KR101674607B1 - Plastic glazing substrate for vehicle - Google Patents
Plastic glazing substrate for vehicle Download PDFInfo
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- KR101674607B1 KR101674607B1 KR1020150085872A KR20150085872A KR101674607B1 KR 101674607 B1 KR101674607 B1 KR 101674607B1 KR 1020150085872 A KR1020150085872 A KR 1020150085872A KR 20150085872 A KR20150085872 A KR 20150085872A KR 101674607 B1 KR101674607 B1 KR 101674607B1
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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
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- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
Abstract
The present invention relates to a plastic glazing substrate for automobiles. More particularly, the present invention relates to a plastic glazing board for an automobile, which exhibits excellent surface hardness, scratch resistance and abrasion resistance and can be used in place of automotive glass.
Description
The present invention relates to a plastic glazing substrate for automobiles. More particularly, the present invention relates to a plastic glazing board for an automobile, which exhibits excellent surface hardness, impact resistance, scratch resistance and abrasion resistance and can be used as an alternative to automotive glass.
Polycarbonate (PC) is a typical thermoplastic material and has excellent balance of physical properties such as transparency, impact resistance, dimensional stability and heat resistance, and is widely used for various applications including electric, electronic products, office equipment, and automobile parts.
In recent years, many studies have been made as a substitute material for automobile glass, taking advantage of the excellent transparency and moldability of polycarbonate resin. When a polycarbonate resin is used to replace parts such as a windowpane of an automobile, there is an advantage that the efficiency of the fuel is enhanced because the vehicle is lightened.
However, the polycarbonate resin is less resistant to abrasion such as scratch resistance and surface hardness than glass, and efforts are needed to improve it. This is largely studied in the direction of improving the polycarbonate resin substrate itself or adding a functional layer on the polycarbonate resin substrate.
When the functional layer is added on the polycarbonate resin substrate, the main physical properties required are scratch resistance, hardness, abrasion resistance, and the like. In addition, polycarbonate resin used as a substitute for glass for automobiles is also required to be processed because a bending molding process is required.
Until now, the main component of the coating layer laminated on the polycarbonate resin for improving the scratch resistance is mainly known as acrylic or silicone, which is not enough to form a coating layer which satisfies all of the above physical properties.
In order to solve the above-mentioned problems, the present invention provides a plastic glazing substrate for automobile which exhibits scratch resistance, hardness, impact resistance, abrasion resistance, and excellent processability.
In order to solve the above problems, according to one aspect of the present invention,
A substrate having a notched IZOD impact strength of at least 25 kJ / m 2 as measured by ASTM D256; And a photocurable coating layer laminated on at least one side of the substrate,
A haze value (Haze) of a haze after a 500 g load test and a 500 g load test according to ASTM D1044 is 10% or less.
INDUSTRIAL APPLICABILITY According to the automotive plastic glazing board of the present invention, scratch resistance, hardness, impact resistance, abrasion resistance, and excellent workability are exhibited and can be effectively applied to replace automotive glass.
In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.
Moreover, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises", "comprising", or "having" are used to designate the presence of stated features, steps, components, or combinations thereof, and are not intended to preclude the presence of one or more other features, Components, or combinations thereof, as a matter of convenience, without departing from the spirit and scope of the invention.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Hereinafter, the automotive plastic glazing board of the present invention will be described in more detail.
A plastic glazing substrate for an automobile according to an embodiment of the present invention includes a substrate having a notched IZOD impact strength of 25 kJ / m 2 or more as measured by ASTM D256; And a photo-curable coating layer laminated on at least one side of the substrate, wherein the haze change value (Δ Haze) after the 500 times of the taber abrasion test under a load of 1000 g according to ASTM D1044 is 10% or less .
Plastic glazing boards for automobiles are lighter in weight than glass and have less problems in shattering when broken, and are being studied as a substitute for automotive windowpanes. However, the abrasion resistance such as scratch resistance and surface hardness is weaker than that of glass, and a method of forming a coating layer on a substrate is used as one of means for compensating for this.
On the other hand, in order to achieve the scratch resistance, it is necessary to form the coating layer to a sufficient thickness or to deposit it in multiple layers. In this case, the productivity may decrease or adhesion with the resin as the substrate may decrease. In addition, the acrylate monomer mainly used as a binder in the coating layer has a problem of curling or cracking during the curing process due to severe curing shrinkage upon photo-curing. Particularly, in the case of windowpanes for automobiles, the polycarbonate resin is generally coated on the substrate in the form of a plate or three-dimensional shape. However, the coating layer using only the acrylate monomer may be difficult to coat on the substrate due to poor processability. It is also necessary to improve the coating layer composition to achieve sufficient scratch resistance and hardness at a level similar to that of glass.
Therefore, the plastic glazing board for automobile according to one embodiment of the present invention is a plastic glazing board for a vehicle, in which the coating layer exhibits sufficient scratch resistance, impact resistance, surface hardness and abrasion resistance, There is an advantage that the coating is easy.
