CN113652163A - Isocyanate-resistant release coating formula, release paper thereof, and manufacturing method and application of release paper - Google Patents
Isocyanate-resistant release coating formula, release paper thereof, and manufacturing method and application of release paper Download PDFInfo
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- CN113652163A CN113652163A CN202110725778.9A CN202110725778A CN113652163A CN 113652163 A CN113652163 A CN 113652163A CN 202110725778 A CN202110725778 A CN 202110725778A CN 113652163 A CN113652163 A CN 113652163A
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- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/66—Coatings characterised by a special visual effect, e.g. patterned, textured
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention relates to the technical field of release paper, in particular to a formula of an isocyanate-resistant release coating, release paper, a manufacturing method and application thereof. The formula of the isocyanate-resistant release coating comprises the following components in parts by mass: 15-30 parts of modified polyurethane acrylate, 55-80 parts of acrylate monomer, 1-10 parts of organic silicon resin and 1-5 parts of fumed silica, wherein the total parts of all the components are 100 parts. The invention provides a formula of an isocyanate-resistant release coating, release paper with good comprehensive performance in the aspects of hardness, solvent resistance and release stability, and a corresponding manufacturing method and application.
Description
Technical Field
The invention relates to the technical field of release paper, in particular to a formula of an isocyanate-resistant release coating, release paper, a manufacturing method and application thereof.
Background
In the production of artificial synthetic leather, the dry process (also called transfer coating) is to coat the coating agent (polyurethane or PVC) on the base paper, form a continuous and uniform film after drying, then coat the film with adhesive and laminate with fabric (or wet-process bottom leather), then dry and peel the base paper from the leather, the coating agent (including adhesive layer) film will be transferred from the base paper to the fabric (or leather). The artificial synthetic leather is mainly polyurethane synthetic leather (PU leather) and polyvinyl chloride artificial leather (PVC leather).
Due to market demand and the advance of new chemical fiber fabric technologies, the variety of fabrics (or leathers) used in the process of manufacturing artificial synthetic leather has recently emerged. This makes the artificial synthetic leather products continuously updated and new technical problems and challenges are encountered. The main problem is that because of the adoption of new chemical fiber fabric, the original adhesive has poor adhesion effect on new chemical fiber materials, and therefore, a new chemical adhesive is adopted, which is generally called as a bi-component adhesive, and the main chemical composition of the bi-component adhesive is isocyanate substances. The adhesive can generate chemical reaction at high temperature and has strong material infiltration capacity, so the adhesive effect is very obvious. Because the adhesive acts between the release coating and the fabric, the adhesive can permeate the release coating, so that the base paper cannot be normally separated from the fabric (or leather). Therefore, there is a need for an improvement in release coating formulations to allow for proper separation of the base paper from the fabric.
Disclosure of Invention
One of the purposes of the invention is to provide a release coating formula resistant to isocyanate.
The second purpose of the invention is to provide release paper with the above release coating formula, which has good comprehensive performance in the aspects of hardness, solvent resistance and release stability.
The invention also aims to provide a method for manufacturing the release paper.
The fourth purpose of the invention is to provide the artificial synthetic leather manufactured by adopting the release paper.
In order to achieve the purpose, the invention adopts the following technical scheme:
the formula of the isocyanate-resistant release coating comprises the following components in parts by mass: 15-30 parts of modified polyurethane acrylate, 55-80 parts of acrylate monomer, 1-10 parts of organic silicon resin and 1-5 parts of fumed silica, wherein the total parts of all the components are 100 parts.
Preferably, the modified polyurethane acrylate is prepared by polymerizing isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and tripolymer thereof serving as raw materials with monomer raw materials of hydroxyethyl acrylate and/or hydroxyethyl methacrylate and/or pentaerythritol triacrylate and/or acrylic polycaprolactone; the acrylate functionality is from 2 to 10.
