CN108582936B - High-barrier near-infrared protective film - Google Patents
High-barrier near-infrared protective film Download PDFInfo
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- CN108582936B CN108582936B CN201810141409.3A CN201810141409A CN108582936B CN 108582936 B CN108582936 B CN 108582936B CN 201810141409 A CN201810141409 A CN 201810141409A CN 108582936 B CN108582936 B CN 108582936B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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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
- C08L27/00—Compositions of 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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/212—Electromagnetic interference shielding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/73—Hydrophobic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2571/00—Protective equipment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2231—Oxides; Hydroxides of metals of tin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present case relates to a high resistant near-infrared's protection film, including a substrate layer and at the barrier layer on this substrate layer surface, the barrier layer comprises the material of following parts by weight: 30-45 parts of organic silicon modified polyurethane, 12-18 parts of vinyl ethyl ether-benzyl acrylate copolymer, 8-10 parts of PPE resin, 5-10 parts of plasticizer, 7-15 parts of near infrared absorber and 0.5-2 parts of antioxidant. The invention adopts the composite structure of the substrate layer and the barrier layer, which can effectively ensure that the surface of the metal plate is not damaged when the metal plate is cut by laser; when the cold plastic forming process is carried out, the film cannot wrinkle and cannot be broken; good quality and good protection effect.
Description
Technical Field
The invention relates to the technical field of films, in particular to a high-resistance near infrared protective film.
Background
Laser processing is widely used because of its high processing speed and the ability to implement a dry process, and particularly, infrared lasers are often used in various fields of microfabrication. Laser cutting is known for its high speed, high precision and high kerf finish. Not only saves a large amount of moulds, but also greatly shortens the development period of new products. After laser cutting, some cold plastic working such as bending is generally required to be performed on the metal plate. The existing processing method is that a layer of common protective film is generally adhered and coated on a metal plate, one is that a common protective film product is adhered before laser cutting, but when the laser cutting is carried out, due to the action of low-temperature and high-pressure auxiliary gas, the common protective film can form a large bubble at a cutting part to block the normal work of a laser head, and the laser head can be damaged when the normal work is serious; the common protective film is adopted, when cold plasticity processing procedures such as bending and the like are carried out, the phenomena of wrinkling, embrittlement, breaking and the like of the film can be caused, the mechanical property is poor, the weather resistance is poor, and the film is easy to oxidize in air; some protective films have poor heat insulation effect and poor transparency.
Disclosure of Invention
Aiming at the technical problems in the prior art, the protective film with high resistance and near infrared isolation is provided.
In order to achieve the purpose, the scheme is achieved through the following technical scheme:
the utility model provides a high resistant protection film that separates near-infrared, wherein, includes a substrate layer and the barrier layer on this substrate layer surface, the barrier layer comprises the material of following parts by weight:
preferably, the high-resistance near-infrared protective film is characterized in that the substrate layer is a polyethylene naphthalate layer and a fluoroplastic alloy layer; the polyethylene naphthalate layer is arranged on the bottom surface of the fluoroplastic alloy layer.
Preferably, the high-resistance near-infrared protective film includes 54-60 wt% of polyvinylidene fluoride and 40-48 wt% of ethylene-chlorotrifluoroethylene copolymer.
Preferably, the high-infrared-blocking protective film is formed by adding a plasticizer to a high-infrared-blocking resin.
Preferably, the protective film with high near infrared barrier property comprises 24-28 wt% of tin oxide and 15-20 w% of near infrared absorbentt% of EDTA-copper ammonium complex, 32-38 wt% of Ti3SnC2And 20 to 25 wt% (V)0.5Cr0.5)3AlC2。
Preferably, the high-resistance near-infrared-blocking protective film comprises 40-55 wt% of pentaerythritol triacrylate and 50-60 wt% of 2, 4-dihydroxybenzophenone.
Preferably, the high-resistance near-infrared protective film is characterized in that the number average molecular weight of the organosilicon modified polyurethane is 14000-16000 g/mol.
Preferably, in the protective film with high resistance to near infrared, in the vinyl ethyl ether-benzyl acrylate copolymer, the content of vinyl ethyl ether is 40-50 wt%, and the content of benzyl acrylate is 50-60 wt%; the number average molecular weight of the vinyl ethyl ether-benzyl acrylate copolymer is 5500-6000 g/mol.
Preferably, the high-barrier near-infrared protective film is one of tin oxide, EDTA-cuprammonium complex, and Ti3SnC2And (V)0.5Cr0.5)3AlC2The particle size of (B) is 100-120 nm.
The invention has the beneficial effects that:
(1) the invention adopts the composite structure of the substrate layer and the barrier layer, which can effectively ensure that the surface of the metal plate is not damaged when the metal plate is cut by laser; when the cold plastic forming process is carried out, the film cannot wrinkle and cannot be broken; good quality and good protection effect.
