CN111423609A

CN111423609A - Essential anti-static release film base film and application thereof

Info

Publication number: CN111423609A
Application number: CN202010371258.8A
Authority: CN
Inventors: 张国庆; 张怡
Original assignee: Changzhou Weinuo Plastics Co ltd
Current assignee: Changzhou Weinuo Plastics Co ltd
Priority date: 2020-05-06
Filing date: 2020-05-06
Publication date: 2020-07-17
Anticipated expiration: 2040-05-06
Also published as: CN111423609B

Abstract

The utility model provides an essence type prevents static from type membrane base film and application thereof, prevents static from type membrane base film material for modified HDPE, modified HDPE includes following raw materials: alkenyl compounds and double bond-containing quaternary ammonium salts. The essential antistatic release film base membrane is prepared by doping polymerizable quaternary ammonium salt in a high-density polyethylene polymerization monomer, wherein the quaternary ammonium salt is an excellent cationic antistatic agent and is uniformly dispersed in resin to form a passage for leaking static charges, and groups with the antistatic function cannot migrate and be adhered away, so that the essential antistatic function is exerted. In the invention, a small amount of quaternary ammonium salt containing two or more carbon-carbon double bonds is added into the comonomer of the modified HDPE, so that the antistatic effect of the modified HDPE is improved, and the effect of improving the antistatic effect of the release film in a high-temperature and high-humidity environment is unexpectedly discovered.

Description

Essential anti-static release film base film and application thereof

Technical Field

The invention belongs to the field of plastic films, relates to a release film base film, and particularly relates to an essential anti-static release film base film and application thereof.

Background

The release film comprises a base film layer and a release layer, and is formed by coating a release agent on the surface layer of an environment-friendly base film material, such as PE, PET, OPP and other films on one side or two sides, so that the release film can show extremely light and stable release force for various organic pressure-sensitive adhesives (such as hot-melt adhesives, acrylic and rubber-based pressure-sensitive adhesives). Release films are generally used for isolating viscous materials, and are widely applied to the fields of packaging, printing, flexible electronic circuits, films for sealing materials, die cutting and punching processing and the like.

With the rapid development of the electronic industry, the integration level of electronic circuit boards is higher and higher, and the high density, compact wiring of electronic components on a mainboard and even the wide adoption of surface-mounted components can easily cause electrostatic damage to the circuit board card, and the release film is widely applied to the protective film during the production of the electronic circuit boards because the release film does not have viscosity or slight viscosity after being contacted with a specific material under limited conditions. However, since most release films are insulating plastic films, static electricity is easily generated after the release films are rubbed with other insulating materials, and devices on an electronic circuit board and the like are also damaged destructively, and the release films still do not meet the requirements of electronic product production.

In order to meet the requirements of electronic product production, the prior art mostly adopts a method of coating an antistatic layer containing an antistatic agent on a release film, for example, patent CN201610024920.6 discloses a protective film with diamond flash and antistatic effects and a preparation method thereof, and the protective film comprises three layers from top to bottom: the protective film comprises a protective film layer (10), a using layer (20) and a stripping layer (30), wherein the using layer (20) comprises a UV hardening layer (24), an antistatic layer (22), a B substrate (21) and a B adhesive layer (26), the thickness of the antistatic layer (22) is 1-10 mu m, the B substrate (21) is one of a PET film, a PEN film, a PE film and a BOPET film, the thickness of the B substrate (21) is 20-200 mu m, the light transmittance of the B substrate (21) is higher than 90%, and the haze is 0; the main component of the adhesive layer B (26) is an organic silicon pressure-sensitive adhesive layerThe thickness of the adhesive layer (26) B is 20-100 μm; the antistatic agent is one or a mixture of more of amine derivatives, quaternary ammonium salts, sulfuric ester, phosphate and polyethylene glycol derivatives, and the surface resistance of the antistatic layer (22) is 10⁸～10¹⁰Omega.m; patent CN201521139554.6 discloses a double-sided ultra-light anti-static release film structure, which comprises a surface layer (2), a release agent layer (3) and a substrate layer (4), and is characterized by further comprising an anti-static layer (1), wherein the upper surfaces of the anti-static layer (1), the surface layer (2), the release agent layer (3) and the substrate layer (4) are sequentially attached from top to bottom, the lower surface of the substrate layer (4) is also provided with the anti-static layer (1), the anti-static layer (1) is made of a conductive polymer, and the thickness of the anti-static layer is 3-5 mu m; patent CN201210237332.2 discloses an antistatic release film and a preparation method thereof, which comprises a base film and a functional layer, and is characterized in that the functional layer is prepared from the following components in parts by weight: 0.5-1 part of conductive polymer resin, 1-2 parts of hydrogen-containing silicone oil, 5-10 parts of vinyl organic silicon resin, 0.05-0.2 part of platinum complex catalyst and 0.05-0.2 part of photoinitiator; the conductive polymer resin is polyaniline; the hydrogen-containing silicone oil is tetramethyl dihydro disiloxane; the vinyl organic silicon resin is modified dimethicone resin. The above method of coating the antistatic layer containing the antistatic agent on the base film can certainly provide a certain antistatic effect.

