CN104694035A - Glue breaking and scratch resistant paint surface protective membrane and preparation method thereof - Google Patents
Glue breaking and scratch resistant paint surface protective membrane and preparation method thereof Download PDFInfo
- Publication number
- CN104694035A CN104694035A CN201510082303.7A CN201510082303A CN104694035A CN 104694035 A CN104694035 A CN 104694035A CN 201510082303 A CN201510082303 A CN 201510082303A CN 104694035 A CN104694035 A CN 104694035A
- Authority
- CN
- China
- Prior art keywords
- disconnected
- scratch
- polyurethane film
- preparation
- glue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a glue breaking and scratch resistant paint surface protective membrane and a preparation method thereof. The glue breaking and scratch resistant paint surface protective membrane is prepared from the following components including a scratch resistant polyurethane membrane, a glue breaking resistant pressure sensitive adhesive and a release paper, wherein the scratch resistant polyurethane membrane is prepared by the following steps: carrying out surface modification on one surface of a polyurethane membrane, and introducing a chain segment containing fluorine and silicon on the surface of a polyurethane membrane; in the using process, the surface after surface modification faces outside and is directly contacted with air, so that the scratch, acid and alkali resistances, water and oil repellency and the like of the polyurethane membrane are greatly improved, hydrolysis and ageing of the polyurethane membrane in the using process are lowered, the protection performance is improved, and the service life is prolonged; the glue breaking resistant pressure sensitive adhesive is prepared by the following steps: with acrylic acid polytetrahydrofuran ester as a functional monomer, carrying out copolymerization on the functional monomer, a soft monomer and a hard monomer and is capable of well resisting tensile fracture, so that the glue breaking and scratch resistant paint surface protective membrane can be well applied to the field of automobile membrane sticking.
Description
Technical field
The present invention relates to a kind of lacquer painting protective membrane and preparation method thereof, particularly relate to a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue and preparation method thereof.
Background technology
Since being born from automobile, the step that the mankind pursue automobile maintenance never stops.In order to make love car bright as new all the time, people design a lot of ways, and the waxing that the brightness of raising lacquer painting, minimizing lacquer painting damage has been born.In order to pursue more permanent, effective protected effect, there is the appearance of envelope glaze, coating technique.But along with the prosperity of science and technology, we also get more and more to the requirement of body of a motor car maintenance, easier, more practical, more fashion, so body paint mask is also just taken advantage of a situation and raw.
The automobile finish pad pasting of present use be PVC film, but plasticizer loading is high in PVC film, the situations such as easy generation is plasticizer extraction, affect use properties and work-ing life, and flexibel polyurethane film does not exist the problem of softening agent, and the kind of flexibel polyurethane is varied, and the film that the flexibel polyurethane drawn by certain polymerization is prepared can meet most of performance, as the transparency, soft durometer, tensile strength etc.But flexibel polyurethane film also has it to limit, as easily scratched, hydrolysis etc., therefore, solving the restriction of urethane, just greatly can promote use properties and the work-ing life of urethane, promote it and protect application in pad pasting at lacquer painting.
Pressure-sensitive adhesive is that a class is to pressure-sensitive sizing agent, only need apply certain pressure and just also can produce a class tackiness agent of bonding strength in the moistening adherend surface of energy, be characterized in sticky easy, that takes off is not difficult, shell and do not damage, glue-line can not be solid in a long time, so pressure sensitive adhesive is also referred to as non-setting adhesive, it is of wide application.Because automobile adhesive film is in the process of pasting, lacquer painting is not plane, the situation that the pressure sensitive adhesive existence on pad pasting stretches, and pressure sensitive adhesive exists the possibility of disconnected glue in the process stretched, and just has a strong impact on cohesiveness and the transparency of pad pasting.
Summary of the invention
The object of this invention is to provide a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue and preparation method thereof, anti-disconnected glue anti-scratch lacquer painting protective membrane is by anti-scratch polyurethane film, anti-disconnected glue pressure sensitive adhesive and separate-type paper composition, anti-scratch polyurethane film is that one side has carried out the polyurethane film of surface modification, and the segment introducing fluorine silicon in this face obtains, in use, the one side of surface modification is towards outside, directly contact with air, improve the performance such as anti-scratch performance and water and oil repellant acid-fast alkali-proof of polyurethane film greatly, reduce hydrolysising aging in its use procedure, improve protective value, extend work-ing life, anti-disconnected glue pressure sensitive adhesive is with vinylformic acid polytetrahydrofuran ester for function monomer, and obtain with soft monomer and hard monomer copolymerization, can be good at resisting tension fracture, thus the anti-disconnected anti-scratch lacquer painting protective membrane of glue of the present invention can well be applied and automobile adhesive film field.
Anti-disconnected glue anti-scratch lacquer painting protective membrane of the present invention is made up of anti-scratch polyurethane film, anti-disconnected glue pressure sensitive adhesive and separate-type paper; Described anti-scratch polyurethane film is the polyurethane film of surface containing, for example lower molecular structure,
Described anti-disconnected glue pressure sensitive adhesive obtains primarily of soft monomer, hard monomer and function monomer copolymerization, and described function monomer is vinylformic acid polytetrahydrofuran ester, and its molecular structural formula is:
Wherein n=3 ~ 10;
By GB GB/T 9279-2007, under prescribed conditions, adopt steel ball syringe needle to test, the minimum load drawing saturating described anti-scratch polyurethane film is 3kg;
Described anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.0 ~ 4.0 pounds/25mm.
Anti-scratch polyurethane film surface, containing fluorine silicon chain structure, is conducive to the surface strength improving polyurethane film, reduces frictional force, reduce its surface tension, thus can play the effects such as anti-scratch and water and oil repellant.
The anti-disconnected anti-scratch lacquer painting protective membrane of glue of one as above, described polyurethane film is casting films, and soft durometer scope is 85 ~ 95A.Choose suitable urethane, be conducive to the carrying out of surface modification reaction, the soft durometer of urethane has certain association with its curing cross-linked degree, and reactive group residual within the scope of this soft durometer is many, is conducive to the carrying out of surface modification reaction.
The anti-disconnected anti-scratch lacquer painting protective membrane of glue of one as above, described soft monomer is one or more in ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer; Described hard monomer is acrylamide.