Preferably, the acrylate monomer is one or more of isobornyl acrylate (IBOA), isooctyl acrylate (EHA), Laurate Acrylate (LA), 1, 6 hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), dipropoxypentylglycol diacrylate (2PO-NPGDA), trimethylolpropane triacrylate (TMPTA), triethoxytrimethylolpropane triacrylate (3EO-TMPTA), pentaerythritol triacrylate (PETA), glycidyl ether acrylate (GPTA), and dipentaerythritol hexaacrylate (DPHA).
Preferably, the silicone resin is one or more of an acrylated product of silicone oil, an epoxy-modified silicone resin, an ammonia-modified silicone resin, a polyurethane-modified silicone resin, a fatty acid-modified silicone resin, a silicone rubber resin, and silicone oil.
The invention further provides release paper, which comprises base paper and a release coating, wherein the release coating is formed by curing the release coating formula.
Preferably, the release coating is a 100% solids coating layer. The release paper in the technical scheme has the characteristics of high production efficiency, low transportation cost and low energy consumption.
Preferably, the release coating comprises the following components in percentage by weight: 5% of isophorone diisocyanate-based difunctional urethane acrylate, 10% of isophorone diisocyanate-based trifunctional urethane acrylate, 15% of isophorone diisocyanate-based hexafunctional urethane acrylate, 10% of acrylate monomer (TPGDA), 20% of acrylate monomer (TMPTA), 30% of acrylate monomer (DPHA), 5% of silicone oil acrylated product, 3% of polyurethane modified silicone resin and 2% of fumed silica.
Preferably, the surface of the release coating is formed with patterns. The artificial synthetic leather produced by the technical scheme has the effect of decorative patterns on the surface, is comfortable in touch and has more attractive appearance.
The invention also provides a method for manufacturing the release paper, which comprises the steps of coating excessive release coating formula on raw paper by a feeding system, scraping redundant coating by a scraper, and pressing the raw paper with the bottom coating once into the release paper with the pattern under the traction of a guide roller, passing through the surface of an embossing roller and under the electron beam irradiation of an electron beam irradiation chamber. The technical scheme has the advantages of simplified process steps, simple operation, short curing time and low curing temperature.
The invention also provides application of the release paper in artificial synthetic leather.
According to the invention, a release coating formula consisting of multifunctional polyurethane acrylate, an acrylate monomer, organic silicon resin and fumed silica is selected, and the multifunctional polyurethane acrylate in the new formula can provide higher crosslinking density for the release coating, so that the abnormal release paper stripping caused by the fact that isocyanate in a novel binder component is strongly permeated into the release coating at high temperature is effectively prevented; in addition, the water contact angle of the release coating and the contact surface of the binder can be increased by the selected organic silicon resin, so that the surface energy is reduced, the novel binder is difficult to adsorb, the contact area is reduced, and the effective stripping of the novel binder and the binder is realized.
According to the release paper adopting the formula of the release coating, various patterns are integrally pressed on the surface of the release paper through electron beam irradiation curing, so that the surface of the artificial synthetic leather has the effect of the patterns, and the aesthetic feeling and the added value of the artificial synthetic leather are improved.
Detailed Description
In order to make the technical features, objects and effects of the present invention more clearly understood, a detailed description of embodiments of the present invention will be given below with reference to the accompanying drawings.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Based on the application of the novel adhesive, in order to avoid the strong permeation effect of an isocyanate component at high temperature, a new formula consisting of 15-30 parts of modified polyurethane acrylate, 55-80 parts of acrylate monomer, 1-10 parts of organic silicon resin and 1-5 parts of fumed silica is selected, the total amount of the components is 100 parts, and the multifunctional polyurethane acrylate can provide higher crosslinking density for the release coating, so that the abnormal release paper peeling caused by the fact that the isocyanate in the novel adhesive component is strongly permeated into the release coating at high temperature is effectively prevented, and the water contact angle of the contact surface of the release coating and the adhesive can be increased through the selected organic silicon resin, so that the isocyanate and the adhesive can be effectively peeled.