However, the release film prepared by the above method is often rubbed, washed, or used in air for a long time, and the migration of the antistatic component into the polymer is gradually reduced, so that the antistatic effect is not ideal, and the durability is difficult, so that it is urgently needed to develop an intrinsic antistatic release film.

Disclosure of Invention

In order to solve the above problems, the present invention provides an essential antistatic release film base film, which is prepared from an essential antistatic resin obtained by copolymerizing a polymerizable quaternary ammonium salt with ethylene, wherein the quaternary ammonium salt is an excellent cationic antistatic agent, and the quaternary ammonium salt is uniformly dispersed in the resin to form a passage for leaking static charges, and simultaneously, groups having an antistatic function do not migrate and are not adhered, thereby performing an essential antistatic function.

The utility model provides an essence type is prevented static from type membrane base film, prevent static from type membrane base film material for modified HDPE, modified HDPE includes following raw materials: alkenyl compounds and double bond-containing quaternary ammonium salts.

The alkenyl compound is at least one of ethylene, propylene, butene, pentene and hexene, and the double-bond quaternary ammonium salt is a compound of a quaternary ammonium salt containing one carbon-carbon double bond and a quaternary ammonium salt containing two or more carbon-carbon double bonds.

The quaternary ammonium salt containing one carbon-carbon double bond is at least one selected from dimethyl allyl ammonium chloride and N-4-vinyl phenyl-N, N-dimethyl ammonium chloride; the quaternary ammonium salt containing two or more carbon-carbon double bonds is selected from at least one of dimethyl diallyl ammonium chloride and diallyl diethyl ammonium chloride.

The modified HDPE comprises the following raw materials in parts by weight: 80-90 parts of ethylene, 0.5-1.5 parts of propylene, 1-3 parts of 1-butene and 10-15 parts of double-bond quaternary ammonium salt, wherein the weight ratio of the quaternary ammonium salt containing one carbon-carbon double bond to the quaternary ammonium salt containing two or more carbon-carbon double bonds is 10-15: 1-2.

The modified HDPE is prepared by adopting a slurry polymerization method and comprises the following steps:

1) adding a catalyst into the kettle-type reactor subjected to nitrogen displacement;

2) adding the dried alkenyl compound, the double-bond quaternary ammonium salt and the mixed circulating diluent into a kettle type reactor, introducing hydrogen, and heating;

3) taking out the polymerization product in the last step for flash evaporation, centrifuging the slurry after flash evaporation, recovering a solid filter cake, sending the solid filter cake to a nitrogen-protected dryer for removing volatile components, and finally sending the dried powder to a fluidized bed for drying again to obtain the HDPE polymer particles.

The reaction conditions of the temperature rise reaction in the step 2) are 70-105 ℃, the total pressure is 1.8-2.2MPa, and the hydrogen partial pressure is 1-4%.

Step 1) the catalyst is a main catalyst and is load type TiCl₄/MgCl₂The cocatalyst is triethylaluminum, whichThe quantity concentration (calculated by titanium) of the main catalyst substance is 2 × 10-5-2 × 10-4 mol/L, and the molar ratio of Al to Ti is 150-.

And 2) the mixed circulating diluent is a mixed solvent of n-hexane and ethyl acetate, and the volume ratio of the n-hexane to the ethyl acetate is 10: 1-2.

The dimethyl allyl ammonium chloride comprises the following raw materials in parts by weight: 80 parts of N, N-dimethyl allylamine, 50-130 parts of a quaternizing agent and 0.08-0.4 part of p-hydroxyanisole serving as a polymerization inhibitor, wherein the quaternizing agent has no special requirement, and the quaternizing agent is alkyl halide commonly used in the field and comprises but is not limited to at least one of methyl chloride and ethyl bromide.