(2) The invention takes organosilicon modified polyurethane as the main body of the barrier layer; by adding the vinyl ethyl ether-benzyl acrylate copolymer, the mechanical property, weather resistance, chemical resistance, color retention and water resistance of the barrier layer are improved; the PPE resin is added to improve the dimensional stability and the water resistance of the barrier layer; the plasticizer is tricresyl phosphate; the flame retardance, mildew resistance, wear resistance, weather resistance and radiation resistance of the barrier layer are improved by adding tricresyl phosphate, and the flexibility of the film is improved; tin oxide, EDTA-copper ammonium complex, Ti3SnC2And (V)0.5Cr0.5)3AlC2The reasonable proportion is used as an absorbent together, so that the mid-infrared blocking and reflecting capacity of the protective film is improved; pentaerythritol triacrylate and 2, 4-dihydroxybenzophenone as antioxidants improve the thermal processability of the protective film, prevent aging of the polymer film and prolong its service life.
(3) The polyethylene naphthalate layer and the fluoroplastic alloy layer are compounded to serve as the base material layer, and the polyethylene naphthalate layer is good in gas barrier performance, excellent in thermal performance and ultraviolet light absorption capacity; the high-temperature color change resistance, the oxidation resistance, the wear resistance, the flexibility, the expansion strength and the impact strength of the protective film are further improved through the fluoroplastic alloy layer.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
The invention provides a high-barrier near-infrared protective film which comprises a substrate layer and a barrier layer on the surface of the substrate layer, wherein the barrier layer is composed of the following materials in parts by weight:
the organic silicon modified polyurethane is used as the main body of the barrier layer, and has the advantages of high mechanical strength, oxidation stability, flexibility, good rebound resilience, oil resistance, solvent resistance, water resistance and fire resistance of the polyurethane, and the heat resistance and weather resistance of the polyurethane are improved by modifying the polyurethane through organic silicon; by adding the vinyl ethyl ether-benzyl acrylate copolymer, the mechanical property, weather resistance, chemical resistance, color retention and water resistance of the barrier layer are improved; the PPE resin is added to improve the dimensional stability and the water resistance of the barrier layer, the PPE sub-chain contains a large number of aromatic ring structures, the molecular chain has strong sensibility, the resin has high mechanical strength, excellent creep resistance and high heat resistance, the vitrification temperature reaches 211 ℃, the melting point is 268 ℃, the shrinkage rate is low, and the dimensional stability is good.
The substrate layer is a polyethylene naphthalate layer and a fluoroplastic alloy layer; the polyethylene naphthalate layer is arranged on the bottom surface of the fluoroplastic alloy layer. By adopting the polyethylene naphthalate layer and the fluoroplastic alloy layer as the base layer structure, the surface of the metal plate can be effectively prevented from being damaged when the metal plate is subjected to laser cutting by laser; when cold plastic forming working procedures such as bending are carried out, the film cannot wrinkle and cannot be broken; good quality and good protection effect. The structure of the naphthalene of the polyethylene naphthalate layer is more easily planar, so that one of the most outstanding performances of PEN is good gas barrier performance, the naphthalene ring improves the aromaticity of macromolecules, the PEN has excellent thermal performance, the dual-ring structure of the naphthalene has strong ultraviolet light absorption capacity, the PEN has stable mechanical properties, and the elastic modulus, the strength, the creep and the service life of the PEN can still keep equivalent stability even under the conditions of high temperature and high pressure; the high-temperature color change resistance, the oxidation resistance, the wear resistance, the flexibility, the expansion strength and the impact strength of the protective film are further improved through the fluoroplastic alloy layer.
Wherein the fluoroplastic alloy layer comprises 54-60 wt% of polyvinylidene fluoride and 40-48 wt% of ethylene-chlorotrifluoroethylene copolymer; the performance of the fluoroplastic alloy layer can reach the best through reasonable compatibility of polyvinylidene fluoride and ethylene-chlorotrifluoroethylene copolymer.
Wherein the plasticizer is tricresyl phosphate. The compatibility of the tricresyl phosphate with organosilicon modified polyurethane, PPE resin and vinyl ethyl ether-benzyl acrylate copolymer is good, the flame retardance, mildew resistance, wear resistance, weather resistance and radiation resistance of the barrier layer are improved, and the flexibility of the film is increased.
Wherein the near infrared absorbent comprises 24-28 wt% of tin oxide, 15-20 wt% of EDTA-copper ammonium complex and 32-38 wt% of Ti3SnC2And 20 to 25 wt% (V)0.5Cr0.5)3AlC2. Tin oxide, EDTA-copper ammonium complex, Ti3SnC2And (V)0.5Cr0.5)3AlC2The components are used as absorbent together according to a reasonable proportionThe medium infrared blocking and reflecting capacity of the protective film is high.
Wherein the antioxidant comprises 40-55 wt% of pentaerythritol triacrylate and 50-60 wt% of 2, 4-dihydroxy benzophenone. Pentaerythritol triacrylate and 2, 4-dihydroxybenzophenone as antioxidants improve the thermal processability of the protective film, prevent aging of the polymer film and prolong its service life.
