastics industry limited-liability company manufactures, its K value is 73.0 ~ 76.5;
Note 5:2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate.
The peelable composition physical property of table 2 embodiment and comparative example
Note 5: viscosity stability with excellent, good, can, bad be evaluation grade.
The peelable protective film characteristic of table 3 embodiment and comparative example
Note 6: the glue-line first surface surface of peelable protective film is under 100 ~ 120 DEG C of conditions, and prebake conditions is after 3 minutes, observes first surface surface and has with printing table, inviscid.
Note 7: the glue-line of peelable protective film still has toughness after baking, with excellent, good, can, bad be evaluation grade.
Note 8: immerse temperature 40 DEG C and in sodium hydroxid (NaOH) solvent of concentration 3.17% 2 minutes, with excellent, good, bad to adhere to for evaluation alkali resistance can not peel off grade.
Note 9: to immerse in temperature 46 DEG C of chloroazotic acid range of solvents 2 minutes, with excellent, good, bad to adhere to for evaluation acid resistance can not peel off grade.
result:
1, the peelable composite formula of comparative example 1-4, only select vinyl chloride-vinyl acetate copolymer or high and low molecular weight polyvinylchloride emulsion polymerization powder wherein one to two kind to arrange in pairs or groups with the softening agent of single kind and use, and do not make smoked silica and the aluminium hydroxide of apparatus adjusting adhesive purposes.
And the peelable composition of embodiment 1-6, selecting arranges in pairs or groups vinyl chloride-vinyl acetate copolymer together with the PVC emulsifying polymer powder of high and low molecular weight uses, and collocation selects benzenetricarboxylic acid ester plasticizer to use together with diisobutyrate softening agent, allocate other special component formula again, such as, have the compositions such as the smoked silica that adds tool adjusting adhesive purposes and aluminium hydroxide.
In comparison, showing viscosity, TI value, the viscosity stability of peelable composition and resisting in the fluidity that hangs down, according to shown in table 2, the physical property of the peelable composition of embodiment 1-6, all many compared with the peelable composition excellence of comparative example 1-4.
Especially the TI value of the peelable composition of embodiment 1-6, between 2.05 ~ 2.16, shake-change property is little, and stable viscosity is conducive to coating waste water, is also conducive to placing and storing to obtained peelable protective film.
2, the peelable protective film that embodiment 1-6 is obtained, according to shown in table 3, possesses stripping strength between 50 ~ 80g/cm characteristic, meets and is tearing off in process when the stripping strength of peelable protective film is between 35 ~ 100g/cm the condition that there will not be cull.
The peelable protective film that comparative example 1-4 is obtained, according to shown in table 3, its stripping strength does not then drop within the scope of 35 ~ 100g/cm.Comparative example 3 full dose vinyl chloride-vinyl acetate copolymer, the protective membrane stripping strength of comparative example 4 high-content vinyl acetate between to for plastic is higher, not easily peels off.
In comparison, the peelable protective film of embodiment 1-6, possesses and can to peel off easily and can not to the excellent characteristics being left cull by glue thing.
3, illustrate with preceding paragraph; in the resistance to baking of performance peelable protective film, divesting property and tack ability; especially resistance to concussion, resistance to flushing, water tolerance, acid resistance, alkali resistance aspect; according to shown in table 3; the physical property of the peelable protective film that embodiment 1-6 obtains is all excellent compared with the peelable protective film of comparative example 1-4.
Accordingly, the peelable protective film of embodiment 1-6 has splendid adhesive ability, when be attached to by glue thing as temporarily protect purposes use time, there will not be the problem of stripping.
4, the acid resistance of embodiment 4-6, alkali resistance attachment are not peeled off, and are better than embodiment 1-3 and are more better than comparative example 1-4, display aluminium hydroxide and the impact effect of barium sulfate good.
Claims (9)
1. the composition of a peelable protective film; it is characterized in that: do not using under solvent; the vinyl chloride-vinyl acetate copolymer of specific vinyl acetate content is used to coordinate speciality plasticizer jointly to form with high and low molecular weight polyvinylchloride emulsion polymerization powder; test with rotational viscosimeter; possess impose a condition into the TI value under 0.5rpm viscosity/2.5rpm viscosity between 2.00 ~ 2.20 physical property; based on composition total weight, comprise following Cheng Fen ︰
A) vinyl chloride-vinyl acetate copolymer, K value, between 69 ~ 71, accounts for 10 ~ 65wt%; Wherein, the content of vinyl acetate between to for plastic is 1.0 ~ 12.5%;
B) high molecular weight pvc emulsion polymerization powder, its mean polymerisation degree between 77.5 ~ 81, accounts for 3 ~ 20wt% between 1650 ~ 1850, K value;
C) lower molecular weight PVC emulsifying polymer powder, its mean polymerisation degree between 1350 ~ 1550, K value between 73.0 ~ 76.5; Account for 3 ~ 20wt%;
D) benzenetricarboxylic acid ester plasticizer, accounts for 5 ~ 40wt%;
E) 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate (TXIB) softening agent, account for 1 ~ 20wt%; Wherein, the usage quantity ratio of benzenetricarboxylic acid ester plasticizer and 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate softening agent is 1.0 ~ 9.0 according to weight ratio;
F) without phenol calcium zinc stabilizer, 0.5 ~ 3wt% is accounted for;
G) smoked silica, accounts for 1 ~ 10wt%;
H) aluminium hydroxide, accounts for 0.1 ~ 20wt%;
I) barium sulfate, accounts for 0.1 ~ 20wt%, and wherein, the median size of described barium sulfate, between 1 ~ 50nm;
J) calcium carbonate, accounts for 0.1 ~ 20wt%, and wherein, the median size of described calcium carbonate, between 30 ~ 100nm.
