CN106674464B - Polyurethane resin for coating OPP film and preparation method thereof - Google Patents
Polyurethane resin for coating OPP film and preparation method thereof Download PDFInfo
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- CN106674464B CN106674464B CN201611226907.5A CN201611226907A CN106674464B CN 106674464 B CN106674464 B CN 106674464B CN 201611226907 A CN201611226907 A CN 201611226907A CN 106674464 B CN106674464 B CN 106674464B
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- 238000000576 coating method Methods 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 81
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title description 14
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 50
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 10
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- -1 poly-adipic acid neopentyl glycol ester diol Chemical class 0.000 claims description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000012643 polycondensation polymerization Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 16
- 238000001035 drying Methods 0.000 abstract description 15
- 239000004970 Chain extender Substances 0.000 abstract description 9
- 239000000377 silicon dioxide Substances 0.000 abstract description 8
- 239000007888 film coating Substances 0.000 abstract description 7
- 238000009501 film coating Methods 0.000 abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 7
- 125000003827 glycol group Chemical group 0.000 abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 4
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000009472 formulation Methods 0.000 description 6
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 238000007761 roller coating Methods 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 4
- 239000002649 leather substitute Substances 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
- C09D175/06—Polyurethanes from polyesters
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
- C08J2475/06—Polyurethanes from polyesters
Landscapes
- 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)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a polyurethane resin suitable for coating an OPP film. The polyurethane resin mainly comprises the following components in percentage by mass: 8.0% -12.0% of diphenylmethane-4, 4' -diisocyanate; 13% -17% of poly neopentyl glycol adipate glycol; 4% -6% of glycol chain extender 1 and glycol chain extender 2; 30-40% of solvent 1, 30-40% of solvent 2, 40-20% of solvent 3 and 0.15-0.3% of silicon dioxide matting powder. The polyurethane resin is used in the field of OPP film coating, and has the characteristics of high drying speed, good film forming performance and no pinholes or bubbles on the surface of a skin film.
Description
Technical Field
The invention relates to the technical field of polyurethane resin preparation, in particular to polyurethane resin for OPP film coating and a preparation method thereof.
Background
The dry type PU synthetic leather is generally prepared by coating and scraping polyurethane resin on release paper in a coating and scraping mode, drying and cooling, coating bonding layer resin for the second time, then attaching with base cloth, pressing, drying, cooling, and peeling off the release paper to obtain the dry type PU synthetic leather. After the release paper is peeled, the release paper can be used repeatedly. The release paper is used as a transfer base material, and has the advantages of diversified patterns and capability of forming synthetic leather with different lines. However, the release paper used as a transfer substrate has the disadvantages of high price and limited use times, and is generally not suitable for batch processes, so that technicians in the synthetic leather industry, especially in the field of textile coating, consider using an OPP film as a transfer substrate to partially replace the release paper.
Compared with release paper, the OPP film as a transfer substrate has the characteristics of low surface free energy and low price. After the polyurethane resin is coated on the substrate and dried, the substrate can be directly rolled into a subsequent process for standby without a continuous base fabric compounding and releasing process, and the intermittent process is simple and convenient to operate.
However, the OPP film also has drawbacks, first, poor heat resistance, resulting in the OPP film being easily deformed during the drying process. Secondly, the surface free energy is low and the adhesion to the coated substrate is poor, so that the OPP film needs to be corona treated before use. In order to prevent the deformation of the OPP film, the temperature of an oven cannot exceed 100 ℃ in the heating and drying process, and meanwhile, the processing speed needs to be increased, the retention time in the oven needs to be shortened, and the general speed is more than 30 m/min. How to make the solvent in the polyurethane resin dry and volatilize fast in the short time, need guarantee again that the involucra surface can not leave surface defects such as pinhole, bubble, dark bubble, can guarantee again simultaneously that polyurethane resin film forming back has better fastness of adhering to with the OPP membrane, the problem that technical staff in the field need to solve has always.
