CN117603483A - Low-roughness high-surface-energy MLCC release film and preparation method thereof - Google Patents
Low-roughness high-surface-energy MLCC release film and preparation method thereof Download PDFInfo
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- -1 alkane polyol Chemical class 0.000 claims description 31
- 229920005862 polyol Polymers 0.000 claims description 22
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- 238000003756 stirring Methods 0.000 claims description 14
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 13
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- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 6
- 150000003377 silicon compounds Chemical class 0.000 claims description 6
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- 238000000034 method Methods 0.000 claims description 2
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- 230000001476 alcoholic effect Effects 0.000 claims 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000012973 diazabicyclooctane Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- 230000007480 spreading Effects 0.000 description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000003985 ceramic capacitor Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 3
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- 229920002799 BoPET Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
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- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2461/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2461/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a low-roughness high-surface-energy MLCC release film and a preparation method thereof, wherein the release film comprises a substrate layer, an undercoat layer and a release layer which are sequentially laminated, the undercoat layer is obtained by coating aqueous modified polyurethane coating liquid on the substrate layer and then drying, and the preparation raw materials of the aqueous modified polyurethane coating liquid comprise the following components in parts by weight: 100 parts of water-based polyester resin, 2-5 parts of a first curing agent, 0.5-3 parts of a first catalyst, 0.5-2 parts of a leveling agent, 800-1000 parts of deionized water and 50-600 parts of an alcohol solvent. The release film has excellent roughness level and high smoothness, has excellent surface energy compared with a silicone oil system, is beneficial to the casting of a thin layer of a raw ceramic chip, and can avoid the risk of uneven casting of the raw ceramic chip as much as possible; the release film has better residual capacity, low transfer rate and controllable release force in a certain interval.
Description
Technical Field
The invention relates to the field of release film materials, in particular to a low-roughness high-surface-energy MLCC release film and a preparation method thereof.
Background
Release films, also known as release films, barrier films, separation films. In order to increase the release force of the plastic film, the plastic film is usually subjected to corona treatment, fluorine-coated treatment, or silicon-coated release agent on the surface layer of the film material, such as PET, PE, OPP; so that the adhesive can show extremely light and stable release force for various different organic pressure sensitive adhesives. The clay layer used by the laminated ceramic capacitor (MLCC) is formed by uniformly coating liquid clay (namely ceramic slurry) on the surface of a release film, and stably spreading the liquid clay (namely ceramic slurry) on the surface of the release film through high temperature, drying and shaping. The release surface must have good roughness and excellent slurry adaptation performance, and achieve the effect of easy peeling.
With the rapid development of the world electronic industry, the MLCC is taken as a basic element of the electronic industry, and the rapid development is brought forward, and the application range is increased
The wider the application, the application in various military and civil electronic equipment such as computers, mobile phones, precise electronic instruments, radar communication and the like is widely performed. The performance of MLCCs is also being pursued more and more, and in the case of ceramic green sheets, as ceramic capacitors become smaller and have greater capacity, layers become thinner and thinner, which has led to lower roughness requirements, highly smooth surface appearance, and higher surface energy requirements for release films as carriers.
In the manufacturing process of the multilayer ceramic capacitor, the ceramic slurry needs to be subjected to casting coating, and the casting coating process needs to use a special MLCC release film material (commonly called as casting carrier film) with excellent performance. The MLCC release film has the advantages of high flatness, low roughness, low transfer rate, strong slurry suitability, good slurry spreading effect and the like. At present, the domestic low-roughness MLCC release film mainly depends on import. In the case of ceramic green sheets, as ceramic capacitors become smaller and have larger capacity, layers become thinner and thinner, and domestic manufacturing cannot provide a stable MLCC casting carrier film with corresponding properties, resulting in failure to obtain a high quality level of the thinned thickness uniformity of the ceramic film green sheets. Severely limiting the localization of high quality miniaturized MLCCs.