The automotive plastic glazing board of the present invention includes a substrate having a notched IZOD impact strength of 25 kJ / m 2 or more measured by ASTM D256 and a photocurable coating layer laminated on at least one side of the substrate.
More specifically, the substrate on which the photocurable coating layer is formed has a notched IZOD impact strength of 25 kJ / m 2 or more, for example, 25 to 120 kJ / m 2 , as measured by ASTM D256, or And may have an impact strength of 40 to 100 kJ / m 2 .
The substrate may be a substrate including a polycarbonate resin while satisfying the notch Izod impact strength described above. The polycarbonate resin is excellent in transparency, light transmittance, moldability, heat resistance and the like and can be suitably used for a plastic glazing substrate for automobiles.
On the other hand, it is generally known that polycarbonate resins have poor scratch resistance, abrasion resistance, surface hardness, etc. However, according to one embodiment of the present invention, by using a substrate satisfying a constant notch Izod impact strength, A plastic glazing substrate for replacing glass for automobiles can be provided by securing abrasion resistance due to the photo-curable coating layer described later.
The thickness of the substrate is not particularly limited, but may have a thickness of from about 2 to about 10 mm, or from about 3 to about 5 mm to exhibit hardness at a level similar or equivalent to glass. In addition, the substrate may have other additional functions, for example, a UV shielding function, so as to be suitable for use in automobile windowpanes.
The automotive plastic glazing board comprises a photocurable coating layer laminated on at least one side of the substrate and has a haze change value (Haze) after 500 times of the taber wear test under a load of 1000 g according to ASTM D1044, Is 10% or less.
That is, the plastic glazing substrate according to the present invention has a high abrasion resistance of not more than 10% after a 500-test of 500 g of haze under a load of 1000 g according to ASTM D1044, It can be suitably used as a plastic glazing substrate.
Within the range that satisfies the aforementioned haze change value, the photocurable coating layer may have various compositions.
For example, according to one embodiment of the invention, the photocurable coating layer comprises a crosslinked copolymer of a photocurable elastomer and a 3- to 6-functional acrylate monomer, And inorganic fine particles dispersed in the crosslinked copolymer.
In a plastic glazing substrate according to an embodiment of the present invention, the photocurable coating layer comprises a crosslinked copolymer of a photocurable elastomer and a 3- to 6-functional acrylate-based monomer.
Throughout the present specification, the acrylate egg, acrylate as well as methacrylate, or a derivative having a substituent introduced into acrylate or methacrylate are all included.
In addition, throughout the present specification, the photo-curable elastomer means a polymer material containing a functional group capable of crosslinking polymerization by ultraviolet irradiation and exhibiting elasticity. In accordance with one embodiment of the present invention, the photocurable elastomer has a melt index of at least about 15%, such as from about 15 to about 200%, or from about 20 to about 200%, or from about 20 to about 200%, as measured by ASTM D638 It can have an elongation of 150%. When the photo-curable elastomer having the elongation in the above-described range is used, a photo-curable coating layer which satisfies all the physical properties can be formed.
The photo-curable elastomer can impart scratch resistance, abrasion resistance, flexibility, and impact resistance to the coating layer formed by cross-linking with the 3 to 6 functional acrylate monomers to form a coating layer after curing.
According to an embodiment of the present invention, when the total weight of the crosslinked copolymer is 100 parts by weight, the crosslinked copolymer may contain 5-20 parts by weight of the photocurable elastomer, the 3- or 6-functional acrylate monomer 80 To 95 parts by weight may be cross-linked. According to one embodiment of the present invention, by including the cross-linked copolymer in which the 3 to 6 functional acrylate monomer and the photo-curable elastomer are crosslinked to the weight portion, , Abrasion resistance and scratch resistance can be achieved.
According to one embodiment of the present invention, the photocurable elastomer has a weight average molecular weight of from about 1,000 to about 600,000 g / mol, or from about 10,000 to about 600,000 g / mol Lt; / RTI > or oligomer.
The photo-curable elastomer may be at least one selected from the group consisting of, for example, polycaprolactone, urethane acrylate-based polymer, and polyrotaxane.
Among the materials usable as the photo-curable elastomer, polycaprolactone is formed by the ring-opening polymerization of caprolactone and has excellent physical properties such as flexibility, impact resistance and durability.
The urethane acrylate-based polymer has urethane bonds and has excellent elasticity and durability.
The polyrotaxane refers to a compound in which a dumbbell shaped molecule and a macrocycle are structurally intercalated. Wherein the dumbbell-shaped molecule comprises a constant linear molecule and a blocking group disposed at both ends of the linear molecule, wherein the linear molecule penetrates the interior of the cyclic compound and the cyclic compound moves along the linear molecule And is prevented from being separated by the sealer.
According to one embodiment of the present invention, there is provided a cyclic compound having a lactone-based compound to which a (meth) acrylate-based compound is introduced at the terminal thereof; Linear molecules passing through the cyclic compound; And a blocking group disposed at both ends of the linear molecule to prevent the elimination of the cyclic compound.