At present, polyurethane resin for OPP coating on the market is basically dissolved and diluted to 500CPs-1000CPs/25 ℃ by adopting butanone or ethyl acetate as a solvent, then the resin is coated on an OPP film by adopting a roller coating mode, the polyurethane resin coating liquid system coating OPP film is dried in an oven, the solvent evaporation (evaporation) and the polyurethane film forming process are carried out, the solvent evaporation speed is related to the vapor pressure of the solvent, and the vapor pressure is more volatile the greater. In order to increase the drying speed, a volatile solvent with high saturated vapor pressure (which is also the reason for commonly preparing butanone or ethyl acetate in the market at present) should be used as much as possible; generally, the boiling point of the volatile solvent is relatively low, the surface of the polyurethane resin working slurry is high in film forming speed in the drying process, the internal solvent easily penetrates through the film forming surface in the rapid drying process to cause the surface of the film to form pinholes, and bubbles are formed on the surface when the internal solvent is serious. In the drying process in an oven at 60-100 ℃, because the vehicle speed is fast, and because the saturated vapor pressure of butanone or ethyl acetate is large, the molecules volatilize fast, and the defects of pinholes, bubbles and the like are easily left in the film forming process of the polyurethane resin.
This disadvantage is usually remedied in production by post-addition of silicone antifoams. However, the silicone defoaming agent can only effectively play a role under the condition of low vehicle speed (generally, the vehicle speed is controlled below 15 m/s, and small bubbles in a coating liquid system can be eliminated in time), but the OPP film coating effect is not obvious (the bubbles can not be eliminated in time) under the condition of high vehicle speed (>30 m/s) in the production process, pinholes are often generated, defective products of the bubbles cannot meet the requirement of normal production on the yield, and meanwhile, the vehicle speed is low, and the production efficiency is low.
Because the OPP film has low heat resistance, the solvent for preparing the polyurethane resin coating liquid can only adopt butanone or ethyl acetate low-boiling point solvent to achieve the aim of quick drying, namely, on the premise that a polyurethane resin coating liquid system cannot be changed and a production line cannot be changed, the problem of generating bubbles and pinholes after the OPP film is coated can be solved only by changing the system of the polyurethane resin or adjusting the structure of the polyurethane resin.
In addition, because the coating process of the OPP film mostly adopts an intermittent production process, namely the coated OPP film is rolled for reprocessing of different purposes, the smoothness of the film surface is required to be good, the anti-adhesion performance of the rolled film is good, and the film is convenient to store and use.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a polyurethane resin for coating an OPP film, which has good adhesion with the OPP film when used for coating the OPP film. The OPP film is a polypropylene film, and because polypropylene molecules are nonpolar, the surface free energy of the polypropylene film is low, so that the adhesion fastness of the traditional polyurethane resin and the OPP film can be influenced, and the surface free energy of the OPP film is generally required to be improved through surface corona treatment; in order to further improve the adhesion fastness between the polyurethane resin and the OPP film, long-chain diol can be introduced into the resin molecule by adjusting the structure of the polyurethane resin, so that the polarity of the whole polyurethane resin molecule is reduced, and the adhesion fastness between the polyurethane resin and the OPP film is improved.
The second technical problem to be solved by the invention is to provide a solvent system, so that when the polyurethane resin in the solvent system is used for coating an OPP film, no pinholes or bubbles are generated in the process of quick drying in an oven at 60-100 ℃ and under the condition that the vehicle speed is more than 30 m/s; or the quantity and the degree of pinholes and bubbles are greatly reduced, so that the defective rate of defective products caused by the pinholes and the bubbles in the production process is low, and the yield is controlled to be more than 98%; meanwhile, the improvement of the speed of the vehicle ensures that the retention time in the OPP film drying oven is shortened, and greatly improves the production efficiency.