In addition, the MLCC ceramic slurry is often produced from various additives such as magnetic powder (nano-sized barium titanate, titanium oxide, magnesium titanate, etc.), a mixed solvent (a series of solvents such as toluene, ethanol, water, etc.), a dispersant, a leveling agent, etc. The uniformity of the surface tension of the slurry is poor due to the difference in the surface tension of the various materials. In general, the silicon-based release film has relatively small surface tension (a water drop angle of about 110 °) and is hydrophobic. When the high-quality miniaturized MLCC ceramic film is coated and loaded, the slurry cannot be well distributed, so that the problems of shrinkage cavity, pits, uneven thickness and the like of the surface production line of the release film can be solved, and a plurality of high-quality MLCCs cannot be produced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-roughness high-surface-energy MLCC release film and a preparation method thereof aiming at the defects in the prior art. The invention provides a low-roughness high-surface-energy MLCC functional release film which can be used for casting small-configuration thin-layer ceramic slurry and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme: the utility model provides a low roughness, high surface energy MLCC release film, includes substrate layer, undercoat and the release layer that stacks gradually and sets up, the undercoat is through the aqueous modified polyurethane coating liquid of coating on the substrate layer, through drying, the preparation raw materials of aqueous modified polyurethane coating liquid includes according to parts by weight: 100 parts of water-based polyester resin, 2-5 parts of a first curing agent, 0.5-3 parts of a first catalyst, 0.5-2 parts of a leveling agent, 800-1000 parts of deionized water and 50-600 parts of an alcohol solvent.
Preferably, the molecular weight of the aqueous polyester resin is 7000 to 10000.
Preferably, the first catalyst is one or more of inorganic acid or organic acid, the leveling agent is aqueous polyurethane leveling agent, and the alcohol solvent is one or two of ethanol or isopropanol.
Preferably, the first curing agent is melamine resin, the first catalyst is p-toluenesulfonic acid, and the leveling agent is BYK333.
Preferably, the release layer is obtained by coating release coating liquid on a bottom coating and then drying, and the release coating liquid is prepared from the following raw materials in parts by weight: 100 parts of long-chain alkane polyol polymer, 2-10 parts of organic silicon compound, 5-10 parts of second curing agent, 1-3 parts of second catalyst, 350-700 parts of toluene solvent and 300-700 parts of ketone solvent.
Preferably, the multi-long chain alkane polyol polymer has a molecular weight of 70000 to 120000 and a viscosity of 20 to 100CPS.
Preferably, the second curing agent is one or more of methylated melamine resin curing agents, and the ketone solvent is one or more selected from methyl ethyl ketone, butanone and diethyl ketone.
Preferably, the multi-long chain alkane polyol polymer is an aliphatic hydrocarbon polyol polymer SY770; the organosilicon compound is polyether modified hydroxyl-containing polydimethylsiloxane; the second curing agent is hexamethylene diisocyanate based polyisocyanate; the second catalyst is dibutyl tin dilaurate, and the ketone solvent is methyl ethyl ketone
Preferably, the thickness of the primer layer is 150-300nm, and the thickness of the release layer is 100-450nm.
The invention also provides a preparation method of the low-roughness high-surface-energy MLCC release film, which comprises the following steps:
s1, mixing 100 parts by weight of aqueous polyester resin, 2-5 parts by weight of a first curing agent, 0.5-3 parts by weight of a first catalyst, 0.5-2 parts by weight of a leveling agent, 800-1000 parts by weight of deionized water and 50-600 parts by weight of an alcohol solvent, and stirring at 500-700rpm for 0.5-2 hours to obtain aqueous modified polyurethane coating liquid;
s2, mixing 100 parts of long-chain alkane polyol polymer, 2-10 parts of organic silicon compound, 350-700 parts of toluene solvent and 300-700 parts of ketone solvent, stirring for 10-30min at 500-700rpm, then adding 5-10 parts of second curing agent and 1-3 parts of second catalyst, and stirring for 5-20min to obtain release coating liquid;
s3, uniformly coating the aqueous modified polyurethane coating liquid prepared in the step S1 on a substrate at 90 ℃ to the upper part
Drying at 120 ℃ for 30-90 s to obtain a bottom coating;
s4, uniformly coating the release coating liquid prepared in the step S2 on the bottom coating, and drying at 90-120 ℃ for 30-90S to obtain a release layer, thus obtaining the low-roughness high-surface-energy MLCC release film.