A preparation method for the anti-disconnected anti-scratch lacquer painting protective membrane of glue, comprises the following steps:
1) preparation of anti-scratch polyurethane film
The synthesis of a, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde;
By 3,3,3-trifluoro propionic aldehyde and NaOH solution mixing, reaction, separating-purifying, obtain 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde, structural formula is:
The synthesis of the dialdehyde of b, fluorine silicon;
Then add in acetone by described 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol, reaction, separating-purifying, obtains the dialdehyde of fluorine silicon, and its structural formula is:
The preparation of the surface-modifying agent of c, polyurethane film;
Be made into homogeneous solution by blended to the dialdehyde of fluorine silicon, light trigger and water, prepare the surface-modifying agent of polyurethane film;
The preparation of d, anti-scratch polyurethane film;
The surface-modifying agent of described polyurethane film is coated in uniformly described polyurethane film one side, then through UV-irradiation initiation reaction, dries, obtain described anti-scratch polyurethane film;
2) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of e, function monomer vinylformic acid polytetrahydrofuran ester;
PTMG is dissolved in methylene dichloride, is then added drop-wise in vinylformic acid acyl chlorides and reacts, generate vinylformic acid polytetrahydrofuran ester;
The preparation of f, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer and hard monomer are dissolved in a solvent, then add in reactor by 1/3rd of mixing solutions, be warming up to 70 ~ 90 DEG C, add initiator, then drip remaining mixing solutions, dropwise in 2 ~ 3h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.5 ~ 1h, after continuing reaction 1 ~ 2h, is cooled to room temperature; Add linking agent to stir, discharging, disconnected glue pressure sensitive adhesive must be resisted.
3) preparation of the anti-disconnected anti-scratch lacquer painting protective membrane of glue;
At described anti-scratch polyurethane film without glue pressure sensitive adhesive anti-disconnected in the one side of surface modification, dry, then carry out pressing with separate-type paper.
The preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue as above, in step a, the concentration of described NaOH solution is 2 ~ 4mol/L, and in this concentration range, NaOH can well initiation reaction, and provides good alkaline environment for the carrying out of reaction; Described 3,3,3-trifluoro propionic aldehyde and NaOH solution are 1:5 ~ 7 in mass ratio, temperature of reaction is 40 ~ 50 DEG C, and the reaction times is 2 ~ 3h, under this raw material ratio, temperature of reaction and the condition in reaction times, the transformation efficiency of 3-hydroxyl-2,4-bis-(the trifluoromethyl)-butyraldehyde obtained is higher.
The preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue as above, in step b, described 3-hydroxyl-2, 4-bis-(trifluoromethyl)-butyraldehyde and 1, 1, 3, 3, 5, 5, 7, 7-prestox-1, 7-tetrasiloxane glycol is 3 ~ 4:1 in molar ratio, described acetone and 1, 1, 3, 3, 5, 5, 7, 7-prestox-1, 7-tetrasiloxane glycol is 5 ~ 10:1 in mass ratio, temperature of reaction is 50 ~ 60 DEG C, reaction times is 3 ~ 5h, control 3-hydroxyl-2, 4-bis-(trifluoromethyl)-butyraldehyde is excessive, suitable reaction conditions, increase the transformation efficiency of reaction, guarantee that final product is the dialdehyde of fluorine silicon.
The preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue as above, in step c, the dialdehyde of described fluorine silicon, light trigger and water are 46 ~ 48:0.5 ~ 1:50 in mass ratio.Under this ratio, the modest viscosity of mixing liquid, is conducive to process for processing, has good reactivity at this ratio lower surface properties-correcting agent and polyurethane film surface simultaneously.
The preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue as above, in steps d, the coated weight of the surface-modifying agent of described polyurethane film is 1 ~ 3g/m
2, bake out temperature is 70 ~ 80 DEG C, and drying time is 15 ~ 30min.Coated weight is less than 1g/m
2, modified effect is not good, and the protected effect that can reach is not obvious, and coated weight is greater than 3g/m
2, then the curing cross-linked effect produced is too strong, affects the performance to polyurethane film, as soft durometer etc., can not meet working conditions; Coated weight controls at 1 ~ 3g/m
2be because the effect reached within the scope of this is best, good protected effect can be played, the requirement of use can be reached again.
The preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue as above, in step e, the number-average molecular weight of PTMG is 600 ~ 2000; The PTMG concentration be dissolved in methylene dichloride is 20 ~ 30wt%; The mol ratio of PTMG and vinylformic acid acyl chlorides is 1 ~ 1.3:1; Temperature of reaction is 10 ~ 30 DEG C, and reaction times 2 ~ 3h carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, and the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying.
The preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue as above, in step f, described initiator is azo-bis-isobutyl cyanide or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described linking agent is polyisocyanates; Described solvent is ethyl acetate.
The preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue as above, step 3) in, the amount of described anti-disconnected glue pressure sensitive adhesive is 40 ~ 60g/m
2, bake out temperature is 40 ~ 120 DEG C, and drying time is 8 ~ 12min.
The principle of the dialdehyde surface modified polyurethane film of fluorine silicon is:
Beneficial effect:
A kind of anti-disconnected glue anti-scratch lacquer painting protective membrane is made up of anti-scratch polyurethane film, anti-disconnected glue pressure sensitive adhesive and separate-type paper, anti-scratch polyurethane film adopts the surface-modifying agent of polyurethane film to carry out surface modification to the one side of polyurethane film to obtain, while the active group on aldehyde radical and polyurethane film surface carries out crosslinking reaction, also introduce the segment of fluorine silicon, improve anti-scratch performance and the water and oil repellant acid-fast alkali-proof performance of polyurethane film greatly, greatly reduce hydrolysising aging in its use procedure, improve protective value, extend work-ing life; Anti-disconnected glue pressure sensitive adhesive is with vinylformic acid polytetrahydrofuran ester for function monomer, and obtain with soft monomer and hard monomer copolymerization, can be good at resisting tension fracture, thus the anti-disconnected anti-scratch lacquer painting protective membrane of glue of the present invention can well be applied and automobile adhesive film field.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
The anti-disconnected anti-scratch lacquer painting protective membrane of glue of one of the present invention, anti-disconnected glue anti-scratch lacquer painting protective membrane is made up of anti-scratch polyurethane film, anti-disconnected glue pressure sensitive adhesive and separate-type paper; Anti-scratch polyurethane film is the polyurethane film of surface containing, for example lower molecular structure,
This polyurethane film is casting films, soft durometer scope is 85 ~ 95A, anti-disconnected glue pressure sensitive adhesive obtains primarily of one or more in soft monomer ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, hard monomer acrylamide and function monomer copolymerization, function monomer is vinylformic acid polytetrahydrofuran ester, and its molecular structural formula is:
Wherein n=3 ~ 10;
By GB GB/T 9279-2007, under prescribed conditions, adopt steel ball syringe needle to test, the minimum load drawing saturating anti-scratch polyurethane film is 3kg; Anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.0 ~ 4.0 pounds/25mm.