The preparation method of the dimethyl allyl ammonium chloride comprises the following steps:

s1, adding deionized water into a reaction kettle containing N, N-dimethylallylamine under the nitrogen atmosphere, uniformly stirring, and dropwise adding an HCl solution into the mixed solution to ensure that the pH value of the mixed solution is 6.5-7.5;

s2, adding polymerization inhibitor p-hydroxyanisole into the mixed solution, stirring uniformly, heating to 50 ℃, and keeping the temperature constant;

s3, adding a quaternizing agent into the constant-temperature mixed solution dropwise until the solution is clear, and continuing stirring for 0.5-1 h;

and S4, precipitating the mixture after the reaction, filtering and drying to obtain the quaternary ammonium salt.

The application of the essential antistatic release film base film is that a release agent is coated on a base film layer and the essential antistatic release film is obtained directly or after drying or curing.

The release agent is not particularly required, and may be commonly used in the art, including but not limited to at least one of silicone release agent, non-silicone release agent, fluorine release agent, UV light irradiation type release agent.

The organic silicon release agent comprises the following raw materials: 10 parts of vinyl end group organic silicon resin, 0.5-2 parts of platinum catalyst, 60-200 parts of organic solvent and 0.5-3 parts of cross-linking agent blocked polyisocyanate, wherein the use concentration of the release agent is 5-10%, and the coating dry weight is 0.3-1g/m²

Compared with the prior art, the invention has the beneficial effects that:

the essential antistatic release film base membrane is prepared by doping polymerizable quaternary ammonium salt in a high-density polyethylene polymerization monomer, wherein the quaternary ammonium salt is an excellent cationic antistatic agent and is uniformly dispersed in resin to form a passage for leaking static charges, and groups with the antistatic function cannot migrate and be adhered away, so that the essential antistatic function is exerted.

In the invention, a small amount of quaternary ammonium salt containing two or more carbon-carbon double bonds is added into the comonomer of the modified HDPE, so that the antistatic effect of the modified HDPE is improved, and the effect of improving the antistatic effect of the release film in a high-temperature and high-humidity environment is unexpectedly discovered.

Detailed Description

The present invention will be further described with reference to the following examples, but the present invention is not limited to the descriptions in the following. Unless otherwise specified, "parts" in the examples of the present invention are parts by weight. All reagents used are commercially available in the art.

Example 1

Preparation of dimethyl allyl ammonium chloride:

s1, adding 150 parts of deionized water into a reaction kettle containing 80 parts of N, N-dimethylallylamine under the nitrogen atmosphere, uniformly stirring, and then dropwise adding a standard HCl solution into the mixed solution to enable the pH of the mixed solution to be 7;

s2, adding 0.10 part of polymerization inhibitor p-hydroxyanisole into the mixed solution, stirring uniformly, heating the reaction kettle to 50 ℃, and keeping the temperature constant;

s3, dripping 60 parts of quaternizing agent chloromethane into the constant-temperature mixed solution until the solution is clear, and continuously stirring for reaction for 1 hour;

s4, adding carbon tetrachloride dropwise into the mixture after the reaction until no precipitate is separated out, and filtering and drying to obtain the quaternary ammonium salt.

Preparation of modified HDPE:

1) adding a main catalyst into the kettle-type reactor subjected to nitrogen replacement to obtain supported TiCl₄/MgCl₂Cocatalyst is triethyl aluminum, and the concentration of TiIs 2 × 10^-5mol/L, Al and Ti (molar ratio) 180;

2) adding 80 parts of dried ethylene, 1 part of propylene, 1 part of 1-butene, 13.64 parts of dimethyl allyl ammonium chloride, 1.36 parts of dimethyl diallyl ammonium chloride and a mixed circulating diluent consisting of 181.82 parts of n-hexane and 18.18 parts of ethyl acetate into a kettle type reactor, introducing hydrogen, heating to 90 ℃, and keeping the total pressure at 1.8MPa and the hydrogen partial pressure at 2%;

Preparing an essential antistatic release film:

t1: extruding the modified HDPE on an extruder, wherein the length-diameter ratio of the extruder is 30:1, and the temperature of 5 heating zones of the extruder is as follows: the first area is 110 ℃, the second area is 160 ℃, the third area is 170 ℃, the neck mold is 180 ℃, the head is 190 ℃ to obtain a release film base film, and the thickness is (36 +/-0.05) mu m;

t2: uniformly coating a release agent consisting of 10 parts of vinyl end group organic silicon resin, 2 parts of platinum catalyst, 10 parts of toluene, 76 parts of ethyl acetate and 2 parts of cross-linking agent polyisocyanate on the prepared release film base film, wherein the use concentration of the release agent is 5 percent, and the coating dry weight is 1g/m²And controlling the drying temperature to be 100 ℃ to dry the release film.