The cyclic compound may be used without limitation as long as it has a size enough to penetrate or surround the linear molecule. The cyclic compound may be a hydroxyl group, an amino group, a carboxyl group, a thiol group or an aldehyde group And the like. Specific examples of such cyclic compounds include? -Cyclodextrin,? -Cyclodextrin,? -Cyclodextrin, and mixtures thereof.
As the linear molecule, a compound having a straight chain form can be used without any limitation, provided that the linear molecule has a molecular weight of a certain level or higher. However, a polyalkylene compound or a polylactone compound can be used. Specifically, a polyoxyalkylene compound containing an oxyalkylene repeating unit having 1 to 8 carbon atoms or a polylactone based compound having a lactone repeating unit having 3 to 10 carbon atoms can be used.
On the other hand, the blocking group can be appropriately controlled according to the properties of the produced rotaxane compound, and examples thereof include one selected from the group consisting of a dinitrophenyl group, a cyclodextrin group, an adamantane group, a trityl group, a fluororesin group, Two or more species can be used.
The polyrotasene compound as described above has excellent scratch resistance and can exhibit self-healing ability in the case of scratch or external damage.
According to the plastic glazing board of the present invention, photocuring including the photo-curable elastomer imparts abrasion resistance, hardness and flexibility to a plastic glazing substrate, and particularly excellent scratch resistance and impact resistance can be ensured.
The 3 to 6 functional acrylate monomers include trimethylolpropane triacrylate (TMPTA), trimethylolpropaneethoxy triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PETA), or dipentaerythritol hexaacrylate (DPHA). The 3 to 6 functional acrylate monomers may be used alone or in combination of two or more.
In the plastic glazing substrate of the present invention, the photocurable coating layer includes inorganic fine particles dispersed in the crosslinked copolymer.
According to an embodiment of the present invention, inorganic fine particles having a particle size of nanoscale as the inorganic fine particles, for example, nanoparticles having a particle size of about 100 nm or less, or about 10 to about 100 nm, or about 10 to about 50 nm, Can be used. As the inorganic fine particles, for example, silica fine particles, aluminum oxide particles, titanium oxide particles, or zinc oxide particles can be used.
By including the inorganic fine particles, the hardness of the coating layer can be further improved.
According to an embodiment of the present invention, when the total weight of the photocurable coating layer is 100 parts by weight, it may include about 40 to 90 parts by weight of a crosslinked copolymer and about 10 to about 60 parts by weight of inorganic fine particles, 50 to about 80 parts by weight of the crosslinked copolymer and about 20 to about 50 parts by weight of the inorganic fine particles. By including the crosslinked copolymer and the inorganic fine particles in the above-mentioned range, a plastic glazing substrate having excellent physical properties can be formed.
According to one embodiment of the present invention, the photocurable coating layer has a thickness of 50 mu m or more, for example, about 50 to about 300 mu m. For example, the photocurable coating layer of the present invention may have a thickness of at least about 50 microns, such as from about 50 to about 300 microns, or from about 50 to about 200 microns, or from about 50 to about 150 microns, Lt; / RTI > According to the present invention, the curing shrinkage caused by the acrylate-based monomer in the photo-curing process is canceled by the photo-curable elastomer, so that the coating layer can be formed with a high thickness as described above. As a result, the hardness, impact resistance and wear resistance Can be achieved.
In addition, the photocurable coating layer of the present invention may further include additives commonly used in the art such as a surfactant, a yellowing inhibitor, a leveling agent, and an antifouling agent, in addition to the crosslinked copolymer and the inorganic fine particles described above . The content may be varied within a range that does not deteriorate the physical properties of the plastic glazing substrate of the present invention. Therefore, the content may be included in an amount of about 0.1 to about 10 parts by weight based on 100 parts by weight of the coating layer have.
According to one embodiment of the present invention, for example, the photocurable coating layer may contain a surfactant as an additive, and the surfactant may be a fluorinated acrylate, a fluorinated surfactant or a silicone surfactant having 1 to 2 functionalities . The surfactant may be dispersed or crosslinked in the crosslinked copolymer.
Further, the additive may include a yellowing inhibitor, and examples of the yellowing inhibitor include a benzophenone-based compound or a benzotriazole-based compound.
Also, according to one embodiment of the present invention, for example, the photocurable coating layer may include a UV blocking agent as an additive to enhance weather resistance.
The photocurable coating layer can be formed by photocuring a coating composition comprising the 3- to 6-functional acrylate monomer, the photocurable elastomer, the inorganic fine particles, the photoinitiator, the optional additives and the organic solvent.
Examples of the photoinitiator include 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenyl- 2-benzoyl-2- (dimethylamino) -1- [4- (4-methoxyphenyl) -2-methyl-1-propanone, methylbenzoylformate, -Morpholin yl) phenyl] -1-butanone, 2-methyl-1- [4- (methylcio) , 6-trimethylbenzoyl) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Products currently on the market include Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907 and Esacure KIP 100F. These photoinitiators may be used alone or in combination of two or more.