The beneficial effects of the invention are as follows:
the invention provides a low-roughness high-surface-energy MLCC release film and a preparation method thereof, wherein the release film has excellent roughness level and high smoothness, has excellent surface energy compared with a silicone oil system, is beneficial to casting of a thin layer of a raw ceramic chip, and can avoid the risk of uneven casting of the raw ceramic chip as far as possible; the release film has better residual capacity, low transfer rate and controllable release force in a certain interval;
according to the invention, the surface of the PET base film is coated with the aqueous polyurethane primer solution, so that an excellent adhesion effect is given to the release layer, the release layer and the bottom coating are combined more firmly, and the transfer of the release layer is reduced; secondly, the primer layer can reduce precipitation of small molecules on the surface of the PET, reduce precipitation of small molecules of the PET film in the high-temperature baking process, and improve the flatness of the base film; the excellent leveling agent is added into the primer, so that the leveling effect of the bottom layer is optimal, and the roughness of the substrate layer is improved to the greatest extent; the long-chain alkane polyol polymer and the modified organosilicon compound are introduced into the release layer, the selected aqueous polyurethane primer is mainly produced by directly connecting polyester polyol, the trace amount of long-chain polyester polyol in the primer layer is similar to the polarity of the release layer, the long-chain alkane polyol in the release layer forms a certain chemical bond with carbon-oxygen double bonds and isocyanic acid radicals in the polyurethane primer layer, the adhesive force between the two is greatly improved, the release layer spreads better on the primer layer surface due to the similar polarity of the release layer and the primer layer, the release film is smoother and smoother, the release force is improved to a certain extent by introducing the modified organosilicon compound into the release layer formula, and the release layer has the application of adapting to various ceramic film formulas by introducing the modified organosilicon compound; under the condition of introducing the modified organosilicon compound, the modified organosilicon compound not only has good stripping performance, but also has more excellent stripping performance compared with a non-silicon release film of long-chain alkane, and simultaneously has higher surface tension compared with a traditional organosilicon release film, thereby being beneficial to the coating and spreading of a thin ceramic film.
According to the invention, the base coat is arranged on the base material, so that the roughness level of the base material layer is improved to a certain extent, then the release layer is coated on the base coat, the polarity of the base coat is similar to that of the release layer (the aqueous polyurethane of the base coat is synthesized by oligomer dihydric alcohol or polyhydric alcohol, and long-chain alkane polyhydric alcohol is introduced into the release layer, and the polarities of the base coat and the release layer are similar), and the release layer and isocyanato and carbon-oxygen double bonds in the base coat form a certain chemical bond, so that the release layer has better adhesive force, a more excellent film surface leveling and covering effect can be obtained, and the defect of the base film can be compensated; under the condition that the polarities of the release layers are similar, the release layers have better leveling property, so that better roughness improvement is performed on the base coat; compared with a conventional organic silicon release film, the release layer has better film surface tension and lower film surface roughness, and is favorable for coating and spreading of a thin ceramic film.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a low-roughness high-surface-energy MLCC release film, which comprises a substrate layer, a bottom coating and a release layer which are sequentially laminated.
The base coat is obtained by coating aqueous modified polyurethane coating liquid on a substrate layer and then drying, and the preparation raw materials of the aqueous modified polyurethane coating liquid comprise the following components in parts by weight: 100 parts of water-based polyester resin, 2-5 parts of a first curing agent, 0.5-3 parts of a first catalyst, 0.5-2 parts of a leveling agent, 800-1000 parts of deionized water and 50-600 parts of an alcohol solvent.
In a preferred embodiment, the aqueous polyester resin has a molecular weight of 7000 to 10000 and a solids content of 35% to 45%.
In a preferred embodiment, the first curative is a melamine resin.
In a preferred embodiment, the first catalyst is one or more of an inorganic acid or an organic acid, more preferably p-toluene sulfonic acid.
The leveling agent is aqueous polyurethane leveling agent, more preferably BYK333
The alcohol solvent is one or two of ethanol and isopropanol, more preferably isopropanol.