Example 2

The rest was the same as in example 1, except that the double bond-containing quaternary ammonium salt was replaced with 12.5 parts of dimethylallylammonium chloride, 2.5 parts of dimethyldipropylammonium chloride during the preparation of the modified HDPE.

Example 3

The rest is the same as in example 1, except that the double bond-containing quaternary ammonium salt was replaced with 14.06 parts of dimethylallylammonium chloride, 0.94 part of dimethyldipropylammonium chloride during the preparation of the modified HDPE.

Example 4

The rest was the same as in example 1, except that the double bond-containing quaternary ammonium salt was replaced with 13.24 parts of dimethylallylammonium chloride and 1.76 parts of dimethyldipropylammonium chloride in the preparation of the modified HDPE.

Example 5

The rest was the same as in example 1, except that the double bond-containing quaternary ammonium salt was replaced with 10 parts of dimethylallylammonium chloride and 5 parts of dimethyldipropylammonium chloride in the preparation of the modified HDPE.

Example 6

The procedure was as in example 1 except that the double bond-containing quaternary ammonium salt was replaced with 14.12 parts of dimethylallylammonium chloride and 0.88 part of dimethyldipropylammonium chloride in the preparation of the modified HDPE.

Example 7

The procedure was as in example 1 except that the double bond-containing quaternary ammonium salt was replaced with 9.09 parts of dimethylallylammonium chloride and 0.91 part of dimethyldipropylammonium chloride in the preparation of the modified HDPE.

Example 8

The rest is the same as in example 1, except that the double bond-containing quaternary ammonium salt was replaced with 8.33 parts of dimethylallylammonium chloride, 1.67 parts of dimethyldipropylammonium chloride during the preparation of the modified HDPE.

Example 9

The procedure was as in example 1 except that the modified HDPE was prepared with Al and Ti (in molar ratio) of 150.

Example 10

The procedure was as in example 1 except that the modified HDPE was prepared with Al and Ti (molar ratio) of 120.

Example 11

The procedure was as in example 1 except that the modified HDPE was prepared using Al to Ti (molar ratio) of 210.

Example 12

The rest is the same as example 1, except that the mixed recycle diluent during the preparation of the modified HDPE consists of 166.67 parts of n-hexane and 33.33 parts of ethyl acetate.

Example 13

The rest is the same as example 1, except that the mixed recycle diluent during the preparation of the modified HDPE consists of 180 parts n-hexane and 20 parts ethyl acetate.

Example 14

The rest is the same as example 1, except that the mixed recycle diluent during the preparation of the modified HDPE consists of 184.62 parts n-hexane and 15.38 parts ethyl acetate.

Comparative example 1

The rest is the same as example 1 except that the double bond-containing quaternary ammonium salt used in the preparation of the modified HDPE is 15 parts of dimethylallylammonium chloride.

Comparative example 2

The rest is the same as example 1, except that the double bond-containing quaternary ammonium salt used in the preparation of the modified HDPE is 15 parts of dimethyldipropylammonium chloride.

Comparative example 3

1) Adding a main catalyst into the kettle-type reactor subjected to nitrogen replacement to obtain supported TiCl₄/MgCl₂The cocatalyst is triethyl aluminum, and the concentration of Ti is 2 × 10^-5mol/L, Al and Ti (molar ratio) 180;

2) adding 80 parts of dried ethylene, 1 part of dried propylene, 1 part of dried 1-butene and 15 parts of dried stearyl trimethyl ammonium chloride serving as an antistatic agent and a mixed circulating diluent consisting of 181.82 parts of normal hexane and 18.18 parts of ethyl acetate into a kettle type reactor, introducing hydrogen, heating to 90 ℃, and carrying out total pressure of 1.8MPa and hydrogen partial pressure of 2%;

Application example

The release films prepared in the above examples and comparative examples were subjected to the following performance tests, and the results are shown in table 1.

Tensile property: the tests were carried out with reference to the standard GB/T13022-1991.

Antistatic performance: the test was performed with reference to the standard GB/T1410-2006.

High temperature and high humidity test: and (3) storing the alloy in a constant temperature and humidity box at 50 +/-2 ℃ and RH 80 +/-3% for 48h, testing the antistatic performance again, and calculating to obtain the surface resistance retention rate after high temperature and high humidity.

Release force: the 180 ° peel force test (peel speed 300mm/min) was performed with reference to the TESA7475 test (based on the typical peel force test methods of FINAT 10and FINAT 11).