In some specific embodiments, the modified polyurethane acrylate is prepared by polymerizing isophorone diisocyanate, hexamethylene diisocyanate, a trimer thereof and diphenylmethane diisocyanate serving as raw materials with monomer raw materials of hydroxyethyl acrylate and/or hydroxyethyl methacrylate and/or pentaerythritol triacrylate and/or polycaprolactone acrylate; the acrylate functionality is from 2 to 10.
In some preferred embodiments, the acrylate monomer is one or more of isobornyl acrylate (IBOA), isooctyl acrylate (EHA), Laurate Acrylate (LA), 1, 6 hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (2PO-NPGDA), trimethylolpropane triacrylate (TMPTA), triethoxytrimethylolpropane triacrylate (3EO-TMPTA), pentaerythritol triacrylate (PETA), glycidyl ether acrylate (GPTA), and pentaerythritol hexaacrylate (DPHA).
In some preferred embodiments, the silicone resin is one or more of an acrylated product of a silicone oil, an epoxy-modified silicone resin, an ammonia-modified silicone resin, a polyurethane-modified silicone resin, a fatty acid-modified silicone resin, a silicone rubber resin, and a silicone oil.
Example 1
Taking 20% of isophorone diisocyanate as raw material of trifunctional polyurethane acrylate, 10% of isophorone diisocyanate as raw material of difunctional polyurethane acrylate, 40% of acrylate monomer (TPGDA), 20% of acrylate monomer (TMPTA), 7% of silicone oil acrylated product and 3% of fumed silica in parts by mass, and putting the components into a container in sequence at room temperature for mixing and stirring to fully dissolve solid components, thereby obtaining uniform and nearly transparent coating.
Coating excessive coating on the surface of base paper by a feeding system, scraping the excessive coating by a scraper, pressing patterns on the surface of the base paper with the base coating by a guide roller, and curing the coating under the irradiation of electron beams of an electron beam irradiation chamber to form a release coating attached to the surface of the base paper, thereby preparing the release paper. Specifically, the irradiation energy of the electron beam is selected to be 0.5KGY, the release coating formed by one-time penetration and solidification of the lower electron beam energy has various haze and lines, and the artificial synthetic leather produced by applying the method has corresponding patterns on the surface, is comfortable in touch and has more attractive appearance. The artificial synthetic leather can be polyurethane synthetic leather (PU leather) or polyvinyl chloride synthetic leather (PVC leather).
In a preferred embodiment, the release coating is a 100% solid coating layer. Has the characteristics of high production efficiency, low transportation cost and low energy consumption.
Example 2
According to the mass parts, 15% of isophorone diisocyanate-based difunctional urethane acrylate, 5% of isophorone diisocyanate-based trifunctional urethane acrylate, 10% of isophorone diisocyanate-based hexafunctional urethane acrylate, 30% of acrylate monomer (TPGDA), 10% of acrylate monomer (TMPTA), 20% of acrylate monomer (DPHA), 7% of silicone oil acrylated product and 3% of fumed silica are taken, and the corresponding release paper is prepared by adopting the method in example 1.
Example 3
By mass parts, 10% of isophorone diisocyanate-based difunctional urethane acrylate, 10% of isophorone diisocyanate-based trifunctional urethane acrylate, 10% of isophorone diisocyanate-based hexafunctional urethane acrylate, 20% of acrylate monomer (TPGDA), 20% of acrylate monomer (TMPTA), 20% of acrylate monomer (DPHA), 3% of silicone oil acrylated product, 4% of polyurethane modified silicone resin, and 3% of fumed silica, were taken, and the corresponding release paper was prepared in the manner of example 1.
Example 4
According to the mass parts, 5% of isophorone diisocyanate-based difunctional urethane acrylate, 15% of isophorone diisocyanate-based trifunctional urethane acrylate, 10% of isophorone diisocyanate-based hexafunctional urethane acrylate, 10% of acrylate monomer (TPGDA), 20% of acrylate monomer (TMPTA), 30% of acrylate monomer (DPHA), 5% of silicone oil acrylated product, 3% of polyurethane modified silicone resin and 2% of fumed silica are taken, and the corresponding release paper is prepared by adopting the mode of example 1.