Embodiment 1
A preparation method for the anti-disconnected anti-scratch lacquer painting protective membrane of glue, comprises the following steps:
1) preparation of anti-scratch polyurethane film
The synthesis of a, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde;
Be the NaOH solution mixing of 2mol/L by 3,3,3-trifluoro propionic aldehyde and concentration, 3,3,3-trifluoro propionic aldehyde and NaOH solution are 1:5 in mass ratio, reaction, and temperature of reaction is 40 DEG C, and the reaction times is 2h, separating-purifying, obtain 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde, structural formula is:
The synthesis of the dialdehyde of b, fluorine silicon;
Then by 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol adds in acetone, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mol ratio is 3:1, acetone and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mass ratio is 5:1, reaction, temperature of reaction is 50 DEG C, and the reaction times is 5h, separating-purifying, obtains the dialdehyde of fluorine silicon, and its structural formula is:
The preparation of the surface-modifying agent of c, polyurethane film;
Be made into homogeneous solution by blended to the dialdehyde of fluorine silicon, light trigger and water, the dialdehyde of fluorine silicon, light trigger and water are 46:0.5:50 in mass ratio, prepare the surface-modifying agent of polyurethane film;
The preparation of d, anti-scratch polyurethane film;
The surface-modifying agent of polyurethane film is coated in uniformly polyurethane film one side, coated weight is 1g/m
2, then through UV-irradiation initiation reaction, dry, bake out temperature is 70 DEG C, and drying time is 15min, obtains anti-scratch polyurethane film, and anti-scratch polyurethane film is the polyurethane film of surface containing, for example lower molecular structure,
This polyurethane film is casting films, and soft durometer scope is 85A, and by GB GB/T 9279-2007, under prescribed conditions, adopt steel ball syringe needle to test, the minimum load drawing saturating anti-scratch polyurethane film is 3kg;
2) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of e, function monomer vinylformic acid polytetrahydrofuran ester;
By number-average molecular weight be 600 PTMG be dissolved in methylene dichloride, the PTMG concentration be dissolved in methylene dichloride is 20wt%, then be added drop-wise in vinylformic acid acyl chlorides and react, the mol ratio of PTMG and vinylformic acid acyl chlorides is 1:1, temperature of reaction is 10 DEG C, reaction times 2h, carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=3;
The preparation of f, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer ethyl propenoate and hard monomer acrylamide are dissolved in solvent ethyl acetate, then add in reactor by 1/3rd of mixing solutions, be warming up to 70 DEG C, add initiator azo-bis-isobutyl cyanide, then drip remaining mixing solutions, dropwise in 2h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.5h, after continuing reaction 1h, is cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.0 pounds/25mm;
3) preparation of the anti-disconnected anti-scratch lacquer painting protective membrane of glue;
At anti-scratch polyurethane film without glue pressure sensitive adhesive anti-disconnected in the one side of surface modification, the amount of upper anti-disconnected glue pressure sensitive adhesive is 40g/m
2,dry, bake out temperature is 40 DEG C, and drying time is 8min, then carries out pressing with separate-type paper.
Embodiment 2
A preparation method for the anti-disconnected anti-scratch lacquer painting protective membrane of glue, comprises the following steps:
1) preparation of anti-scratch polyurethane film
The synthesis of a, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde;
Be the NaOH solution mixing of 4mol/L by 3,3,3-trifluoro propionic aldehyde and concentration, 3,3,3-trifluoro propionic aldehyde and NaOH solution are 1:7 in mass ratio, reaction, and temperature of reaction is 50 DEG C, and the reaction times is 3h, separating-purifying, obtain 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde, structural formula is:
The synthesis of the dialdehyde of b, fluorine silicon;
Then by 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol adds in acetone, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mol ratio is 4:1, acetone and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mass ratio is 10:1, reaction, temperature of reaction is 60 DEG C, and the reaction times is 5h, separating-purifying, obtains the dialdehyde of fluorine silicon, and its structural formula is:
The preparation of the surface-modifying agent of c, polyurethane film;
Be made into homogeneous solution by blended to the dialdehyde of fluorine silicon, light trigger and water, the dialdehyde of fluorine silicon, light trigger and water are 48:1:50 in mass ratio, prepare the surface-modifying agent of polyurethane film;
The preparation of d, anti-scratch polyurethane film;
The surface-modifying agent of polyurethane film is coated in uniformly polyurethane film one side, coated weight is 3g/m
2, then through UV-irradiation initiation reaction, dry, bake out temperature is 80 DEG C, and drying time is 30min, obtains anti-scratch polyurethane film, and anti-scratch polyurethane film is the polyurethane film of surface containing, for example lower molecular structure,
This polyurethane film is casting films, and soft durometer scope is 95A, and by GB GB/T 9279-2007, under prescribed conditions, adopt steel ball syringe needle to test, the minimum load drawing saturating anti-scratch polyurethane film is 3kg;
2) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of e, function monomer vinylformic acid polytetrahydrofuran ester;
By number-average molecular weight be 2000 PTMG be dissolved in methylene dichloride, the PTMG concentration be dissolved in methylene dichloride is 30wt%, then be added drop-wise in vinylformic acid acyl chlorides and react, the mol ratio of PTMG and vinylformic acid acyl chlorides is 1.3:1, temperature of reaction is 30 DEG C, reaction times 3h, carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=10;
The preparation of f, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer butyl acrylate and hard monomer acrylamide are dissolved in solvent ethyl acetate, then add in reactor by 1/3rd of mixing solutions, be warming up to 90 DEG C, add initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), then drip remaining mixing solutions, dropwise in 3h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 1h, after continuing reaction 2h, is cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 4.0 pounds/25mm;
3) preparation of the anti-disconnected anti-scratch lacquer painting protective membrane of glue;
At anti-scratch polyurethane film without glue pressure sensitive adhesive anti-disconnected in the one side of surface modification, the amount of upper anti-disconnected glue pressure sensitive adhesive is 60g/m
2,dry, bake out temperature is 120 DEG C, and drying time is 12min, then carries out pressing with separate-type paper.