Examples of the organic solvent include alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol, alkoxy alcohol solvents such as 2-methoxyethanol, 2-ethoxyethanol and 1-methoxy-2-propanol, Ketone solvents such as ethyl ketone, methyl isobutyl ketone, methyl propyl ketone and cyclohexanone, propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Ether solvents such as diethylene glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol monopropyl ether, diethyl glycol monobutyl ether and diethylene glycol-2-ethylhexyl ether, benzene, toluene, The same aromatic solvent may be used alone or in combination.
According to one embodiment of the present invention, the photocurable coating layer can be formed by applying and curing a coating composition comprising the above-described components onto a substrate. The photocurable coating layer may be formed on at least one side or both sides of the substrate.
In this case, the method of applying the coating composition is not particularly limited as long as it can be used in the art to which the present technology belongs. For example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, A gravure coating method, a comma coating method, a slot die coating method, a lip coating method, a solution casting method, or a spray method can be used.
Wherein the coating composition has a thickness of at least about 50 microns, such as from about 50 to about 300 microns, or from about 50 to about 200 microns, or from about 50 to about 150 microns, or from about 70 to about 150 microns, Lt; / RTI > According to the plastic glazing board of the present invention, it is possible to manufacture a plastic glazing board having high hardness, impact resistance and abrasion resistance because it has excellent flexibility and adhesion without curling or cracking even when formed with a high thickness as described above.
Next, the applied coating composition is irradiated with ultraviolet light to photo-cure the coating layer.
The amount of ultraviolet radiation may be, for example, about 20 to about 600 mJ / cm 2 , or about 50 to about 500 mJ / cm 2 . The light source for ultraviolet irradiation is not particularly limited as long as it can be used in the technical field to which the present technology belongs. For example, a high pressure mercury lamp, a metal halide lamp, a black light fluorescent lamp and the like can be used. Irradiation with the above-mentioned irradiation amount for about 30 seconds to about 15 minutes, or for about 1 minute to about 10 minutes to perform photocuring.
In the case of a plastic glazing substrate for replacing glass for automobiles, it is important to improve the hardness of the plastic glazing substrate to a level that can replace glass. In order to improve the hardness, Should be increased. However, as the thickness of the coating layer increases, the hardening shrinkage also increases, and the adherence is likely to decrease. Therefore, it is not easy to form a coating layer having a high hardness to such an extent that glass can be substituted without deteriorating the physical properties of the coating layer. In addition, in the case of a polycarbonate substrate used as a substitute for automobile glass, not only the surface hardness but also the physical properties such as impact resistance, scratch resistance and abrasion resistance are very important. In general acrylate cured resin layer, it is not easy to achieve all of these properties.
According to the plastic glazing board of the present invention, the coating layer is formed by crosslinking the photo-curable elastomer and the 3- to 6-functional acrylate monomer to maintain the adhesive force of the coating layer, and the surface hardness, scratch resistance, abrasion resistance, It is possible to provide a plastic glazing substrate of high hardness while satisfying physical properties required for automotive plastic glazing boards such as automobiles.
According to another embodiment of the present invention, the photocurable coating layer comprises a crosslinked copolymer of 3 to 6 functional acrylate monomers, An inorganic microfine particle dispersed in the crosslinked copolymer, and an amphipathic block copolymer.
In the plastic glazing substrate according to another embodiment of the present invention, the photo-curable coating layer includes a crosslinked copolymer with a 3- to 6-functional acrylate monomer and inorganic fine particles dispersed in the crosslinked copolymer do.
The above-mentioned 3 to 6 functional acrylate monomers are crosslinked and polymerized with each other by irradiation of ultraviolet rays together with the above-mentioned acrylate monomers or other binder components Crosslinked copolymer can be formed, and a high hardness can be imparted to the coating layer formed by including the crosslinked copolymer.
The 3 to 6 functional acrylate monomers include trimethylolpropane triacrylate (TMPTA), trimethylolpropaneethoxy triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PETA), or dipentaerythritol hexaacrylate (DPHA). The 3 to 6 functional acrylate monomers may be used alone or in combination of two or more.
According to an embodiment of the present invention, the 3 to 6 functional acrylate monomers may be used in an amount of 100 parts by weight or more per 100 parts by weight of the photocurable coating layer, About 45 to about 85 parts by weight, or about 50 to about 80 parts by weight. When the 3 to 6 functional acrylate monomers are in the above range, a plastic substrate having good physical properties such as hardness, impact resistance, scratch resistance and abrasion resistance can be formed.
A photocurable coating layer according to another embodiment of the present invention comprises an amphiphilic block copolymer.
In the present specification, the amphipathic block copolymer includes both a miscible block and an immiscible block for the 3 to 6 functional acrylate monomers in one molecule ≪ / RTI >
According to an embodiment of the present invention, the miscible block includes a repeating unit exhibiting high affinity or compatibility with the 3- to 6-functional acrylate-based monomer. The miscible block may include, for example, polyethylene oxide (PEO), polypropylene oxide (PPO), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA) Polycaprolactone (PCL), polystyrene (PS), polyacrylic acid (PAA) or the like, but the present invention is not limited thereto. The affinity or compatibility may be determined by measuring the solubility parameter of the binder to be a reference, and distinguishing the miscible block from the miscible block by their relative relationship.