Example 5
According to the mass parts, the corresponding release paper is prepared by taking 10% of isophorone diisocyanate-based difunctional urethane acrylate, 5% of isophorone diisocyanate-based trifunctional urethane acrylate, 15% of isophorone diisocyanate-based hexafunctional urethane acrylate, 10% of acrylate monomer (TPGDA), 20% of acrylate monomer (TMPTA), 40% of acrylate monomer (DPHA), 6% of silicone oil acrylated product, 2% of polyurethane modified silicone resin and 2% of fumed silica, and adopting the mode of example 1.
Example 6
According to the mass parts, the corresponding release paper is prepared by taking 10% of isophorone diisocyanate-based difunctional urethane acrylate, 5% of isophorone diisocyanate-based trifunctional urethane acrylate, 15% of isophorone diisocyanate-based hexafunctional urethane acrylate, 10% of acrylate monomer (TPGDA), 20% of acrylate monomer (TMPTA), 30% of acrylate monomer (DPHA), 4% of silicone oil acrylated product, 4% of polyurethane modified silicone resin and 2% of fumed silica, and adopting the mode of example 1.
Example 7
By mass parts, 5% of isophorone diisocyanate-based difunctional urethane acrylate, 10% of isophorone diisocyanate-based trifunctional urethane acrylate, 15% of isophorone diisocyanate-based hexafunctional urethane acrylate, 10% of acrylate monomer (TPGDA), 20% of acrylate monomer (TMPTA), 30% of acrylate monomer (DPHA), 5% of silicone oil acrylated product, 3% of polyurethane modified silicone resin, and 2% of fumed silica were taken, and the corresponding release paper was prepared in the manner of example 1.
Example 8
According to the mass parts, 5% of isophorone diisocyanate-based difunctional urethane acrylate, 5% of isophorone diisocyanate-based trifunctional urethane acrylate, 20% of isophorone diisocyanate-based hexafunctional urethane acrylate, 10% of acrylate monomer (TPGDA), 10% of acrylate monomer (TMPTA), 40% of acrylate monomer (DPHA), 5% of silicone oil acrylated product, 3% of polyurethane modified silicone resin and 2% of fumed silica are taken, and the corresponding release paper is prepared by adopting the mode of example 1.
The release paper prepared in each of the above examples was subjected to a performance test in the following manner:
1. surface water contact angle: seat drop method (refer to ASTM D5946-2004)
2. Peel strength: the prepared coatings are coated on the base paper according to the thickness of 80 um. Baking at 140 deg.C for 1 min, coating adhesive with 10% isocyanate content on the surface of the coating at a thickness of 50um, baking at 150 deg.C for 30 s to 1 min, attaching a layer of base cloth on the surface, baking at 150 deg.C for 1 min, taking out, cutting into 50mm wide and 100mm long, and testing on a peel force tester (180 degree angle). The average value of ten samples in each time is qualified to be less than 15N/m.
3. Resistance to DMF: the test method comprises the following steps: several drops of DMF were dropped on the surface and left to evaporate completely. The coating surface was observed to be unchanged and free of cracks.
The inventors have experimentally obtained table 1 according to the above test method, and table 1 shows: the release paper produced by the new formula can be effectively peeled under the action of the novel adhesive, and the peeling strength of the release paper meets the industrial standard within 15N/m. The release paper test data prepared by a plurality of polyurethane acrylate formulas with different functionalities can be obtained, and the quantity of the corresponding functional groups of the polyurethane acrylate is positively correlated with the peel strength; the surface water contact angle of the release paper prepared from a plurality of organic silicon resins mixed in different parts by mass is more than 90 degrees, the release paper has good hydrophobicity, and the novel binder is difficult to adsorb; the DMF resistance is excellent.