Embodiment 3
A preparation method for the anti-disconnected anti-scratch lacquer painting protective membrane of glue, comprises the following steps:
1) preparation of anti-scratch polyurethane film
The synthesis of a, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde;
Be the NaOH solution mixing of 3mol/L by 3,3,3-trifluoro propionic aldehyde and concentration, 3,3,3-trifluoro propionic aldehyde and NaOH solution are 1:6 in mass ratio, reaction, and temperature of reaction is 45 DEG C, and the reaction times is 2.5h, separating-purifying, obtain 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde, structural formula is:
The synthesis of the dialdehyde of b, fluorine silicon;
Then by 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol adds in acetone, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mol ratio is 3.5:1, acetone and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mass ratio is 6:1, reaction, temperature of reaction is 55 DEG C, and the reaction times is 5h, separating-purifying, obtains the dialdehyde of fluorine silicon, and its structural formula is:
The preparation of the surface-modifying agent of c, polyurethane film;
Be made into homogeneous solution by blended to the dialdehyde of fluorine silicon, light trigger and water, the dialdehyde of fluorine silicon, light trigger and water are 47:0.6:50 in mass ratio, prepare the surface-modifying agent of polyurethane film;
The preparation of d, anti-scratch polyurethane film;
The surface-modifying agent of polyurethane film is coated in uniformly described polyurethane film one side, coated weight is 2g/m
2, then through UV-irradiation initiation reaction, dry, bake out temperature is 72 DEG C, and drying time is 20min, obtains anti-scratch polyurethane film, and anti-scratch polyurethane film is the polyurethane film of surface containing, for example lower molecular structure,
This polyurethane film is casting films, and soft durometer scope is 90A, and by GB GB/T 9279-2007, under prescribed conditions, adopt steel ball syringe needle to test, the minimum load drawing saturating anti-scratch polyurethane film is 3kg;
2) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of e, function monomer vinylformic acid polytetrahydrofuran ester;
By number-average molecular weight be 1000 PTMG be dissolved in methylene dichloride, the PTMG concentration be dissolved in methylene dichloride is 25wt%, then be added drop-wise in vinylformic acid acyl chlorides and react, the mol ratio of PTMG and vinylformic acid acyl chlorides is 1.1:1, temperature of reaction is 20 DEG C, reaction times 2.5h, carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=5;
The preparation of f, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer Isooctyl acrylate monomer and hard monomer acrylamide are dissolved in solvent ethyl acetate, then add in reactor by 1/3rd of mixing solutions, be warming up to 75 DEG C, add initiator azo-bis-isobutyl cyanide, then drip remaining mixing solutions, dropwise in 2.5h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.6h, after continuing reaction 1.5h, is cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 3.0 pounds/25mm;
3) preparation of the anti-disconnected anti-scratch lacquer painting protective membrane of glue;
At anti-scratch polyurethane film without glue pressure sensitive adhesive anti-disconnected in the one side of surface modification, the amount of upper anti-disconnected glue pressure sensitive adhesive is 50g/m
2,dry, bake out temperature is 60 DEG C, and drying time is 9min, then carries out pressing with separate-type paper.
Embodiment 4
A preparation method for the anti-disconnected anti-scratch lacquer painting protective membrane of glue, comprises the following steps:
1) preparation of anti-scratch polyurethane film
The synthesis of a, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde;
Be the NaOH solution mixing of 2.5mol/L by 3,3,3-trifluoro propionic aldehyde and concentration, 3,3,3-trifluoro propionic aldehyde and NaOH solution are 1:5 in mass ratio, reaction, and temperature of reaction is 48 DEG C, and the reaction times is 2h, separating-purifying, obtain 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde, structural formula is:
The synthesis of the dialdehyde of b, fluorine silicon;
Then by 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol adds in acetone, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mol ratio is 3:1, acetone and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mass ratio is 6:1, reaction, temperature of reaction is 55 DEG C, and the reaction times is 5h, separating-purifying, obtains the dialdehyde of fluorine silicon, and its structural formula is:
The preparation of the surface-modifying agent of c, polyurethane film;
Be made into homogeneous solution by blended to the dialdehyde of fluorine silicon, light trigger and water, the dialdehyde of fluorine silicon, light trigger and water are 46:1:50 in mass ratio, prepare the surface-modifying agent of polyurethane film;
The preparation of d, anti-scratch polyurethane film;
The surface-modifying agent of polyurethane film is coated in uniformly polyurethane film one side, coated weight is 1.5g/m
2, then through UV-irradiation initiation reaction, dry, bake out temperature is 80 DEG C, and drying time is 15min, obtains anti-scratch polyurethane film, and anti-scratch polyurethane film is the polyurethane film of surface containing, for example lower molecular structure,
This polyurethane film is casting films, and soft durometer scope is 86A, and by GB GB/T 9279-2007, under prescribed conditions, adopt steel ball syringe needle to test, the minimum load drawing saturating anti-scratch polyurethane film is 3kg;
2) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of e, function monomer vinylformic acid polytetrahydrofuran ester;
By number-average molecular weight be 700 PTMG be dissolved in methylene dichloride, the PTMG concentration be dissolved in methylene dichloride is 30wt%, then be added drop-wise in vinylformic acid acyl chlorides and react, the mol ratio of PTMG and vinylformic acid acyl chlorides is 1.3:1, temperature of reaction is 30 DEG C, reaction times 2h, carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=6;
The preparation of f, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer ethyl propenoate, butyl acrylate and hard monomer acrylamide are dissolved in a solvent, wherein the mass ratio of ethyl propenoate and butyl acrylate is 1:1, then add in reactor by 1/3rd of mixing solutions, be warming up to 80 DEG C, add initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), then remaining mixing solutions is dripped, dropwise in 2h, then start to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 1h, after continuing reaction 1.5h, be cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 4.0 pounds/25mm;
3) preparation of the anti-disconnected anti-scratch lacquer painting protective membrane of glue;
At anti-scratch polyurethane film without glue pressure sensitive adhesive anti-disconnected in the one side of surface modification, the amount of upper anti-disconnected glue pressure sensitive adhesive is 48g/m
2,dry, bake out temperature is 100 DEG C, and drying time is 8min, then carries out pressing with separate-type paper.