The immiscible block includes a repeating unit exhibiting low affinity or compatibility with the 3- to 6-functional acrylate-based monomer. The immiscible block may be, for example, polypropylene oxide (PPO), polybutylene oxide (PBO), polyhexylene oxide (PHO), polybutadiene (PB), polydimethyl At least one or more compounds selected from the group consisting of polydimethyl siloxane (PDMS), polybutyl acrylate (PBA) or polyalkyl (meth) acrylate (PAMA) having an alkyl group having 2 to 10 carbon atoms But the present invention is not limited thereto.
In the amphiphilic block copolymer, the ratio of the miscible block to the immiscible block is not particularly limited. For example, the composition ratio of each miscible and immiscible block is about 5 : 95 to about 95: 5, or about 3: 7 to about 7: 3, or about 4: 6 to about 6: 4.
According to one embodiment of the present invention, the amphiphilic block copolymer may be a multiblock copolymer such as a diblock copolymer, a triblock copolymer, a tetrablock copolymer or the like, ) Structure, a branched multi-block, or a multi-block structure in a three-dimensional shape, and is not particularly limited. For example, when the amphiphilic block copolymer is a diblock copolymer, the miscible block (M) and the incompatible block (I) may have repeating units of -MI- or -IM- have. -MIM-form or -IMI-form in which the miscible block (M), the incompatible block (I) and the miscible block (M) are alternately arranged when the amphiphilic block copolymer is a triblock copolymer Can have repeating units.
According to one embodiment of the present invention, the number average molecular weight of the amphiphilic block copolymer may be from about 1,000 to about 100,000 g / mol, or from about 2,000 to about 50,000 g / mol.
The amphiphilic block copolymer has self-assembling properties by including both miscible and immiscible blocks with respect to the 3- to 6-functional acrylate-based monomer. Thus, in the process of mixing the amphiphilic block copolymer with other components, the miscible block is directed to the binder side, that is, to the outside, depending on the difference in affinity of each block with respect to the 3- to 6-functional acrylate monomer The immiscible block may be in the opposite direction, i.e., inwardly directed, to have a spherical or spherical micelle shape. The micelle may have a particle diameter of about 100 nm or less, for example, about 5 to about 100 nm. When the particle diameter of the micelle is more than 100 nm, the coating layer may be optically influenced to decrease the transmittance, so that the particle diameter is preferably 100 nm or less.
As described above, the photo-curable coating layer of the present invention can increase the toughness and impact resistance of the coating layer without deteriorating the mechanical properties by including the amphiphilic block copolymer. In particular, the amphiphilic block copolymer may be present in the form of micelles, wherein the micelles are self-assembled such that the blocks miscible with the 3-6 functional acrylate monomers are directed outward so that the amphiphilic block copolymer Effectively absorbs the impact from the outside. Therefore, the photo-curable coating layer containing the amphiphilic block copolymer satisfies physical properties required for an automotive plastic glazing substrate such as surface hardness, scratch resistance, abrasion resistance and impact resistance, and can provide a high-hardness plastic glazing substrate have.
According to one embodiment of the present invention, the amphiphilic block copolymer may be included in an amount of about 0.1 to about 30 parts by weight, or about 0.5 to about 20 parts by weight based on 100 parts by weight of the photocurable coating layer. By incorporating the amphiphilic block copolymer in the above range, it is possible to form a plastic substrate of excellent physical properties having improved impact resistance, scratch resistance, abrasion resistance and workability without deteriorating mechanical properties.
In the plastic glazing substrate according to an embodiment of the present invention, the photocurable coating layer includes inorganic fine particles dispersed in the crosslinked copolymer.
According to an embodiment of the present invention, nanoparticles having a particle size of nanoscale as the inorganic microfine particle, for example, a particle size of about 100 nm or less, or about 10 to about 100 nm, or about 10 to about 50 nm may be used . As the inorganic fine particles, for example, silica fine particles, aluminum oxide particles, titanium oxide particles, or zinc oxide particles can be used.
By including the inorganic fine particles, the hardness of the photo-curable coating layer can be further improved.
According to an embodiment of the present invention, the inorganic fine particles may be included in an amount of about 10 to about 40 parts by weight, or about 10 to about 30 parts by weight based on 100 parts by weight of the photocurable coating layer. By including the inorganic fine particles in the above range, a plastic glazing substrate having excellent physical properties can be formed.
According to one embodiment of the present invention, the photocurable coating layer has a thickness of 50 mu m or more, for example, about 50 to about 300 mu m. For example, the coating layer of the present invention can have a thickness of at least about 50 microns, such as from about 50 to about 300 microns, or from about 50 to about 200 microns, or from about 50 to about 150 microns, or from about 70 to about 150 microns Lt; / RTI > According to the present invention, the curing shrinkage caused by the acrylate-based monomer in the photocuring process is canceled by the amphiphilic block copolymer to form the coating layer with the high thickness as described above, and thus the high porosity, Impact resistance and abrasion resistance can be achieved.