TABLE 1 Release paper Performance test
| Serial number | Surface water contact angle of release paper (bright) | Release paper-New adhesive Peel Strength (N/m) average | DMF resistance |
| Example 1 | 95 | 15.5 | Superior food |
| Example 2 | 95 | 13.5 | Superior food |
| Example 3 | 100 | 12.5 | Superior food |
| Example 4 | 105 | 11.6 | Superior food |
| Example 5 | 95 | 16.5 | Superior food |
| Example 6 | 100 | 14.3 | Superior food |
| Example 7 | 105 | 9.8 | Superior food |
| Example 8 | 105 | 10.5 | Superior food |
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the appended claims.
It should be appreciated by those of skill in the art that while the present invention has been described in terms of several embodiments, not every embodiment includes only a single embodiment. The description is given for clearness of understanding only, and it is to be understood that all matters in the embodiments are to be interpreted as including technical equivalents which are related to the embodiments and which are combined with each other to illustrate the scope of the present invention.
Claims (10)
1. The formula of the isocyanate-resistant release coating is characterized by comprising the following components in parts by mass: 15-30 parts of modified polyurethane acrylate, 55-80 parts of acrylate monomer, 1-10 parts of organic silicon resin and 1-5 parts of fumed silica, wherein the total parts of all the components are 100 parts.
2. The release coating formulation according to claim 1, wherein the modified urethane acrylate is prepared by polymerizing isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and trimer thereof as raw materials with monomer raw materials of hydroxyethyl acrylate and/or hydroxyethyl methacrylate and/or pentaerythritol triacrylate and/or polycaprolactone acrylate; the acrylate functionality is from 2 to 10.
3. The release coating formulation of claim 1, wherein the acrylate monomer is one or more of isobornyl acrylate (IBOA), isooctyl acrylate (EHA), Lauryl Acrylate (LA), 1, 6 hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), dipropoxypentylglycol diacrylate (2PO-NPGDA), trimethylolpropane triacrylate (TMPTA), triethoxytrimethylolpropane triacrylate (3EO-TMPTA), pentaerythritol triacrylate (PETA), glycidyl ether acrylate (GPTA), and pentaerythritol hexaacrylate (DPHA).
4. The release coating formulation according to claim 1, wherein the silicone resin is one or more of an acrylated product of a silicone oil, an epoxy-modified silicone resin, an ammonia-modified silicone resin, a urethane-modified silicone resin, a fatty acid-modified silicone resin, a silicone rubber resin, and a silicone oil.
5. Release paper comprising base paper and a release coating, characterized in that the release coating is cured from a release coating formulation according to any of the preceding claims.
6. The release paper of claim 5, wherein the release coating is a 100% solids coating layer.
7. The release paper according to claim 6, wherein the release coating formulation comprises, in percent: 5% of isophorone diisocyanate-based difunctional urethane acrylate, 10% of isophorone diisocyanate-based trifunctional urethane acrylate, 15% of isophorone diisocyanate-based hexafunctional urethane acrylate, 10% of acrylate monomer (TPGDA), 20% of acrylate monomer (TMPTA), 30% of acrylate monomer (DPHA), 5% of silicone oil acrylated product, 3% of polyurethane modified silicone resin and 2% of fumed silica.
8. The release paper according to claim 5, wherein a pattern is formed on the surface of the release coating.
9. A method for preparing the release paper as claimed in claim 5, characterized in that the excess release coating formulation is applied to a base paper by a feeding system, excess coating is scraped off by a scraper, and the base paper with the base coating is drawn by a guide roller and passed over the surface of an embossing roller and is pressed into the release paper with a pattern at a time under electron beam irradiation in an electron beam irradiation chamber.
10. Use of the release paper according to claim 5 in artificial synthetic leather.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110725778.9A CN113652163A (en) | 2021-06-29 | 2021-06-29 | Isocyanate-resistant release coating formula, release paper thereof, and manufacturing method and application of release paper |
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| CN202110725778.9A CN113652163A (en) | 2021-06-29 | 2021-06-29 | Isocyanate-resistant release coating formula, release paper thereof, and manufacturing method and application of release paper |
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Application publication date: 20211116 |