Embodiment 5
A preparation method for the anti-disconnected anti-scratch lacquer painting protective membrane of glue, comprises the following steps:
1) preparation of anti-scratch polyurethane film
The synthesis of a, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde;
Be the NaOH solution mixing of 4mol/L by 3,3,3-trifluoro propionic aldehyde and concentration, 3,3,3-trifluoro propionic aldehyde and NaOH solution are 1:5 in mass ratio, reaction, and temperature of reaction is 50 DEG C, and the reaction times is 2h, separating-purifying, obtain 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde, structural formula is:
The synthesis of the dialdehyde of b, fluorine silicon;
Then by 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol adds in acetone, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mol ratio is 3.5:1, acetone and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mass ratio is 9:1, reaction, temperature of reaction is 56 DEG C, and the reaction times is 5h, separating-purifying, obtains the dialdehyde of fluorine silicon, and its structural formula is:
The preparation of the surface-modifying agent of c, polyurethane film;
Be made into homogeneous solution by blended to the dialdehyde of fluorine silicon, light trigger and water, the dialdehyde of fluorine silicon, light trigger and water are 48:0.7:50 in mass ratio, prepare the surface-modifying agent of polyurethane film;
The preparation of d, anti-scratch polyurethane film;
The surface-modifying agent of polyurethane film is coated in uniformly polyurethane film one side, coated weight is 1g/m
2, then through UV-irradiation initiation reaction, dry, bake out temperature is 80 DEG C, and drying time is 280min, obtains anti-scratch polyurethane film, and anti-scratch polyurethane film is the polyurethane film of surface containing, for example lower molecular structure,
This polyurethane film is casting films, and soft durometer scope is 88A, by GB GB/T 9279-2007, under prescribed conditions,
Adopt steel ball syringe needle to test, the minimum load drawing saturating anti-scratch polyurethane film is 3kg;
2) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of e, function monomer vinylformic acid polytetrahydrofuran ester;
By number-average molecular weight be 1600 PTMG be dissolved in methylene dichloride, the PTMG concentration be dissolved in methylene dichloride is 22wt%, then be added drop-wise in vinylformic acid acyl chlorides and react, the mol ratio of PTMG and vinylformic acid acyl chlorides is 1.2:1, temperature of reaction is 16 DEG C, reaction times 2.6h, carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=8;
The preparation of f, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer butyl acrylate, Isooctyl acrylate monomer and hard monomer acrylamide are dissolved in solvent ethyl acetate, wherein the mass ratio of butyl acrylate and Isooctyl acrylate monomer is 1:2, then add in reactor by 1/3rd of mixing solutions, be warming up to 90 DEG C, add initiator, then remaining mixing solutions is dripped, dropwise in 2h, then start to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 1h, after continuing reaction 1.2h, be cooled to room temperature; Add linking agent to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.5 pounds/25mm;
3) preparation of the anti-disconnected anti-scratch lacquer painting protective membrane of glue;
At anti-scratch polyurethane film without glue pressure sensitive adhesive anti-disconnected in the one side of surface modification, the amount of upper anti-disconnected glue pressure sensitive adhesive is 56g/m
2,dry, bake out temperature is 80 DEG C, and drying time is 9min, then carries out pressing with separate-type paper.
Embodiment 6
A preparation method for the anti-disconnected anti-scratch lacquer painting protective membrane of glue, comprises the following steps:
1) preparation of anti-scratch polyurethane film
The synthesis of a, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde;
It is the NaOH solution mixing of 2.6mol/L by 3,3,3-trifluoro propionic aldehyde and concentration, 3,3,3-trifluoro propionic aldehyde and NaOH solution are 1:5.5 in mass ratio, reaction, temperature of reaction is 40 DEG C, reaction times is 3h, and separating-purifying obtains 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde, structural formula is:
The synthesis of the dialdehyde of b, fluorine silicon;
Then by 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol adds in acetone, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mol ratio is 3.5:1, acetone and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mass ratio is 10:1, reaction, temperature of reaction is 50 DEG C, and the reaction times is 5h, separating-purifying, obtains the dialdehyde of fluorine silicon, and its structural formula is:
The preparation of the surface-modifying agent of c, polyurethane film;
Be made into homogeneous solution by blended to the dialdehyde of fluorine silicon, light trigger and water, the dialdehyde of fluorine silicon, light trigger and water are 48:1:50 in mass ratio, prepare the surface-modifying agent of polyurethane film;
The preparation of d, anti-scratch polyurethane film;
The surface-modifying agent of polyurethane film is coated in uniformly polyurethane film one side, coated weight is 3g/m
2, then through UV-irradiation initiation reaction, dry, bake out temperature is 70 DEG C, and drying time is 30min, obtains anti-scratch polyurethane film, and anti-scratch polyurethane film is the polyurethane film of surface containing, for example lower molecular structure,
This polyurethane film is casting films, and soft durometer scope is 94A, and by GB GB/T 9279-2007, under prescribed conditions, adopt steel ball syringe needle to test, the minimum load drawing saturating anti-scratch polyurethane film is 3kg;
2) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of e, function monomer vinylformic acid polytetrahydrofuran ester;
By number-average molecular weight be 1000 PTMG be dissolved in methylene dichloride, the PTMG concentration be dissolved in methylene dichloride is 28wt%, then be added drop-wise in vinylformic acid acyl chlorides and react, the mol ratio of PTMG and vinylformic acid acyl chlorides is 1:1, temperature of reaction is 18 DEG C, reaction times 2.2h, carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=7;
The preparation of f, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer ethyl propenoate, Isooctyl acrylate monomer and hard monomer acrylamide are dissolved in solvent ethyl acetate, the wherein mass ratio 2:1 of ethyl propenoate and Isooctyl acrylate monomer, for then adding in reactor by 1/3rd of mixing solutions, be warming up to 76 DEG C, add initiator azo-bis-isobutyl cyanide, then remaining mixing solutions is dripped, dropwise in 2.2h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.6h, after continuing reaction 1.2h, be cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.2 pounds/25mm;
3) preparation of the anti-disconnected anti-scratch lacquer painting protective membrane of glue;
At anti-scratch polyurethane film without glue pressure sensitive adhesive anti-disconnected in the one side of surface modification, the amount of upper anti-disconnected glue pressure sensitive adhesive is 45g/m
2,dry, bake out temperature is 90 DEG C, and drying time is 10min, then carries out pressing with separate-type paper.