In the invention, the release layer is obtained by coating release coating liquid on a bottom coating and then drying, and the preparation raw materials of the release coating liquid comprise the following components in parts by weight: 100 parts of long-chain alkane polyol polymer, 2-10 parts of organic silicon compound, 5-10 parts of second curing agent, 1-3 parts of second catalyst, 350-700 parts of toluene solvent and 300-700 parts of ketone solvent.
In a preferred embodiment, the poly-long chain alkane polyol polymer has a molecular weight of 70000 to 120000, a viscosity of 20 to 100CPS, and a solids content of 23% to 27%.
In a preferred embodiment, the second curative is one or more of a methylated melamine resin based curative.
In a preferred embodiment, the ketone solvent is one or more selected from methyl ethyl ketone, butanone and diethyl ketone.
In a preferred embodiment, the multi-long chain alkane polyol polymer is an aliphatic hydrocarbon polyol polymer SY770; the organosilicon compound is polyether modified hydroxyl-containing polydimethylsiloxane; the second curing agent is hexamethylene diisocyanate based polyisocyanate; the second catalyst is dibutyl tin dilaurate, and the ketone solvent is methyl ethyl ketone
In a preferred embodiment, the primer layer has a thickness of 150-300nm and the release layer has a thickness of 100-450nm.
In a preferred embodiment, the substrate layer is a high flatness PET base film (roughness Ra23-30nm Rz800nm-1200 nm) with a thickness of 23-38 μm.
The invention also provides a preparation method of the low-roughness high-surface-energy MLCC release film, which comprises the following steps:
s1, mixing 100 parts by weight of aqueous polyester resin, 2-5 parts by weight of a first curing agent, 0.5-3 parts by weight of a first catalyst, 0.5-2 parts by weight of a leveling agent, 800-1000 parts by weight of deionized water and 50-600 parts by weight of an alcohol solvent, and stirring at 500-700rpm for 0.5-2 hours to obtain aqueous modified polyurethane coating liquid;
s2, mixing 100 parts of long-chain alkane polyol polymer, 2-10 parts of organic silicon compound, 350-700 parts of toluene solvent and 300-700 parts of ketone solvent, stirring for 10-30min at 500-700rpm, then adding 5-10 parts of second curing agent and 1-3 parts of second catalyst, and stirring for 5-20min to obtain release coating liquid;
s3, uniformly coating the aqueous modified polyurethane coating liquid prepared in the step S1 on a substrate at 90 ℃ to the upper part
Drying at 120 ℃ for 30-90 s to obtain a bottom coating;
s4, uniformly coating the release coating liquid prepared in the step S2 on the bottom coating, and drying at 90-120 ℃ for 30-90S to obtain a release layer, thus obtaining the low-roughness high-surface-energy MLCC release film.
In the coating operation, a coating workshop is a thousand-level dust-free workshop, the workshop is required to be at a constant temperature of 23+/-3 ℃, and a coating head is required to be at a constant temperature of 23+/-3 ℃ and constant humidity of 55+/-5%.
The foregoing is a general inventive concept and the following detailed examples and comparative examples are provided on the basis thereof to further illustrate the invention.
Example 1
S1, mixing 100 parts by weight of aqueous polyester resin (HYDRAN VR-001 DIC), 2 parts by weight of melamine resin (AMIDIR PM-80DIC Co., ltd.), 1 part by weight of PTS (Guangdong Weng Jiang p-toluenesulfonate chemical reagent Co., ltd.), 0.5 part by weight of aqueous leveling agent (BYK 333 Pick chemical), 1000 parts by weight of deionized water and 50 parts by weight of isopropanol solvent, and stirring at 600rpm for 1 hour to obtain aqueous modified polyurethane coating liquid;
the aqueous modified polyurethane coating liquid was uniformly coated on a PET substrate (thickness: 30 μm) using a wire bar, and dried at 110℃for 60 seconds, to form a 150nm thick undercoat layer on the PET substrate, to obtain a semi-finished product 1.