Wherein the number average molecular weight of the organosilicon modified polyurethane is 14000-16000 g/mol; if the number average molecular weight is less than 14000g/mol, the mechanical processing performance of the film is reduced, so that the film cannot meet the requirements on toughness and processing and forming quality; if the number average molecular weight is more than 16000g/mol, flexibility and heat resistance of the polymer are affected.
In the vinyl ethyl ether-benzyl acrylate copolymer, the content of vinyl ethyl ether is 40-50 wt%, and the content of benzyl acrylate is 50-60 wt%; the number average molecular weight of the vinyl ethyl ether-benzyl acrylate copolymer is 5500-6000 g/mol. In the vinyl ethyl ether-benzyl acrylate copolymer, the vinyl ethyl ether content and the benzyl acrylate content are limited, and the number average molecular weight is also limited, and if the vinyl ethyl ether-benzyl acrylate copolymer deviates from the numerical value range, the proportion of the additive to the whole system is unbalanced, so that the corresponding performance in the protective film is reduced.
Wherein the tin oxide, EDTA-copper ammonium complex, and Ti3SnC2And (V)0.5Cr0.5)3AlC2The particle size of (B) is 100-120 nm. By reacting tin oxide, EDTA-copper ammonium complex, Ti3SnC2And (V)0.5Cr0.5)3AlC2The particle size of (a) is limited, and the particle size range enables the protective film to be well balanced between high barrier property and high light transmission.
Specific examples and comparative examples and performance test results are listed below:
the following table lists the results of the performance tests of the examples and comparative examples.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (8)
1. The utility model provides a high resistant protection film that separates near-infrared, its characterized in that includes a substrate layer and the barrier layer on this substrate layer surface, the barrier layer comprises the material of following parts by weight:
in the vinyl ethyl ether-benzyl acrylate copolymer, the content of vinyl ethyl ether is 40-50 wt%, and the content of benzyl acrylate is 50-60 wt%; the number average molecular weight of the vinyl ethyl ether-benzyl acrylate copolymer is 5500-6000.
2. The high-barrier near-infrared protective film according to claim 1, wherein the substrate layer is a polyethylene naphthalate layer and a fluoroplastic alloy layer; the polyethylene naphthalate layer is arranged on the bottom surface of the fluoroplastic alloy layer.
3. The high-barrier near-infrared protective film according to claim 2, wherein the fluoroplastic alloy layer comprises 55 to 60 wt% of polyvinylidene fluoride and 40 to 45 wt% of ethylene-chlorotrifluoroethylene copolymer.
4. The high-barrier near-infrared protective film according to claim 1, wherein the plasticizer is tricresyl phosphate.
5. The high-barrier near-infrared protective film according to claim 1, wherein the near-infrared absorber comprises 24 to 28 wt% of tin oxide, 15 to 20 wt% of EDTA-cuprammonium complex, 32 to 38 wt% of Ti3SnC2And 20 to 25 wt% (V)0.5Cr0.5)3AlC2。
6. The high-barrier near-infrared protective film according to claim 1, wherein the antioxidant comprises 40 wt% of pentaerythritol triacrylate and 60 wt% of 2, 4-dihydroxybenzophenone.
7. The high-barrier near-infrared protective film according to claim 1, wherein the number average molecular weight of the silicone-modified polyurethane is 14000 to 16000.
8. The high-near-infrared-blocking protective film according to claim 5, wherein the tin oxide, EDTA-cuprammonium complex, Ti3SnC2And (V)0.5Cr0.5)3AlC2The particle size of (B) is 100-120 nm.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0079708A1 (en) * | 1981-11-09 | 1983-05-25 | Sumitomo Electric Industries Limited | Infrared transmitting material consisting of silver chloride and silver bromide |
WO2000027629A1 (en) * | 1998-11-06 | 2000-05-18 | 1334495 Ontario Inc. | Thermally reflective substrate coating |
US6366397B1 (en) * | 2000-03-10 | 2002-04-02 | Ntt Advanced Technology Corporation | Infrared radiation reflector and infrared radiation transmitting composition |
CN103269852A (en) * | 2010-10-25 | 2013-08-28 | 拜耳知识产权有限责任公司 | Multilayer plastic structure having low energy transmission |
-
2018
- 2018-02-11 CN CN201810141409.3A patent/CN108582936B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0079708A1 (en) * | 1981-11-09 | 1983-05-25 | Sumitomo Electric Industries Limited | Infrared transmitting material consisting of silver chloride and silver bromide |
WO2000027629A1 (en) * | 1998-11-06 | 2000-05-18 | 1334495 Ontario Inc. | Thermally reflective substrate coating |
US6366397B1 (en) * | 2000-03-10 | 2002-04-02 | Ntt Advanced Technology Corporation | Infrared radiation reflector and infrared radiation transmitting composition |
CN103269852A (en) * | 2010-10-25 | 2013-08-28 | 拜耳知识产权有限责任公司 | Multilayer plastic structure having low energy transmission |
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