TABLE 1

The essential type anti-static release film base membrane is prepared by doping polymerizable quaternary ammonium salt in a high-density polyethylene polymerization monomer, wherein the quaternary ammonium salt is an excellent cationic antistatic agent and is uniformly dispersed in resin to form a passage for leaking static charges, and groups with the anti-static function cannot migrate and be adhered away, so that the lasting anti-static function is exerted.

According to the invention, a small amount of quaternary ammonium salt monomer containing two carbon-carbon double bonds, such as dimethyl diallyl ammonium chloride, is added into the comonomer of the modified HDPE to generate a certain amount of branched and/or crosslinked high molecular structure, so that the antistatic performance of the modified HDPE is further improved, the unexpected discovery that the quaternary ammonium salt monomer containing two carbon-carbon double bonds has the function of improving the antistatic performance of the release film in a high-temperature and high-humidity environment is realized, the service life and the stability of the release film in high-humidity and high-temperature conditions are improved, the release film is particularly suitable for being used in southern areas with humidity in summer, and the damage to the antistatic performance caused by high-temperature and high-humidity work or a processing environment is effectively prevented.

The anti-static isolating membrane prepared by the invention has the advantages that; good and stable release force, the release force is between 5 and 10gf/inch, belongs to the category of light release force, and can be used for practical production.

The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.

Claims

1. The utility model provides an essence type is prevented static from type membrane base film, prevent static from type membrane base film material for modified HDPE, its characterized in that, modified HDPE is obtained through including following raw materials copolymerization: alkenyl compounds and double bond-containing quaternary ammonium salts.

2. The intrinsic antistatic release film base film according to claim 1, wherein the alkenyl compound is at least one selected from ethylene, propylene, butene, pentene and hexene, and the double-bond containing quaternary ammonium salt is a compound of a quaternary ammonium salt containing one carbon-carbon double bond and a quaternary ammonium salt containing two or more carbon-carbon double bonds.

3. The intrinsic antistatic release film-based film according to claim 2, wherein the quaternary ammonium salt having one carbon-carbon double bond is at least one selected from the group consisting of dimethyl allyl ammonium chloride, N-4-vinyl phenyl-N, N-dimethyl ammonium chloride; the quaternary ammonium salt containing two or more carbon-carbon double bonds is selected from at least one of dimethyl diallyl ammonium chloride and diallyl diethyl ammonium chloride.

4. The intrinsic antistatic release film base film according to claim 2, wherein the modified HDPE comprises the following raw materials in parts by weight: 80-90 parts of ethylene, 0.5-1.5 parts of propylene, 1-3 parts of 1-butene and 10-15 parts of double-bond quaternary ammonium salt, wherein the weight ratio of the quaternary ammonium salt containing one carbon-carbon double bond to the quaternary ammonium salt containing two or more carbon-carbon double bonds is 10-15: 1-2.

5. The intrinsic antistatic release film base film according to claim 1, wherein the modified HDPE is prepared by a slurry polymerization method, comprising the following steps:

6. The intrinsic antistatic release film-based film of claim 5, wherein the catalyst of step 1) is supported TiCl as main catalyst₄/MgCl₂The cocatalyst is triethyl aluminum, and the amount concentration of the main catalyst substance is 2 × 10 in terms of titanium^-5-2×10^-4mol/L, and the molar ratio of Al to Ti is 150-180.

7. The intrinsic antistatic release film-based film according to claim 5, wherein the mixed circulating diluent in the step 2) is a mixed solvent of n-hexane and ethyl acetate, and the volume ratio of the n-hexane to the ethyl acetate is 10: 1-2.

8. The intrinsic antistatic release film base film according to claim 3, wherein the dimethylallyl ammonium chloride is prepared from the following raw materials in parts by weight: 80 parts of N, N-dimethyl allylamine, 50-130 parts of a quaternizing agent and 0.08-0.4 part of a polymerization inhibitor p-hydroxyanisole, wherein the quaternizing agent comprises at least one of chloromethane and bromoethane.

9. Use of the basic film of the intrinsic antistatic release film according to any one of claims 1 to 8, wherein the release agent is coated on the basic film layer, and the obtained film is directly dried or cured to obtain the intrinsic antistatic release film.

10. Use of the intrinsic antistatic release film-based film as defined in claim 9Characterized in that the release agent comprises the following raw materials: 10 parts of vinyl end group organic silicon resin, 0.5-2 parts of platinum catalyst, 60-200 parts of organic solvent and 0.5-3 parts of cross-linking agent blocked polyisocyanate, wherein the use concentration of the release agent is 5-10%, and the coating dry weight is 0.3-1g/m²。