Example 2
S1, mixing 100 parts by weight of aqueous polyester resin (HYDRAN VR-001 DIC), 5 parts by weight of melamine resin (AMIDIR PM-80DIC Co., ltd.), 1 part by weight of PTS (Guangdong Weng Jiang p-toluenesulfonate chemical reagent Co., ltd.), 1 part by weight of aqueous leveling agent (BYK 333 Pick chemical), 900 parts by weight of deionized water and 540 parts by weight of isopropanol solvent, and stirring at 600rpm for 1 hour to obtain aqueous modified polyurethane coating liquid;
the aqueous modified polyurethane coating liquid was uniformly coated on a PET substrate (thickness: 30 μm) using a wire bar, and dried at 110℃for 60 seconds, to form a 200nm thick undercoat layer on the PET substrate, to obtain a semi-finished product 2.
Example 3
S1, mixing 100 parts by weight of aqueous polyester resin (HYDRAN VR-001 DIC), 3 parts by weight of melamine resin (AMIDIR PM-80DIC Co., ltd.), 2 parts by weight of PTS (Guangdong Weng Jiang p-toluenesulfonate chemical reagent Co., ltd.), 1 part by weight of aqueous leveling agent (BYK 333 Pick chemical), 800 parts by weight of deionized water and 525 parts by weight of isopropanol solvent, and stirring at 600rpm for 1 hour to obtain aqueous modified polyurethane coating liquid;
the aqueous modified polyurethane coating liquid was uniformly coated on a PET substrate (thickness: 30 μm) using a wire bar, and dried at 110℃for 60 seconds, to form a 300nm thick undercoat layer on the PET substrate, to obtain a semi-finished product 3.
The semi-finished products obtained in examples 1-3 and the base film comparative example were subjected to roughness performance test using a 3D microscope tester, and the test results are shown in table 1 below:
TABLE 1
From the test results of Table 2, it can be seen that by applying the undercoat layer on the substrate layer, the roughness was significantly improved, the roughness Rz value was decreased from 1000nm to 470nm, and the roughness Rp value was decreased from 600nm to 400nm. Under the test of a 3D microscope, the semi-finished product film surface is smoother and smoother, and the roughness test value is obviously reduced.
Example 4
100 parts of aliphatic hydrocarbon polyol polymer solution (SY 770 Shanghai brand chemical Co., ltd.), 2 parts of polyether modified hydroxyl-containing polydimethylsiloxane (BYK-377 Pick chemical), 700 parts of toluene solvent and 700 parts of methyl ethyl ketone solvent are mixed according to parts by weight, stirred at 600rpm for 15min, then 5 parts of hexamethylene diisocyanate-based polyisocyanate (HT 100 Wanhua chemical) and 1 part of dibutyltin dilaurate (DABCO T-12 Herry) are added, and stirred for 10min to obtain release coating liquid;
and uniformly coating the release coating liquid on the bottom coating of the semi-finished product 3 prepared in the embodiment 3 by using a wire rod, drying at 110 ℃ for 100 seconds, and forming a release layer with the thickness of 100nm on the bottom coating to obtain a release film finished product.
Example 5
100 parts of aliphatic hydrocarbon polyol polymer solution (SY 770 Shanghai brand chemical Co., ltd.), 5 parts of polyether modified hydroxyl-containing polydimethylsiloxane (BYK-377 Pick chemical), 500 parts of toluene solvent and 600 parts of methyl ethyl ketone solvent are mixed according to parts by weight, stirred for 15min at 600rpm, 7 parts of hexamethylene diisocyanate-based polyisocyanate (HT 100 Wanhua chemical) and 2 parts of dibutyltin dilaurate (DABCO T-12 Herry) are added, and stirred for 10min to obtain release coating liquid;
and uniformly coating the release coating liquid on the bottom coating of the semi-finished product 3 prepared in the embodiment 3 by using a wire rod, drying at 110 ℃ for 100s, and forming a release layer with the thickness of 200nm on the bottom coating to obtain a release film finished product.
Example 6
100 parts of aliphatic hydrocarbon polyol polymer solution (SY 770 Shanghai brand chemical Co., ltd.), 7 parts of polyether modified hydroxyl-containing polydimethylsiloxane (BYK-377 Pick chemical), 400 parts of toluene solvent and 450 parts of methyl ethyl ketone solvent are mixed according to parts by weight, stirred at 600rpm for 15min, 8 parts of hexamethylene diisocyanate-based polyisocyanate (HT 100 Wanhua chemical) and 2.5 parts of dibutyltin dilaurate (DABCO T-12 Herry) are added, and stirred for 10min to obtain a release coating solution;
and uniformly coating the release coating liquid on the bottom coating of the semi-finished product 3 prepared in the embodiment 3 by using a wire rod, drying at 110 ℃ for 100s, and forming a release layer with the thickness of 300nm on the bottom coating to obtain a release film finished product.