Embodiment 7
A preparation method for the anti-disconnected anti-scratch lacquer painting protective membrane of glue, comprises the following steps:
1) preparation of anti-scratch polyurethane film
The synthesis of a, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde;
Be the NaOH solution mixing of 2mol/L by 3,3,3-trifluoro propionic aldehyde and concentration, 3,3,3-trifluoro propionic aldehyde and NaOH solution are 1:5 in mass ratio, reaction, and temperature of reaction is 48 DEG C, and the reaction times is 2.5h, separating-purifying, obtain 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde, structural formula is:
The synthesis of the dialdehyde of b, fluorine silicon;
Then by 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol adds in acetone, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mol ratio is 3:1, acetone and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mass ratio is 6:1, reaction, temperature of reaction is 55 DEG C, and the reaction times is 5h, separating-purifying, obtains the dialdehyde of fluorine silicon, and its structural formula is:
The preparation of the surface-modifying agent of c, polyurethane film;
Be made into homogeneous solution by blended to the dialdehyde of fluorine silicon, light trigger and water, the dialdehyde of fluorine silicon, light trigger and water are 48:1:50 in mass ratio, prepare the surface-modifying agent of described polyurethane film;
The preparation of d, anti-scratch polyurethane film;
The surface-modifying agent of polyurethane film is coated in uniformly polyurethane film one side, coated weight is 1g/m
2, then through UV-irradiation initiation reaction, dry, bake out temperature is 70 DEG C, and drying time is 30min, obtains anti-scratch polyurethane film, and anti-scratch polyurethane film is the polyurethane film of surface containing, for example lower molecular structure,
This polyurethane film is casting films, and soft durometer scope is 87A, and by GB GB/T 9279-2007, under prescribed conditions, adopt steel ball syringe needle to test, the minimum load drawing saturating anti-scratch polyurethane film is 3kg;
2) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of e, function monomer vinylformic acid polytetrahydrofuran ester;
By number-average molecular weight be 1200 PTMG be dissolved in methylene dichloride, the PTMG concentration be dissolved in methylene dichloride is 28wt%, then be added drop-wise in vinylformic acid acyl chlorides and react, the mol ratio of PTMG and vinylformic acid acyl chlorides is 1.3:1, temperature of reaction is 15 DEG C, reaction times 2h, carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=10;
The preparation of f, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer and hard monomer are dissolved in a solvent, wherein ethyl propenoate, mass ratio between butyl acrylate and Isooctyl acrylate monomer are 1:2:1, then add in reactor by 1/3rd of mixing solutions, be warming up to 90 DEG C, add initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), then remaining mixing solutions is dripped, dropwise in 3h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.8h, after continuing reaction 1h, be cooled to room temperature; Add linking agent polyisocyanates to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.0 pounds/25mm;
3) preparation of the anti-disconnected anti-scratch lacquer painting protective membrane of glue;
At anti-scratch polyurethane film without glue pressure sensitive adhesive anti-disconnected in the one side of surface modification, the amount of upper anti-disconnected glue pressure sensitive adhesive is 60g/m
2,dry, bake out temperature is 40 DEG C, and drying time is 8min, then carries out pressing with separate-type paper.
Embodiment 8
A preparation method for the anti-disconnected anti-scratch lacquer painting protective membrane of glue, comprises the following steps:
1) preparation of anti-scratch polyurethane film
The synthesis of a, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde;
Be the NaOH solution mixing of 2.5mol/L by 3,3,3-trifluoro propionic aldehyde and concentration, 3,3,3-trifluoro propionic aldehyde and NaOH solution are 1:5 in mass ratio, reaction, and temperature of reaction is 40 DEG C, and the reaction times is 3h, separating-purifying, obtain 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde, structural formula is:
The synthesis of the dialdehyde of b, fluorine silicon;
Then by 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol adds in acetone, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mol ratio is 3.2:1, acetone and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol mass ratio is 5:1, reaction, temperature of reaction is 52 DEG C, and the reaction times is 5h, separating-purifying, obtains the dialdehyde of fluorine silicon, and its structural formula is:
The preparation of the surface-modifying agent of c, polyurethane film;
Be made into homogeneous solution by blended to the dialdehyde of fluorine silicon, light trigger and water, the dialdehyde of fluorine silicon, light trigger and water are 46:1:50 in mass ratio, prepare the surface-modifying agent of described polyurethane film;
The preparation of d, anti-scratch polyurethane film;
The surface-modifying agent of polyurethane film is coated in uniformly described polyurethane film one side, coated weight is 1.5g/m
2, then through UV-irradiation initiation reaction, dry, bake out temperature is 72 DEG C, and drying time is 15min, obtains anti-scratch polyurethane film, and anti-scratch polyurethane film is the polyurethane film of surface containing, for example lower molecular structure,
This polyurethane film is casting films, and soft durometer scope is 90A, and by GB GB/T 9279-2007, under prescribed conditions, adopt steel ball syringe needle to test, the minimum load drawing saturating anti-scratch polyurethane film is 3kg;
2) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of e, function monomer vinylformic acid polytetrahydrofuran ester;
By number-average molecular weight be 2000 PTMG be dissolved in methylene dichloride, the PTMG concentration be dissolved in methylene dichloride is 30wt%, then be added drop-wise in vinylformic acid acyl chlorides and react, the mol ratio of PTMG and vinylformic acid acyl chlorides is 1.1:1, temperature of reaction is 18 DEG C, reaction times 2h, carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying, and generate vinylformic acid polytetrahydrofuran ester, its molecular structural formula is:
Wherein n=3;
The preparation of f, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer and hard monomer acrylamide are dissolved in solvent ethyl acetate, wherein the mass ratio of ethyl propenoate, butyl acrylate and Isooctyl acrylate monomer is 1:1:1, then add in reactor by 1/3rd of mixing solutions, be warming up to 90 DEG C, add initiator azo-bis-isobutyl cyanide, then remaining mixing solutions is dripped, dropwise in 2.5h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 1h, after continuing reaction 1h, be cooled to room temperature; Add linking agent to stir, discharging, must resist disconnected glue pressure sensitive adhesive, anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 3.0 pounds/25mm;
3) preparation of the anti-disconnected anti-scratch lacquer painting protective membrane of glue;
At anti-scratch polyurethane film without glue pressure sensitive adhesive anti-disconnected in the one side of surface modification, the amount of upper anti-disconnected glue pressure sensitive adhesive is 5g/m
2,dry, bake out temperature is 80 DEG C, and drying time is 8min, then carries out pressing with separate-type paper.