Other additives included in the photo-curable coating layer, a manufacturing method, and the like are not described because they are applicable to the plastic glazing substrate according to one embodiment of the present invention.
Optionally, the plastic glazing substrate of the present invention may further comprise a separate functional layer on the photocurable coating layer. The type of the functional layer that can be included and the method of attaching the functional layer may vary depending on the application and are not particularly limited in terms of the material and the physical properties.
On the other hand, the photocurable coating layer is excellent in adhesiveness to a substrate without a separate primer layer, and the process steps can be further simplified by omitting the primer layer.
The plastic glazing substrate of the present invention produced as described above exhibits excellent curl characteristics, high porosity, high hardness, impact resistance, abrasion resistance, scratch resistance, high transparency, and light resistance without warping or cracking. In addition, if necessary, various films, layers or films are stacked on the photo-curable coating layer to be widely applicable to high-performance automotive parts.
The plastic glazing substrate of the present invention has excellent abrasion resistance. As described above, the plastic glazing substrate of the present invention has a haze change value (Haze) of 10% or less after 500 times of test of a taber under a load of 1000 g.
The plastic glazing substrate of the present invention can have an impact resistance that is high enough to replace glass. For example, the plastic glazing substrate of the present invention may not crack when 225 g of iron ball falls freely at a height of 180 cm.
The plastic glazing substrate of the present invention may have a pencil hardness of 7H or more, 8H or more, or 9H or more at a load of 1 kg.
In addition, scratches can occur to two or less when a steel wool # 0000 is mounted on a friction tester and then reciprocated 100 times under a load of 500 g.
The plastic glazing substrate of the present invention may have a light transmittance of 90% or more, or 91% or more, and a haze of 1.0% or less, or 0.5% or less.
In addition, the plastic glazing substrate of the present invention may have an initial color b value of 2.0 or less. Also, the difference between the initial color b value and the color b value after 72 hours or more exposure to ultraviolet lamps in the UVB wavelength region may be 0.5 or less, or 0.4 or less.
The plastic glazing substrate of the present invention can be used in various fields, and can be used particularly as a substitute for glass for automobiles.
Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.
< Example >
Manufacturing example One: Photocurable Preparation of elastomer
After the addition of 50 g of polyrotase polymer grafted with caprolactone [A1000, Advanced Soft Material INC] to the reactor, 4.53 g of Karenz-AOI [2-acryloylethyl isocyanate, Showa Denko KK], Dibutyltin dilaurate [DBTDL, Merck ], 110 mg of hydroquinone monomethylene ether and 315 g of methyl ethyl ketone were added and reacted at 70 ° C for 5 hours to obtain a polyrota compound containing a cyclodextrin in which a polylactone based compound having an acrylate compound introduced at its end was bonded as a cyclic compound I got three.
The polyrotaxane thus obtained had a weight average molecular weight of 600,000 g / mol and an elongation of 20% as measured by ASTM D638.
Manufacturing example 2: PMMA-PB-PS ( 폴리 메틸 메록acrylate - polybutadiene -polystyrene) block copolymer
polymethyl methacrylate, polybutadiene, and polystyrene were prepared by atom transfer radical copolymerization to prepare a PMMA-PB-PS block copolymer. At that time, the volume ratio of PMMA: PB: PS was 32:34:34 and the number average molecular weight was about 50,000 g / mol. The mean particle size of the micellar structure formed by the self-assembly of the PMMA-PB-PS block copolymer was about 25 nm.
Manufacturing example 3: PEO - PPO - PEO (polyethylene oxide-polypropylene oxide-polyethylene oxide) block copolymer ( Number average Molecular weight: 30,000 g / mol )
polyethylene oxide, and polypropylene oxide were prepared by atom transfer radical copolymerization to prepare a PEO-PPO-PEO block copolymer. In this case, the volume ratio of PEO: PPO: PEO was 1: 2: 1 and the number average molecular weight was about 30,000 g / mol. The average particle size of the micellar structure formed by the self-assembly of the PEO-PPO-PEO block copolymer was about 15 nm .
Manufacturing example 4: PMMA- PBA ( 폴리 메틸 메록acrylate - polybutyl acrylate ) Block copolymer
Polymethyl methacrylate and polybutyl acrylate were prepared by RAFT polymerization (Reversible addition fragment chain transfer polymerization) to prepare PMMA-PBA block copolymer. At this time, the volume ratio of PMMA: PBA was 1: 1 and the number average molecular weight was about 29,000 g / mol. The average particle size of the micellar structure formed by the self-assembly of the PMMA-PBA block copolymer was about 15 nm.
Preparation Example 5: Preparation of PDMS- PMMA ( polydimethyl siloxane - polymethyl methacrylate) block copolymer
polydimethyl siloxane and polymethyl methacrylate were prepared by atom transfer radical copolymerization to prepare a PDMS-PMMA block copolymer. In this case, the volume ratio of PMMA: PDMS was 1: 1 and the number average molecular weight was about 30,000 g / mol. The average particle size of the micellar structure formed by the self-assembly of the PDMS-PMMA block copolymer was about 23 nm.
Example One
9 g (silica 3.6 g, DPHA 5.4 g) of silica-dipentaerythritol hexaacrylate (DPHA) complex in which 40 wt% of nano silica having a particle size of 20 to 30 nm was dispersed, 1 g of polyrotase in Production Example 1, (Trade name: Darocur TPO), 0.1 g of a benzotriazole yellowing inhibitor (trade name: Tinuvin 400), 0.05 g of a fluorine surfactant (trade name: FC4430) and 1 g of methyl ethyl ketone were mixed to prepare a coating composition.
The coating composition was applied on a 30 cm x 30 cm, 3 mm thick PC substrate (notched IZOD impact strength of 80 kJ / m 2 as measured by ASTM D256). Subsequently, a substrate having a coating layer having a thickness of 100 탆 was prepared by irradiating ultraviolet light having a wavelength of 280-350 nm using a high-pressure mercury lamp to perform photo-curing.
Example 2
Except that 1 g of a urethane acrylate polymer (trade name: UA200PA, Shin Nakamura Chemical Co., Ltd., weight average molecular weight 2,600 g / mol, elongation of 170% according to ASTM D638) was used in place of 1 g of the polyrotasene of Production Example 1 Was prepared in the same manner as in Example 1.
Example 3
Except that 1 g of a urethane acrylate polymer (trade name: UA340P, Shin Nakamura Chemical Co., Ltd., weight average molecular weight 13,000 g / mol, elongation at 150% according to ASTM D638) was used in place of 1 g of the polyrotasane of Production Example 1 Was prepared in the same manner as in Example 1.
Example 4
A substrate was prepared in the same manner as in Example 1 except that the coating layer had a thickness of 150 mu m.
Example 5
8 g (silica 1.6 g, PETA 6.4 g) of pentaerythritol tetraacrylate (PETA) complex in which about 20 wt% of nano silica having a particle diameter of 20 to 30 nm was dispersed, 2 g of PMMA-PB-PS block copolymer of Production Example 2, , 0.1 g of a photoinitiator (trade name: Irgacure 819), 0.1 g of a benzotriazole yellowing inhibitor (trade name: Tinuvin 400), 0.05 g of a fluorine surfactant (trade name: F477) and 2 g of methyl ethyl ketone were mixed to prepare a coating composition.
A substrate was prepared in the same manner as in Example 1 using the above coating composition.
Example 6
A substrate was prepared in the same manner as in Example 5, except that 2 g of the PEO-PPO-PEO block copolymer of Production Example 3 was used in place of the PMMA-PB-PS block copolymer in the coating composition of Example 5.
Example 7
A substrate was prepared in the same manner as in Example 5, except that 2 g of the PMMA-PBA block copolymer of Production Example 4 was used in place of the PMMA-PB-PS block copolymer in the coating composition of Example 5.
Example 8
A substrate was prepared in the same manner as in Example 5, except that 2 g of the PDMS-PMMA block copolymer of Production Example 5 was used in place of the PMMA-PB-PS block copolymer in the coating composition of Example 5. [
Comparative Example One
5 g of silica-dipentaerythritol hexaacrylate (DPHA) complex (2 g of silica, 3 g of DPHA) in which 40 wt% of nano silica having a particle diameter of 20 to 30 nm was dispersed, 5 g of polyrotase in Production Example 1, 0.1 g of a benzotriazole yellowing inhibitor (trade name: Tinuvin 400), 0.05 g of a fluorine surfactant (trade name: FC4430) and 1 g of methyl ethyl ketone were mixed to prepare a coating composition.
Subsequent steps were carried out in the same manner as in Example 1 to prepare a substrate.
Comparative Example 2
4 g (silica 0.8 g, PETA 3.2 g) of pentaerythritol tetraacrylate (PETA) complex in which about 20 wt% of nano silica having a particle diameter of 20 to 30 nm was dispersed, 6 g of PMMA-PB-PS block copolymer of Production Example 2, , 0.1 g of a photoinitiator (trade name: Irgacure 819), 0.1 g of a benzotriazole yellowing inhibitor (trade name: Tinuvin 400), 0.05 g of a fluorine surfactant (trade name: F477) and 2 g of methyl ethyl ketone were mixed to prepare a coating composition.
A substrate was prepared in the same manner as in Example 1 using the above coating composition.
Comparative Example 3
(Silica 0.8 g, PETA 3.2 g), 6 g of the PDMS-PMMA block copolymer of Production Example 5, 6 g of the photoinitiator (manufactured by Mitsubishi Chemical Corporation), 5 g of the pentaerythritol tetraacrylate (PETA) (Trade name: Irgacure 819), 0.1 g of a benzotriazole yellowing inhibitor (trade name: Tinuvin 400), 0.05 g of a fluorine surfactant (trade name: F477) and 2 g of methyl ethyl ketone were mixed to prepare a coating composition.
A substrate was prepared in the same manner as in Example 1 using the above coating composition.
Comparative Example 4
A notched IZOD impact strength of 80 kJ / m 2 as measured by ASTM D256 (thickness: 3 m) on a thick-film 3-m non-coated PC substrate was prepared and compared in the same measurement method.
The main components and thicknesses of the coating layers in the substrates of Examples 1 to 8 and Comparative Examples 1 and 3 are shown in Table 1 below.
< Experimental Example >
<Measurement method>
1) Pencil Hardness
The hardness without scratches was confirmed after three reciprocations with a load of 1.0 kg according to the measurement standard JIS K5400 using a pencil hardness meter.
2) scratch resistance
The steel wool (# 0000) was mounted on a friction tester, and after 100 reciprocations with a load of 500 g, the number of scratches was evaluated. The case where the number of scratches was 2 or less, the case where the number of scratches was 2 or more but less than 5, and the case where the number of scratches was 5 or more,
3) Light resistance
The difference in color b values was measured before and after exposure to ultraviolet lamps in the UVB wavelength range for more than 72 hours.
4) Transmittance and haze
The transmittance and haze were measured using a spectrophotometer (instrument name: COH-400).
5) Impact resistance
Each specimen (substrate) was prepared to have a size of 30 cm x 30 cm (about 12 inch x 12 inch), and maintained at a temperature of 21 to 29 ° C. for 4 hours or more before the impact test to uniformize the temperature of each specimen.
Prepared specimens were clamped between two frames made of 1-inch-thick steel, and the specimens were fixed with a rubber gasket of 3 mm in thickness between the specimens and the frame so that the specimens and the ground were parallel when the impact was applied.
225g of iron ball was dropped freely from a height of 180cm to fall to the center of the specimen. When the sample was dropped on each specimen, the impact resistance was judged by the presence or absence of a crack, and the case where the crack did not occur was evaluated as OK, and the case where the crack occurred was evaluated as X.
6) Wear test
The haze change value (Haze) after a 500 g load test and a 500 g load test using a CS-10F wheel as a taber abrasion test method according to ASTM D1044 for a 10x10 cm sample, , And when the change value of the haze was 10% or less, it was evaluated as good and when it was more than 10%, it was evaluated as bad.
The measurement results of the physical properties of the above Examples and Comparative Examples are shown in Tables 2 and 3 below.
As shown in Tables 2 and 3, the substrates of the examples of the present invention showed good properties in all properties. However, the substrates of Comparative Examples 1 to 4 did not exhibit sufficient characteristics to be applicable to automotive glazing substrates, such as impact resistance, abrasion resistance, and pencil hardness.
Claims (18)
The haze value (DELTA Haze) after the 500 times of the test of the taber abrasion under a load of 1000 g according to ASTM D1044 is 10% or less,
The pencil hardness at a load of 1 kg is not less than 7H,
Cracks do not occur when 225g of iron ball is dropped from 180cm height,
The photocurable coating layer comprises a crosslinked copolymer of 3 to 6 functional acrylate monomers, An inorganic microfine particle dispersed in the crosslinked copolymer, and an amphiphilic block copolymer.
Automotive plastic glazing board.
Wherein the substrate comprises a polycarbonate resin.
Wherein the amphiphilic block copolymer comprises a miscible block that is miscible with the 3- to 6-functional acrylate-based monomer and an immiscible block that is immiscible.
The miscible block may be selected from the group consisting of polyethylene oxide (PEO), polypropylene oxide (PPO), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA), polycaprolactone (PPO), polypropylene oxide (PPO), polypropylene oxide (PCO), polypropylene oxide (PCO), polycaprolactone (PCL), polystyrene (PS), and polyacrylic acid Polybutylene oxide (PBO), polyhexylene oxide (PHO), polybutadiene (PB), polydimethyl siloxane (PDMS), polybutyl acrylate (PBA) And polyalkyl (meth) acrylate (PAMA) having an alkyl group having 2 to 10 carbon atoms. , Automotive glazing plastic substrate comprising.
Wherein the amphipathic block copolymer is in a micelle form having a particle diameter of 100 nm or less.
Wherein the photocurable coating layer comprises 45 to 85 parts by weight of the crosslinked copolymer, 10 to 40 parts by weight of the inorganic fine particles, and 0.1 to 30 parts by weight of the amphiphilic block copolymer, when the total weight of the photocurable coating layer is 100 parts by weight. Automotive plastic glazing board.
Wherein the inorganic fine particles include at least one selected from the group consisting of silica nanoparticles, aluminum oxide fine particles, titanium oxide fine particles, and zinc oxide fine particles.
The 3 to 6 functional acrylate monomers include trimethylolpropane triacrylate (TMPTA), trimethylolpropaneethoxy triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate , Polyethylene terephthalate (PETA), and dipentaerythritol hexaacrylate (DPHA).
Wherein the photocurable coating layer has a thickness of 50 to 300 占 퐉.
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