2. composition as claimed in claim 1, wherein, the vinyl acetate content of described vinyl chloride-vinyl acetate copolymer is 4.0 ~ 6.9%.
3. composition as claimed in claim 1, wherein, described benzenetricarboxylic acid ester plasticizer be selected from trimethyl trimellitate (TMTM), the own ester of trimellitic acid (TETM), the own ester of tri trimellitate (THTM), different three monooctyl esters (TIOTM) of trimellitic acid or trioctyl trimellitate (TOTM) wherein one to be used alone or more than one mix and use.
4. composition as claimed in claim 1, wherein, the usage quantity ratio of described benzenetricarboxylic acid ester plasticizer and 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate softening agent is 4.0 ~ 6.0 according to weight ratio.
5. composition as claimed in claim 1 is according to following feeding sequence get ︰
(1) first benzenetricarboxylic acid ester plasticizer is dropped into mixing machine, then drop into 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate softening agent, then drop into without phenol calcium zinc stabilizer; Start paddle, low rate mixing also sequentially slowly drops into vinyl chloride-vinyl acetate copolymer, then drops into lower molecular weight PVC emulsifying polymer powder, finally drops into high molecular weight pvc emulsion polymerization powder, stirs after 40 minutes and leaves standstill more than 2 hours;
(2) start paddle and improve stirring velocity, sequentially dropping into barium sulfate, calcium carbonate;
(3) stir reduction of speed after 5 minutes to stir, sequentially drop into smoked silica, aluminium hydroxide;
(4) stir after 30 ± 5 minutes and measure viscosity, at 25 DEG C, viscosity is 400 ~ 600ps, churning time apparent viscosity and extend or shorten.
6. the composition as described in claim the 1, wherein, the particle diameter of described smoked silica is between 5 ~ 50nm, and surface-area is between 50 ~ 600m
2/ g.
7. the peelable protective film using the composition of claim 1 to make, is characterized in that, get width 1 centimeter and from fitted peeled off by glue thing time, measure the stripping strength in its 180 degree of directions, possess the characteristic of stripping strength between 35 ~ 100g/cm.
8. peelable protective film as claimed in claim 7, possesses the characteristic of stripping strength between 45 ~ 80g/cm.
9. as claimed in claim 7 or 8 peelable protective film, is first attached to by glue thing, then after following wherein one or more test conditions test, described peelable protective film and by between glue thing, does not peel off completely to estimate observation:
A) under temperature 45 C, frequency 46khz ultrasonic vibrating is carried out 5 minutes;
B) with 10kg/cm
2hydraulic pressure carries out high-pressure washing;
C) 60 DEG C of hot-water soaks 26 minutes are immersed;
D) the 3.17%NaOH basic solution immersing temperature 40 DEG C soaks 2 minutes; Or
E) the chloroazotic acid series acidic solution immersing temperature 46 DEG C soaks 2 minutes.
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| CN201310429915.XA CN103467890B (en) | 2013-09-18 | 2013-09-18 | A kind of peelable protective film and composite formula thereof |
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| CN201310429915.XA CN103467890B (en) | 2013-09-18 | 2013-09-18 | A kind of peelable protective film and composite formula thereof |
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| CN103467890A CN103467890A (en) | 2013-12-25 |
| CN103467890B true CN103467890B (en) | 2016-04-20 |
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| CN103756455B (en) * | 2014-01-14 | 2016-05-18 | 北京天山新材料技术有限公司 | A kind of high temperature resistant peelable protective finish and preparation method thereof |
| CN104761960A (en) * | 2015-03-21 | 2015-07-08 | 广东南海启明光大科技有限公司 | 3D curved surface shielding liquid capable of spraying and thermocuring and preparation method thereof |
| CN105838276B (en) * | 2016-01-29 | 2018-09-21 | 宁波吉象塑胶科技股份有限公司 | A kind of preparation method of adhesive tape |
| CN108034163A (en) * | 2017-12-05 | 2018-05-15 | 沈阳化工股份有限公司 | A kind of PVC vehicle glasses anti-fog film and preparation method thereof |
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| CN1097788A (en) * | 1994-06-04 | 1995-01-25 | 潘治平 | Transfer type easy erasing pressure sensing glue |
| JP3486050B2 (en) * | 1996-04-23 | 2004-01-13 | 株式会社リンレイ | Peelable coating agent water dispersion |
| CN1073136C (en) * | 1998-03-05 | 2001-10-17 | 晏林宝 | Hot-dipping stripped plastic protective film for plastics, mfg. method and application thereof |
| CN101892019A (en) * | 2009-05-20 | 2010-11-24 | E.I.内穆尔杜邦公司 | Strippable multilayer-structure surface protective film and product thereof |
| CN102219965A (en) * | 2011-05-20 | 2011-10-19 | 潍坊胜达科技股份有限公司 | Antistatic flame-resistant environmentally stable peelable protective film and preparation method thereof |
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