Claims (10)
1. the anti-disconnected anti-scratch lacquer painting protective membrane of glue, is characterized in that: described anti-disconnected glue anti-scratch lacquer painting protective membrane is made up of anti-scratch polyurethane film, anti-disconnected glue pressure sensitive adhesive and separate-type paper; Described anti-scratch polyurethane film is the polyurethane film of surface containing, for example lower molecular structure,
Described anti-disconnected glue pressure sensitive adhesive obtains primarily of soft monomer, hard monomer and function monomer copolymerization, and described function monomer is vinylformic acid polytetrahydrofuran ester, and its molecular structural formula is:
Wherein n=3 ~ 10;
By GB GB/T 9279-2007, under prescribed conditions, adopt steel ball syringe needle to test, the minimum load drawing saturating described anti-scratch polyurethane film is 3kg;
Described anti-disconnected glue pressure sensitive adhesive does not rupture when stretching 300%, and 180 ° of separation strengths are 2.0 ~ 4.0 pounds/25mm.
2. the anti-disconnected anti-scratch lacquer painting protective membrane of glue of one according to claim 1, it is characterized in that, described polyurethane film is casting films, and soft durometer scope is 85 ~ 95A.
3. the anti-disconnected anti-scratch lacquer painting protective membrane of glue of one according to claim 1, it is characterized in that, described soft monomer is one or more in ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer; Described hard monomer is acrylamide.
4. a preparation method for the anti-disconnected anti-scratch lacquer painting protective membrane of glue, is characterized in that comprising the following steps:
1) preparation of anti-scratch polyurethane film
The synthesis of a, 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde;
By 3,3,3-trifluoro propionic aldehyde and NaOH solution mixing, reaction, separating-purifying, obtain 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde, structural formula is:
The synthesis of the dialdehyde of b, fluorine silicon;
Then add in acetone by described 3-hydroxyl-2,4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3,5,5,7,7-prestox-1,7-tetrasiloxane glycol, reaction, separating-purifying, obtains the dialdehyde of fluorine silicon, and its structural formula is:
The preparation of the surface-modifying agent of c, polyurethane film;
Be made into homogeneous solution by blended to the dialdehyde of fluorine silicon, light trigger and water, prepare the surface-modifying agent of described polyurethane film;
The preparation of d, anti-scratch polyurethane film;
The surface-modifying agent of described polyurethane film is coated in uniformly described polyurethane film one side, then through UV-irradiation initiation reaction, dries, obtain described anti-scratch polyurethane film;
2) preparation of anti-disconnected glue pressure sensitive adhesive
The preparation of e, function monomer vinylformic acid polytetrahydrofuran ester;
PTMG is dissolved in methylene dichloride, is then added drop-wise in vinylformic acid acyl chlorides and reacts, generate vinylformic acid polytetrahydrofuran ester;
The preparation of f, anti-disconnected glue pressure sensitive adhesive;
Raw materials by weight portion is counted:
Soft monomer and hard monomer are dissolved in a solvent, then add in reactor by 1/3rd of mixing solutions, be warming up to 70 ~ 90 DEG C, add initiator, then drip remaining mixing solutions, dropwise in 2 ~ 3h, start again to drip function monomer vinylformic acid polytetrahydrofuran ester, time for adding is 0.5 ~ 1h, after continuing reaction 1 ~ 2h, is cooled to room temperature; Add linking agent to stir, discharging, disconnected glue pressure sensitive adhesive must be resisted;
3) preparation of the anti-disconnected anti-scratch lacquer painting protective membrane of glue;
At described anti-scratch polyurethane film without glue pressure sensitive adhesive anti-disconnected in the one side of surface modification, dry, then carry out pressing with separate-type paper.
5. the preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue according to claim 4; it is characterized in that; in step a; the concentration of described NaOH solution is 2 ~ 4mol/L; described 3,3,3-trifluoro propionic aldehyde and NaOH solution are 1:5 ~ 7 in mass ratio; temperature of reaction is 40 ~ 50 DEG C, and the reaction times is 2 ~ 3h.
6. the preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue according to claim 4, is characterized in that, in step b, and described 3-hydroxyl-2; 4-bis-(trifluoromethyl)-butyraldehyde and 1,1,3,3; 5,5,7,7-prestox-1; 7-tetrasiloxane glycol is 3 ~ 4:1 in molar ratio, described acetone and 1,1,3; 3,5,5,7; 7-prestox-1,7-tetrasiloxane glycol is 5 ~ 10:1 in mass ratio, and temperature of reaction is 50 ~ 60 DEG C, and the reaction times is 5h.
7. the preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue according to claim 4, is characterized in that, in step c, the dialdehyde of described fluorine silicon, light trigger and water are 46 ~ 48:0.5 ~ 1:50 in mass ratio.
8. the preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue according to claim 4, it is characterized in that, in steps d, the coated weight of the surface-modifying agent of described polyurethane film is 1 ~ 3g/m
2, bake out temperature is 70 ~ 80 DEG C, and drying time is 15 ~ 30min.