Example 7
100 parts of aliphatic hydrocarbon polyol polymer solution (SY 770 Shanghai brand chemical Co., ltd.), 10 parts of polyether modified hydroxyl-containing polydimethylsiloxane (BYK-377 Pick chemical), 450 parts of toluene solvent and 500 parts of methyl ethyl ketone solvent are mixed according to parts by weight, stirred at 600rpm for 15min, 10 parts of hexamethylene diisocyanate-based polyisocyanate (HT 100 Wanhua chemical) and 3 parts of dibutyltin dilaurate (DABCO T-12 Herry) are added, and stirred for 10min to obtain release coating liquid;
and uniformly coating the release coating liquid on the bottom coating of the semi-finished product 3 prepared in the embodiment 3 by using a wire rod, drying at 110 ℃ for 100s, and forming a release layer with the thickness of 400nm on the bottom coating to obtain a release film finished product.
Comparative example 1
100 parts of aliphatic hydrocarbon polyol polymer solution (SY 770 Shanghai brand chemical Co., ltd.), 2 parts of polyether modified hydroxyl-containing polydimethylsiloxane (BYK-377 Pick chemical), 450 parts of toluene solvent and 500 parts of methyl ethyl ketone solvent are mixed according to parts by weight, stirred for 15min at 600rpm, 10 parts of hexamethylene diisocyanate-based polyisocyanate (HT 100 Wanhua chemical) and 3 parts of dibutyltin dilaurate (DABCO T-12 Herry) are added, and stirred for 10min to obtain release coating liquid;
and uniformly coating the release coating liquid on the bottom coating of the semi-finished product 3 prepared in the embodiment 3 by using a wire rod, drying at 110 ℃ for 100s, and forming a release layer with the thickness of 400nm on the bottom coating to obtain a release film finished product.
Comparative example 2
Adding 100 parts by weight of vinyl-terminated silicone oil (LTC 310 DOW), 400 parts by weight of toluene solution and 1200 parts by weight of methyl ethyl ketone solution into a reaction kettle, stirring for 15min at 600rpm, and then adding 0.5 part by weight of methyl hydrogen-containing silicone oil (SYL 7028 DOW), 0.5 part by weight of adhesion additive (SYL 297 DOW) and 3 parts by weight of organic platinum compound (SYL 4000 DOW), and stirring for 20min to obtain a release coating liquid (traditional formula);
and uniformly coating the release coating liquid on the bottom coating of the semi-finished product 3 prepared in the embodiment 3 by using a wire rod, drying at 110 ℃ for 100s, and forming a release layer with the thickness of 400nm on the bottom coating to obtain a release film finished product.
The semi-finished products prepared in example 3, release films prepared in examples 4 to 7 and comparative examples 1 to 2 were subjected to performance tests, and the test results are shown in table 2 below:
TABLE 2
Note that: the roughness test equipment is a 3D microscope tester.
As can be seen from the test results in Table 2, the addition of the release layer on the primer layer further reduces the roughness of the finished release film, the Rz value is reduced from 450nm to about 300nm, and the Rp value is reduced from 400nm to about 200 nm; as can be seen from comparison of example 7 and comparative example 1, compared with the release layer directly coated with the same thickness, the release layer is coated on the bottom coating, the residual adhesive force of the whole finished product is higher, the release force is also lower, the roughness level of the film surface is better, and the film surface is smoother; as can be seen from example 7 and comparative example 1, the residual adhesion of the present invention is lower, the coating transfer rate, relative to the silicone oil release film; the water drop angle test value is lower, and the surface energy of the film mask is higher; when the release layer spreads on the same base coat, the spreading effect of the invention is better, the roughness of the film surface is better and the test value is smaller under the condition that the roughness is presented by a 3D microscope; by the introduction of the organosilicon compound, by example 4/5/6/7 and comparative example 1/2, different release force values are presented relative to the initial non-silicon release layer and the organosilicon release layer, the release force values being adjustable;
although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (10)
1. The MLCC release film with low roughness and high surface energy is characterized by comprising a substrate layer, an undercoat layer and a release layer which are sequentially laminated, wherein the undercoat layer is obtained by coating aqueous modified polyurethane coating liquid on the substrate layer and then drying, and the preparation raw materials of the aqueous modified polyurethane coating liquid comprise the following components in parts by weight: 100 parts of water-based polyester resin, 2-5 parts of a first curing agent, 0.5-3 parts of a first catalyst, 0.5-2 parts of a leveling agent, 800-1000 parts of deionized water and 50-600 parts of an alcohol solvent.
2. The low roughness, high surface energy MLCC release film of claim 1, wherein said aqueous polyester resin has a molecular weight of 7000-10000.
3. The low roughness, high surface energy MLCC release film of claim 1, wherein said first catalyst is one or more of an inorganic acid or an organic acid, said leveling agent is an aqueous polyurethane leveling agent, and said alcoholic solvent is one or both of ethanol or isopropanol.
4. The low roughness, high surface energy MLCC release film of claim 3, wherein said first curing agent is melamine resin, said first catalyst is p-toluene sulfonic acid, and said leveling agent is BYK333.
5. The low-roughness high-surface-energy MLCC release film of claim 1, wherein the release layer is obtained by coating a release coating liquid on a bottom coating layer and then drying, and the release coating liquid is prepared from the following raw materials in parts by weight: 100 parts of long-chain alkane polyol polymer, 2-10 parts of organic silicon compound, 5-10 parts of second curing agent, 1-3 parts of second catalyst, 350-700 parts of toluene solvent and 300-700 parts of ketone solvent.
6. The low roughness, high surface energy MLCC release film of claim 5, wherein said poly long chain alkane polyol polymer has a molecular weight of 70000-120000 and a viscosity of 20-100CPS.
7. The low roughness, high surface energy MLCC release film of claim 5, wherein said second curing agent is one or more of methylated melamine resin based curing agents and said ketone based solvent is one or more selected from methyl ethyl ketone, butanone and diethyl ketone.
8. The low roughness, high surface energy MLCC release film of claim 5, wherein said multi-long chain alkane polyol polymer is an aliphatic hydrocarbon polyol polymer SY770; the organosilicon compound is polyether modified hydroxyl-containing polydimethylsiloxane; the second curing agent is hexamethylene diisocyanate based polyisocyanate; the second catalyst is dibutyl tin dilaurate, and the ketone solvent is methyl ethyl ketone.
9. The low roughness, high surface energy MLCC release film of claim 1, wherein said primer layer has a thickness of 150-300nm and said release layer has a thickness of 100-450nm.
10. A method for preparing the low-roughness, high-surface-energy MLCC release film according to any one of claims 1-9, comprising the steps of:
s1, mixing 100 parts by weight of aqueous polyester resin, 2-5 parts by weight of a first curing agent, 0.5-3 parts by weight of a first catalyst, 0.5-2 parts by weight of a leveling agent, 800-1000 parts by weight of deionized water and 50-600 parts by weight of an alcohol solvent, and stirring at 500-700rpm for 0.5-2 hours to obtain aqueous modified polyurethane coating liquid;
s2, mixing 100 parts of long-chain alkane polyol polymer, 2-10 parts of organic silicon compound, 350-700 parts of toluene solvent and 300-700 parts of ketone solvent, stirring for 10-30min at 500-700rpm, then adding 5-10 parts of second curing agent and 1-3 parts of second catalyst, and stirring for 5-20min to obtain release coating liquid;
s3, uniformly coating the aqueous modified polyurethane coating liquid prepared in the step S1 on a substrate, and drying at 90-120 ℃ for 30-90S to obtain a bottom coating;
s4, uniformly coating the release coating liquid prepared in the step S2 on the bottom coating, and drying at 90-120 ℃ for 30-90S to obtain a release layer, thus obtaining the low-roughness high-surface-energy MLCC release film.
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