Theoretically, this can be achieved by adjusting the saturated vapor pressure and boiling point of the solvent system in the polyurethane resin system. The solvent with low saturated vapor pressure is used, so that the saturated vapor pressure of a resin system is reduced, the volatilization speed of the solvent is slowed down, the film forming speed of the surface of the resin is ensured to be consistent with the film forming speed of the interior of the resin, and the formation of pinholes or bubbles is reduced. However, considering that the heat resistance of the OPP film is low, the amount of N, N-dimethylformamide as a high boiling point solvent is appropriately reduced, the amount of a solvent having a boiling point of about 100 ℃ and a low saturated vapor pressure is increased, and the solubility of the polyurethane resin system is ensured in consideration of the solubility of the solvent in the polyurethane resin in view of the structure of the polyurethane resin. According to the invention, by designing the structure of the polyurethane resin and selecting the polyester polyol, the glycol chain extender and the solvent, the crystallinity of the formed polyurethane resin meets the dissolving requirement of the solvent on the polyurethane resin, the saturated vapor pressure of the solvent of the polyurethane resin system is greatly reduced, the defects of pinholes, bubbles and the like are avoided when the polyurethane resin is dried quickly at the temperature of below 100 ℃, or the quantity and degree of the pinholes and bubbles are greatly reduced, and the requirement on the yield in production is met.
The invention aims to solve the technical problem of providing polyurethane resin, which has good smoothness on the surface, is convenient to store in the process of rolling the leather membrane and prevents adhesion.
Due to the existence of the side group, the poly neopentyl glycol adipate diol has extremely low crystallinity and wide solvent compatibility; in addition, the polyurethane resin synthesized by poly neopentyl glycol adipate diol has strong film feeling and excellent surface smoothness after being coated with an OPP film.
The technical problem to be solved by the method is realized by the following technical scheme:
the polyurethane resin for coating the OPP film is prepared from the following raw materials in percentage by mass:
in a preferred embodiment of the present invention, the number average molecular weight of the poly neopentyl glycol adipate diol is preferably 1000-2000.
In a preferred embodiment of the present invention, the diol chain extender 1 is preferably 1, 9-nonanediol or 1, 10-decanediol.
In a preferred embodiment of the present invention, the diol chain extender 2 is a mixture of 80% to 90% of 2-methyl-1, 8-octanediol and 10% to 20% of 1, 9-nonanediol, preferably ND15 from Kuraray.
In a preferred embodiment of the present invention, the molar ratio of the glycol chain extender 1 to the glycol chain extender 2 is preferably 4: 1.
In the embodiment of the present invention, the solvent 1 is preferably N, N-dimethylformamide, the solvent 2 is preferably dimethyl carbonate or diethyl carbonate, and the solvent 3 is preferably one of methyl isobutyl ketone, methyl propyl ketone and methyl isopropyl ketone.
In the embodiment of the invention, the silicon dioxide matting powder is matting powder with the average particle size of 3.0-4.0 microns and the silicon dioxide content of more than or equal to 98 percent, and is preferably OK412 of degussa. The coating of the silicon dioxide matting powder is excellent and smooth in hand feeling, and in the embodiment of the invention, the neopentyl glycol adipate glycol is used in cooperation, so that the surface of the formed polyurethane resin has good smoothness, the polyurethane resin is convenient to store in the process of rolling the coating, and the adhesion is effectively prevented.
Surprisingly, the addition of the silicon dioxide matting powder not only enables the surface of a film formed after the polyurethane resin coating solution coats an OPP film to be smooth and effectively prevents the occurrence of adhesion, but also more importantly, compared with the traditional polyurethane resin in which an organic silicon defoaming agent is added in the process of preparing the coating solution, the polyurethane resin does not need to be added with an organic silicon defoaming agent; because the introduction of the silicon dioxide matting powder in the polyurethane resin system has played a better defoaming effect simultaneously, and in the high-speed stirring process before the use of the coating liquid, and in the roller coating process, compared with the later addition of an organic silicon defoaming agent, the silicon dioxide matting powder does not generate bubbles, but plays a defoaming effect, so that the bubbles are not introduced in the whole roller coating process, and the generation of pinholes or bubbles after the coating and drying of the OPP film is ensured by matching with a solvent of a low saturated vapor pressure system of the polyurethane resin.
As another aspect of the present invention, the present invention also provides a method for preparing a polyurethane resin for OPP film coating, comprising the steps of:
the preparation method comprises the following steps:
(1) putting poly adipic acid-neopentyl glycol ester diol polyol, a diol chain extender 1, a diol chain extender 2 and a solvent 1 and a solvent 2 which are calculated according to the solid content of the reaction into a reaction kettle, stirring and mixing uniformly, cooling to 60 ℃, putting diphenylmethane-4, 4' -diisocyanate, and starting the reaction, wherein the solid content of the reaction is 40-45%, and the NCO/OH is 0.90-0.95; the reaction temperature is 70-80 ℃, and the step (2) is started when hydrogen peroxide is tested to be not yellow, namely no NCO remains;
(2) adding the diphenylmethane-4, 4' -diisocyanate for viscosity increase, and adding the residual solvent when the viscosity reaches 50 ℃ and is 200pa.s-250 pa.s; when the final viscosity reached 20 ℃ and 120pa.s-160pa.s, the reaction was terminated, and silica matting powder was added and stirred for 4 hours to obtain an OPP coating polyurethane resin.
The polyurethane resin for coating the OPP film, which is prepared by the technical scheme and the preparation method, is diluted to 500CPS-1000CPs/25 ℃ by butanone or ethyl acetate before coating, and then the resin is coated on the OPP film in a roller coating mode and dried in an oven at the temperature of 60-100 ℃, wherein the length of the oven is 20 meters, and the yield of the finished film reaches more than 98% when the vehicle speed is 30 meters-50 meters per second.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Wherein, PE-3320, PE-3315 and PE-3310 are poly-adipic acid neopentyl glycol ester diol with the number average molecular weight of 2000, 1500 and 1000 respectively synthesized by the polycondensation reaction of adipic acid and neopentyl glycol; ND-15 is a mixture of 80% -90% 2-methyl-1, 8-octanediol and 10% -20% 1, 9-nonanediol from Kuraray. DMC is dimethyl carbonate, DEC is diethyl carbonate, DMF is N, N-dimethylformamide, and OK412 is Texaco matting powder.
Example 1:
the polyurethane resin formulation 1 for OPP film coating was as follows:
the preparation method of the polyurethane resin 1 for coating the OPP film is as follows:
(1) 150 parts of PE-3320, 42.35 parts of 1, 9-nonanediol, 10.59 parts of ND-15 and 214 parts of DMF (dimethyl formamide) calculated according to the solid content of the reaction, 214 parts of DMC are put into a reaction kettle, stirred and mixed uniformly, the temperature is reduced to 60 ℃, 91.35 parts of diphenylmethane-4, 4' -diisocyanate are put into the reaction kettle, the reaction is started, the solid content of the reaction is 40.7 percent, and the NCO/OH is 0.90; the reaction temperature is 70-80 ℃, and the step (2) is started when hydrogen peroxide is tested to be not yellow, namely no NCO remains;
(2) adding 10.15 parts of diphenylmethane-4, 4' -diisocyanate for viscosity increase, and adding the rest 286 parts of methyl isobutyl ketone when the viscosity reaches 50 ℃ and the viscosity reaches 200-250 pa.s; when the final viscosity reached 20 ℃ C., 120Pa.s-160Pa.s, the reaction was terminated, and 1.52 parts of DiOK 412 was added and stirred for 4 hours to obtain OPP coating polyurethane resin 1.
Example 2:
the formulation of the polyurethane resin 2 for coating the OPP film was as follows:
the preparation method of the polyurethane resin 2 for coating the OPP film is as follows:
(1) 170 parts of PE-3320, 38.63 parts of 1, 10-decanediol, 8.88 parts of ND-15 and 291 parts of DMF (dimethyl formamide) calculated according to the solid content of the reaction, 80 parts of DEC are put into a reaction kettle, stirred and mixed uniformly, cooled to 60 ℃, and then 86.1 parts of diphenylmethane-4, 4' -diisocyanate are added to start the reaction, the solid content of the reaction is 45%, and the NCO/OH is 0.95; the reaction temperature is 70-80 ℃, and the step (2) is started when hydrogen peroxide is tested to be not yellow, namely no NCO remains;
(2) adding 4.53 parts of diphenylmethane-4, 4' -diisocyanate for viscosity increase, and adding the rest 138 parts of DEC and 218 parts of methyl propyl ketone when the viscosity reaches 50 ℃ and the viscosity reaches 200pa.s-250 pa.s; when the final viscosity reached 20 ℃ C., 120Pa.s-160Pa.s, the reaction was terminated, and 3.08 parts of OK412 was added and stirred for 4 hours to obtain OPP coating polyurethane resin 2.
Example 3:
the formulation of the polyurethane resin 3 for coating the OPP film was as follows:
the preparation method of the polyurethane resin 3 for coating the OPP film is as follows:
(1) 150 parts of PE-3320, 42.35 parts of 1, 9-nonanediol, 10.59 parts of ND-15, 287 parts of DMF (dimethyl formamide) calculated according to the solid content of the reaction, 87 parts of DMC are put into a reaction kettle, stirred and mixed uniformly, the temperature is reduced to 60 ℃, 93.38 parts of diphenylmethane-4, 4' -diisocyanate are added, the reaction is started, the solid content of the reaction is 44.2 percent, and the NCO/OH is 0.92; the reaction temperature is 70-80 ℃, and the step (2) is started when hydrogen peroxide is tested to be not yellow, namely no NCO remains;
(2) 8.12 parts of diphenylmethane-4, 4' -diisocyanate are added to increase viscosity, and when the viscosity reaches 50 ℃ and the viscosity reaches 200Pa.s-250Pa.s, the remaining 200 parts of DMC and 144 parts of methyl isopropyl ketone are added; when the final viscosity reached 20 ℃ C., 120Pa.s-160Pa.s, the reaction was terminated, and 3.05 parts of DiOK 412 was added and stirred for 4 hours to obtain OPP coating polyurethane resin 3.
Example 4:
the formulation of the polyurethane resin 4 for coating the OPP film was as follows:
the preparation method of the urethane resin 4 for coating an OPP film is as follows:
(1) 160 parts of PE-3310, 33.87 parts of 1, 10-decanediol, 7.79 parts of ND-15 and 213 parts of DMF (dimethyl formamide) calculated according to the solid content of the reaction are put into a reaction kettle, 200 parts of DEC are stirred and mixed uniformly, then the temperature is reduced to 60 ℃, 95.76 parts of diphenylmethane-4, 4' -diisocyanate are put into the kettle, the reaction is started, the solid content of the reaction is 41.9 percent, and the NCO/OH is 0.95; the reaction temperature is 70-80 ℃, and the step (2) is started when hydrogen peroxide is tested to be not yellow, namely no NCO remains;
(2) adding 5.04 parts of diphenylmethane-4, 4' -diisocyanate for viscosity increase, and adding the rest 84 parts of DEC and 213 parts of methyl isopropyl ketone when the viscosity reaches 50 ℃ and the viscosity reaches 200pa.s-250 pa.s; when the final viscosity reached 20 ℃ C., 120Pa.s-160Pa.s, the reaction was terminated, and 1.51 parts of OK412 was added and stirred for 4 hours to obtain OPP coating urethane resin 4.
Example 5:
the polyurethane resin formulation 5 for OPP film coating was as follows:
the preparation method of the polyurethane resin 5 for coating the OPP film is as follows:
(1) 140 parts of PE-3310, 44.8 parts of 1, 9-nonanediol, 11.2 parts of ND-15 and 224 parts of DMF (dimethyl formamide) calculated according to the solid content of the reaction, 224 parts of DEC are put into a reaction kettle, stirred and mixed uniformly, cooled to 60 ℃, and then added with 110.3 parts of diphenylmethane-4, 4' -diisocyanate to start the reaction, wherein the solid content of the reaction is 40.6 percent, and the NCO/OH is 0.90; the reaction temperature is 70-80 ℃, and the step (2) is started when hydrogen peroxide is tested to be not yellow, namely no NCO remains;
(2) adding 12.2 parts of diphenylmethane-4, 4' -diisocyanate for viscosity increase, and adding the rest 299 parts of methyl isobutyl ketone when the viscosity reaches 50 ℃ and the viscosity reaches 200pa.s-250 pa.s; when the final viscosity reached 20 ℃ C., 120Pa.s-160Pa.s, the reaction was terminated, and 1.59 parts of DiOK 412 was added and stirred for 4 hours to obtain OPP coating urethane resin 5.
Example 6:
the polyurethane resin formulation 6 for OPP film coating was as follows:
the preparation method of the polyurethane resin 5 for coating the OPP film is as follows:
(1) 150 parts of PE-3315, 37.65 parts of 1, 9-nonanediol, 9.41 parts of ND-15 and 209 parts of DMF (dimethyl formamide) calculated according to the solid content of the reaction, 209 parts of DMC are put into a reaction kettle, stirred and mixed uniformly, then the temperature is reduced to 60 ℃, 93.6 parts of diphenylmethane-4, 4' -diisocyanate are added, the reaction is started, the solid content of the reaction is 41.0%, and the NCO/OH is 0.95; the reaction temperature is 70-80 ℃, and the step (2) is started when hydrogen peroxide is tested to be not yellow, namely no NCO remains;
(2) adding 4.9 parts of diphenylmethane-4, 4' -diisocyanate, increasing viscosity, and adding the rest 70 parts of DMC and 209 parts of methyl propyl ketone when the viscosity reaches 50 ℃ and the viscosity reaches 200Pa.s-250 Pa.s; when the final viscosity reached 20 ℃ C., 120Pa.s-160Pa.s, the reaction was terminated, and 2.96 parts of OK412 was added and stirred for 4 hours to obtain OPP coating urethane resin 6.
Dissolving the prepared polyurethane resin 1-6 for OPP coating with 140 parts of butanone or 140 parts of ethyl acetate to prepare coating liquid for coating the OPP film, wherein the labels of the coating liquid are respectively coating liquid 1-coating liquid 6, and the preparation formula is as follows:
polyurethane resins of examples 1-6: 100 portions of
Butanone or ethyl acetate: 140 portions of
Coating the coating liquid 1-6 on the OPP film by adopting a roller coating mode, drying in an oven at the temperature of 60-100 ℃, wherein the length of the oven is 20 m, the speed of the oven is 50 m/s, and the obtained OPP coating film is marked as coating film 1-coating film 6.
The preparation method comprises the following steps of (1) marking the traditional polyurethane resin HDS-1050 as a comparison resin, marking a coating liquid prepared from butanone as a comparison coating liquid 1, marking a coating liquid prepared from ethyl acetate as a comparison coating liquid 2, and preparing a formula:
HDS-1050:100 parts
Butanone or ethyl acetate: 140 portions of
DC-163：0.02
And (3) coating the comparison coating liquid 1 and the comparison coating liquid 2 on the OPP film in a roll coating mode, drying in an oven at the temperature of 60-100 ℃, wherein the length of the oven is 20 m, the speed of the vehicle is 50 m/s, and the labels of the obtained OPP coating films are the comparison coating film 1 and the comparison coating film 2 respectively.
The results of evaluation and comparison of the surface smoothness of the coating films of examples and comparative coating films, the pinhole and bubble condition of the coating films, the adhesion of the coating films to the OPP films, and the yield after coating films are shown in table 1.
TABLE 1
Coating liquid and coating film performance index evaluation table
As can be seen from Table 1, the coating films 1 to 6 did not peel off after coating, indicating that the coating films had good adhesion and the polyurethane resin of the present invention had good adhesion. The yield of the coating film 1-the coating film 6 is over 98 percent, which shows that the polyurethane resin of the invention solves the problems of pinholes and bubbles in the coating process. The coating films 1 to 6 have relatively good surface smoothness, and the formed OPP film does not have the problem of adhesion after being rolled, while the comparative coating films 1 and 2 have poor surface smoothness and are easy to adhere after being rolled. Therefore, the embodiment of the invention well solves the problems in the traditional polyurethane resin coating OPP film process, and achieves the purpose of the invention.
Claims (2)
1. The polyurethane resin for coating the OPP film is characterized by being prepared from the following raw materials in parts by mass:
PE-3320： 150；
1, 9-nonanediol: 42.35 of the total weight of the powder;
ND-15： 10.59；
MDI： 101.5；
DMF： 287；
DMC： 287；
methyl isopropyl ketone: 144, 144;
OK412： 3.05；
the ND-15 is a mixture consisting of 80-90% of 2-methyl-1, 8-octanediol and 10-20% of 1, 9-nonanediol which are prepared by Kuraray company;
the PE-3320 is poly-adipic acid neopentyl glycol ester diol with the number average molecular weight of 2000, which is synthesized by condensation polymerization of adipic acid and neopentyl glycol.
2. A method for preparing the polyurethane resin for coating an OPP film according to claim 1, which comprises the steps of:
(1) 150 parts of PE-3320, 42.35 parts of 1, 9-nonanediol, 10.59 parts of ND-15, 287 parts of DMF (dimethyl formamide) calculated according to the solid content of the reaction and 87 parts of DMC are put into a reaction kettle, stirred and mixed uniformly, cooled to 60 ℃, and then 93.38 parts of diphenylmethane-4, 4' -diisocyanate are put into the reaction kettle to start the reaction, wherein the solid content of the reaction is 44.2 percent, and NCO/OH = 0.92; the reaction temperature is 70-80 ℃, and the step (2) is started when hydrogen peroxide is tested to be not yellow, namely no NCO remains;
(2) 8.12 parts of diphenylmethane-4, 4' -diisocyanate are added to increase viscosity, and when the viscosity reaches 50 ℃ and the viscosity reaches 200Pa.s-250Pa.s, the remaining 200 parts of DMC and 144 parts of methyl isopropyl ketone are added; when the final viscosity reached 20 ℃ C, 120Pa.s to 160Pa.s, the reaction was terminated, and 3.05 parts of OK412 was added and stirred for 4 hours to obtain a polyurethane resin for OPP coating.
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| CN102227315A (en) * | 2008-12-09 | 2011-10-26 | 伊诺维亚薄膜有限公司 | Printable coating |
| CN103237860A (en) * | 2010-11-24 | 2013-08-07 | 乐金华奥斯有限公司 | Adhesive composition for touch panel, adhesive film, and touch panel |
| CN104140516A (en) * | 2014-04-18 | 2014-11-12 | 上海华峰新材料研发科技有限公司 | Two-component adhesive layer polyurethane resin for synthetic leather and preparation method of two-component adhesive layer polyurethane resin |
| CN104640897A (en) * | 2012-09-25 | 2015-05-20 | 拜耳材料科技股份有限公司 | Polyisocyanate-polyaddition products |
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| US20070021554A1 (en) * | 2005-07-01 | 2007-01-25 | Urban Marek W | Waterborne UV-crosslinkable thiol-ene polyurethane dispersions |
| US8022164B1 (en) * | 2010-03-04 | 2011-09-20 | Microvast, Inc. | Two-component solvent-free polyurethane adhesives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102227315A (en) * | 2008-12-09 | 2011-10-26 | 伊诺维亚薄膜有限公司 | Printable coating |
| CN103237860A (en) * | 2010-11-24 | 2013-08-07 | 乐金华奥斯有限公司 | Adhesive composition for touch panel, adhesive film, and touch panel |
| CN104640897A (en) * | 2012-09-25 | 2015-05-20 | 拜耳材料科技股份有限公司 | Polyisocyanate-polyaddition products |
| CN104140516A (en) * | 2014-04-18 | 2014-11-12 | 上海华峰新材料研发科技有限公司 | Two-component adhesive layer polyurethane resin for synthetic leather and preparation method of two-component adhesive layer polyurethane resin |
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