9. the preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue according to claim 4, it is characterized in that, in step e, the number-average molecular weight of PTMG is 600 ~ 2000; The PTMG concentration be dissolved in methylene dichloride is 20 ~ 30wt%; The mol ratio of PTMG and vinylformic acid acyl chlorides is 1 ~ 1.3:1; Temperature of reaction is 10 ~ 30 DEG C, and reaction times 2 ~ 3h carrys out the hydrogen chloride gas produced in absorption reaction process with triethylamine in reaction process, and the mol ratio of triethylamine and vinylformic acid acyl chlorides is 1:1; Reaction product is through extracting and separating, underpressure distillation and vacuum-drying; Described initiator is azo-bis-isobutyl cyanide or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described linking agent is polyisocyanates; Described solvent is ethyl acetate.
10. the preparation method of a kind of anti-disconnected anti-scratch lacquer painting protective membrane of glue according to claim 4, is characterized in that, step 3) in, the amount of described anti-disconnected glue pressure sensitive adhesive is 40 ~ 60g/m
2, bake out temperature is 40 ~ 120 DEG C, and drying time is 8 ~ 12min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510082303.7A CN104694035B (en) | 2015-02-15 | 2015-02-15 | Glue breaking and scratch resistant paint surface protective membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510082303.7A CN104694035B (en) | 2015-02-15 | 2015-02-15 | Glue breaking and scratch resistant paint surface protective membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104694035A true CN104694035A (en) | 2015-06-10 |
| CN104694035B CN104694035B (en) | 2017-05-03 |
Family
ID=53341601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510082303.7A Active CN104694035B (en) | 2015-02-15 | 2015-02-15 | Glue breaking and scratch resistant paint surface protective membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104694035B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111331981A (en) * | 2020-04-01 | 2020-06-26 | 东莞市瑞年塑胶科技有限公司 | Electrostatic adsorption flame-retardant film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070249770A1 (en) * | 2004-06-21 | 2007-10-25 | Sekisui Chemical Co., Ltd. | Binder Resin Composition, Paste and Green Sheet |
| CN101760967A (en) * | 2008-11-14 | 2010-06-30 | 杨玉生 | Waterproof and oilproof finishing agent for fabric and leather and preparation thereof |
| CN204939372U (en) * | 2015-07-28 | 2016-01-06 | 太湖金张科技股份有限公司 | A kind of optics double sticky tape |
-
2015
- 2015-02-15 CN CN201510082303.7A patent/CN104694035B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070249770A1 (en) * | 2004-06-21 | 2007-10-25 | Sekisui Chemical Co., Ltd. | Binder Resin Composition, Paste and Green Sheet |
| CN101760967A (en) * | 2008-11-14 | 2010-06-30 | 杨玉生 | Waterproof and oilproof finishing agent for fabric and leather and preparation thereof |
| CN204939372U (en) * | 2015-07-28 | 2016-01-06 | 太湖金张科技股份有限公司 | A kind of optics double sticky tape |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111331981A (en) * | 2020-04-01 | 2020-06-26 | 东莞市瑞年塑胶科技有限公司 | Electrostatic adsorption flame-retardant film |
| CN111331981B (en) * | 2020-04-01 | 2021-03-19 | 东莞市瑞年塑胶科技有限公司 | Electrostatic adsorption flame-retardant film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104694035B (en) | 2017-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102504717B (en) | Adhesive tape for bonding low-surface-energy material and preparation method thereof | |
| CN111058334B (en) | Modified polyacrylate waterproof anti-sticking agent, preparation method and application | |
| US20160122597A1 (en) | Preparation of pressure sensitive adhesive dispersions from multi-stage emulsion polymerization for applications of protective films | |
| CN109867743B (en) | Room-temperature self-crosslinking water-based acrylic resin dispersion and preparation method thereof | |
| CN104342073A (en) | Organic silicon modified phenyl emulsion pressure-sensitive adhesive with high release force and low residue as well as preparation method thereof and application | |
| CN103952105A (en) | Fluorosilicone modified aqueous pressure-sensitive adhesive used for polyethylene protection film, and preparation method thereof | |
| US7345111B2 (en) | Acrylic polymer emulsion and glove formed from the same | |
| CN110452620A (en) | Optical adhesive tape and preparation method thereof, optical cement | |
| CN103980414A (en) | Polyacrylate pressure-sensitive adhesive emulsion for polyethylene protection film and preparation method thereof | |
| CN108384476A (en) | A kind of polarizing plate protective film pressure sensitive adhesive preparation method and its protective film | |
| CN116554797B (en) | Composite adhesive tape for lithium battery and preparation method thereof | |
| CN110698585A (en) | High-temperature-resistant modified acrylate pressure-sensitive adhesive and preparation method thereof | |
| CN102533184B (en) | Water-based pressure-sensitive adhesive of polyethylene protective film and preparation method thereof | |
| CN103819994B (en) | A kind of polypropylene film coating UV light-cured acrylate aqueous polymer dispersion | |
| CN104650311A (en) | Self-dispersing UV photo-curing urethane acrylate aqueous copolymer, preparation method of aqueous copolymer and aqueous emulsion prepared from aqueous copolymer | |
| CN108794682B (en) | Normal-temperature ketone hydrazine self-crosslinking acrylic resin emulsion and preparation method and application thereof | |
| CN104694035A (en) | Glue breaking and scratch resistant paint surface protective membrane and preparation method thereof | |
| CN104774572A (en) | Protective film for automobile and preparation method thereof | |
| CN110790875B (en) | Organic silicon modified acrylic emulsion adhesive and preparation method thereof | |
| CN105885745A (en) | Silicon-fluorine modified polyacrylate pressure-sensitive adhesive emulsion for PVC high-temperature-resistant adhesive tape, preparation method and application | |
| CN104694038A (en) | Glue-breaking-resistant paint surface protecting cover and preparation method thereof | |
| CN106010379B (en) | A kind of battery label water soluble acrylic acid ester pressure-sensitive and preparation method thereof | |
| CN114736580A (en) | Water-based release adhesive and preparation method and application thereof | |
| CN104694037A (en) | Adhesive-fracture-resistant car protective film and preparation method thereof | |
| CN113637433A (en) | Water-based acrylate pressure-sensitive adhesive and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |