CN1320998C - Multilayer type thin plate - Google Patents
Multilayer type thin plate Download PDFInfo
- Publication number
- CN1320998C CN1320998C CNB021321787A CN02132178A CN1320998C CN 1320998 C CN1320998 C CN 1320998C CN B021321787 A CNB021321787 A CN B021321787A CN 02132178 A CN02132178 A CN 02132178A CN 1320998 C CN1320998 C CN 1320998C
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- Prior art keywords
- methyl methacrylate
- butadiene
- acrylonitrile
- thin plate
- plexiglass
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Classifications
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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
- B32B27/08—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 of synthetic resin
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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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
- B32B2307/584—Scratch 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
- B32B2319/00—Synthetic rubber
Abstract
The present invention relates to an outdoor multilayer type transparent thin plate, especially to an outdoor multilayer type transparent thin plate with a double-layer type structure or a three-layer type structure and having excellent impact-resistance, scratch-proof, durability and transparency properties, which comprises an outer layer of polymethyl methacrylate resin and an inner layer of methyl methacrylate-propylene-butadiene-styrene resin.
Description
Technical field
The present invention relates to a kind of outdoor multiple field transparent thin board, particularly a kind of outdoor multiple field transparent thin board with good shock-resistant, marresistance, durability and transparency.
Background technology
As a kind of traditional transparency and impact-resistant outdoor light sheet material of requiring, day fluffy such as being used for, be used for building the roof material and be used for soundproof wall.Usually mainly use Merlon and polymethyl methacrylate (PMMA) resin sheet, and also use PETG (PET) thin plate and polyvinyl chloride (PVC) thin plate suitable the time.
Therefore the Merlon thin plate has good mechanical performance, uses in the environment the most extensively out of doors, for example is used for soundproof wall, day fluffy etc., and still, it is easy to fade because of ultraviolet ray, and has relatively poor marresistance.In order to remedy these deficiencies, be added with the Merlon of extra quantity ultra-violet stabilizer and Merlon together with the thickness co-extruded of regulation to improve the durability on surface, and a kind of material of being made up of methyl methacrylate (MMA) compound or silicon compound carries out the thick gel coating of 5-30 μ m to be handled, with the raising marresistance, thereby increase surface strength.
But if out of doors after following a period of time of condition, material is damaged by the ultraviolet ray in the sunshine and has changed the chemical composition of material, and the adhesion strength between Merlon and the material surface handled with gel coating lowers.This causes the separation between them, and the effect that therefore strengthens marresistance reduces, and surface quality reduces.In addition, compare with other transparent materials, manufacturing expense is very high.
The polymethyl methacrylate thin plate has good durability, when being used for outdoor environment, fade hardly, and manufacturing expense is relatively low.But because its impact strength is too low, thereby easily owing to little external impact is broken, it is mainly used in those products that generally is not subjected to external impact, for example is used for outdoor sign, cheap soundproof wall etc.In order to remedy the low impact strength of polymethyl methacrylate; develop a kind of polymethyl methacrylate thin plate by adding acryl rubber as an impact reinforcing agent, but impact strength is restricted and manufacturing expense is very high with the HI high impact that increases impact strength a little.
The polyethyleneterephthalate thin plate has low manufacturing expense, still, when be exposed to outdoor long-time after, its physical property is destroyed by ultraviolet ray, and it has low heat distortion temperature, thereby under the environment of summer high-temperature, it can the sagging or distortion because of own wt.In addition, the polyvinyl chloride thin plate has good processing characteristics and low manufacturing expense, but it produces the chloride that can cause environmental problem, thereby its use is restricted in developed country.It also has low heat distortion temperature, thereby can produce distortion under the outdoor condition of high temperature.
Japan's publication discloses a kind of method for preparing thermoplastic multilayer formula thin plate for 2000-272056 number, this thin plate combines with polymethyl methacrylate remedying the durability of general acrylonitrile-butadiene-styrene resin, but its application is confined to opaque product.
Although the balance of the unique good initial physical performance of transparent propene nitrile-butadiene styrene resin thin plate, but the rubber constituent in the resin is damaged by the ultraviolet ray in the sunshine, and, when be exposed to outdoor long-time after, take place significantly to fade, physical property is damaged rapidly, so they can not be used for the open air, is confined to indoor use.
In addition, if thin plate is produced by mixed methyl methyl acrylate-acrylonitrile-butadiene-styrene resin and polymethacrylate resin, because different refraction index between methyl methacrylate-acrylonitrile-butadiene-styrene resin and polymethacrylate resin, it is opaque, thereby can not obtain required transparent resin.Up to now, the technology for preparing the multiple field transparent thin board with polymethyl methacrylate/methyl methacrylate-acrylonitrile-butadiene-styrene resin does not also develop.
Correspondingly, need exploitation to have the multiple field transparent thin board of good impact strength, marresistance, durability and transparency, thereby can use out of doors.
Summary of the invention
In order to address these problems, an object of the present invention is to provide a kind of outdoor multiple field transparent thin board of low manufacturing expense that has, it has transparency and impact strength, and compares with the Merlon thin plate, and it improves marresistance and durability significantly.In order to reach this purpose, the invention provides a kind of multilayer type thin plate, comprising:
(a) skin that includes polymethyl methacrylate (PMMA) resin; With
(b) internal layer that includes methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) (MABS) resin.
Now the present invention is elaborated.
The inventor has good marresistance in research, durability, when transparency and impact-resistant outdoor transparent thin board, verified good durability and marresistance can be by to polymethyl methacrylate and methyl methacrylate-acrylonitrile-butadiene-styrene resin hot melt co-extrusion PROCESS FOR TREATMENT and their are introduced skin obtain, and good impact strength can obtain by methyl methacrylate-acrylonitrile-butadiene-styrene resin being incorporated into internal layer, like this, can not expect the durability of using arbitrary these resins to obtain separately, marresistance, shock-resistant and transparency can be met simultaneously, and finishes the present invention.
Outdoor multiple field transparent thin board among the present invention is characterised in that, comprise that a skin and that includes plexiglass includes the internal layer of methyl methacrylate-acrylonitrile-butadiene-styrene resin, it has internal layer-outer field two-layer stratigraphic structure or skin-internal layer-outer field three-layer type formula structure like this.
Be used for the polymer that plexiglass of the present invention is the monomethyl methyl acrylate, it can prepare by independent polymerization methyl methacrylate, or by methyl methacrylate and other acrylate monomers, as styrene, cyclohexyl maleimide etc. waits copolymerization with polymerisation in bulk, suspension polymerisation or polymerisation in solution.
For polymethyl methacrylate, under final transparent thin board will be subjected to stress situation from external force or own wt hardly, can use and not contain alkyl acrylate rubber, or with other acrylic monomers, as the pure plexiglass of the copolymer of styrene, cyclohexyl maleimide etc.
But, when finished product is installed with the form of curved surface, if perhaps under the situation that can be subjected to a large amount of external force or self stress after the installation, because variation along with the time, may break in exquisite surface, be preferably the plexiglass that use is reinforced with alkyl acrylate rubber, to absorb stress.
For the reinforcing agent that is used for strengthening impact strength, the grafting in the above of alkyl acrylate rubber.To the plexiglass of per 100 parts of weight, the suitable 60 parts of weight of as many as of the content of alkyl acrylate rubber.
Alkyl acrylate rubber as reinforcing agent is a compound, comprises that at least a vitrification point is 0 ℃ or lower acrylic acid alkyl ester polymer, and the most suitable use butylacrylic acid.And, if necessary, can use butylacrylic acid rubber and other monomer, as the rubber enhancing copolymer of methacrylate, methyl methacrylate or styrene etc.
Rubber strengthens acrylic resin by methyl methacrylate and styrene or cyclohexyl maleimide etc., copolymerization under the situation that alkyl acrylate rubber exists for 10-60% weight.
If it is 10 parts of weight or still less that rubber strengthens rubber content in the plexiglass, it is not very satisfactory that rubber strengthens effect, when its content surpassed 60 parts of weight, transparency reduced and the expense of product increases and increased overall manufacturing expense.
Methyl methacrylate-the acrylonitrile-butadiene-styrene resin that is used for the present invention can prepare by the rubber polymer of copolymerization 8-30 part weight and the aromatic ethylene compound of 15-30 part weight, the vinyl cyanide compound of 15 parts of weight and the alkyl acrylate of 40-60 part weight; Or prepare by methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) polymer that mixed grafting has a high rubber content, this polymer is by the rubber polymer with 30-60 part weight, the aromatic ethylene compound of 10-15 part weight, the alkyl acrylate of 5 parts of weight or vinyl cyanide compound still less and 20-40 part weight and a polymer polymerizing and obtain, and this polymer gets a free aromatic ethylene compound, vinyl cyanide compound, alkyl acrylate, the polymer of one phenyl maleimide polymerization, control the cooperation ratio of monomer simultaneously, its refraction index and grafting methyl methacrylate-acrylonitrile-butadiene-styrene resin is consistent like this.
Although the impact strength of rubber polymer becomes big along with particle diameter usually and increases, if but particle diameter is too big, then be difficult to by the rubber polymer transmission ray in final methyl methacrylate-acrylonitrile-butadiene-styrene resin, therefore, transparency reduces rapidly.Simultaneously, along with particle diameter diminishes, transparency increases, but can not obtain satisfied impact strength.Therefore, the particle size that is used for preparing the rubber polymer of methyl methacrylate-acrylonitrile-butadiene-styrene resin is suitably for 0.2-0.4 μ m, and that more suitable is 0.25-0.35 μ m.
Composition for rubber polymer, be more suitable for using polybutadiene or Polybutadiene-styrene copolymer, though and unrestricted here with the monomer of polybutadiene copolymerization, be more suitable for having the monomer of the refraction index of scope between 1.50-1.55 for those make the rubber polymer of preparation.
For monomer as preparation grafting methyl methacrylate-acrylonitrile-butadiene-styrene resin, though it is also unrestricted here, but be more suitable for using styrene as aromatic ethylene compound, acrylonitrile is as vinyl cyanide compound, methyl methacrylate is as alkyl acrylate, just-and phenyl maleimide is as phenyl maleimide.
In the preparation of methyl methacrylate-acrylonitrile-butadiene-styrene resin, the refraction index that makes rubber polymer and matrix polymer is approximate mutually to be very important, because the refraction index of the monomer of the every kind of matrix that is contained influences the refraction index of matrix certainly, so the cooperation ratio of each monomer should be controlled so that the refraction index of matrix is close with the refraction index of rubber polymer.
Outdoor multiple field transparent thin board among the present invention is that the thin plate by the co-extrusion two-layer stratigraphic structure prepares, and this thin plate comprises the outer and monomethyl methyl acrylate-acrylonitrile-butadiene-styrene resin internal layer of a plexiglass; Perhaps prepare by the thin plate of co-extrusion with three layers structure, this thin plate comprises the upper and lower of plexiglass that rubber strengthens or general polymethyl methacrylate and the intermediate layer of monomethyl methyl acrylate-acrylonitrile-butadiene-styrene resin.Total thickness of outdoor multiple field transparent thin board is suitably for 0.8-15mm, and in total lamella thickness, the outer field thickness of each plexiglass is suitably for 0.1-1.5mm.If the outer field thickness of each plexiglass is less than 0.1mm, durability can not be met so, and if surpass 2mm, but the fine manufacturing expense of durability increases and impact strength decreased so.
Have good durability with the outer field plexiglass of multiple field transparent thin board out of doors, it can stop a large amount of ultraviolet rays, but ultraviolet ray can not be blocked fully.Therefore, if add light stabilizer at methyl methacrylate-acrylonitrile-butadiene-styrene resin internal layer, so the light stabilizer of Jia Ruing catch and remove by penetrate the plexiglass layer and enter the inside the atomic group that ultraviolet ray produced, perhaps its absorption ultraviolet ray changes it into heat energy, so that multilayer type thin plate fade or the damage of physical property minimizes, particularly in the intermediate layer of methyl methacrylate-acrylonitrile-butadiene-styrene resin, thereby improve the durability of thin plate.The kind of light stabilizer and quantity, although it is unrestricted, but also need select the feasible transparency of not damaging thin plate, and normally, at the outer field thickness of plexiglass is under 0.2mm or the situation still less, is fit to increase light stabilizer in methyl methacrylate-acrylonitrile-butadiene-styrene resin internal layer or in the plexiglass skin.
In addition, in hybrid resin, the antioxidant that adding processing that can be suitable needs in handling, heat stabilizer, lubricant, pigment etc.
In addition, outdoor multiple field transparent thin board of the present invention comprise plexiglass as skin to give case hardness, therefore marresistance obtains substantial raising, and it also further gives good surface gloss, durability, impact strength and transparency.
The present invention also provides a kind of method for preparing multi-layered sheet, and its step comprises:
A) use the extruder preparation to include the skin of polymethyl methacrylate (PMMA) resin;
B) use the extruder preparation to include the internal layer of methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) (MABS) resin; With
C) hot melt coextruded multilayer thin plate, it has the double-decker that is made of outer and internal layer, or the three-decker that is made of two skins and the internal layer between them.
According to the method for preparing multi-layered sheet provided by the invention, wherein plexiglass is the Polymerization of Methyl thing, methyl methacrylate and cinnamic copolymer, or the copolymer of methyl methacrylate and cyclohexyl maleimide.
According to the method for preparing multi-layered sheet provided by the invention, wherein to comprise the glass transition temperature that surpasses 60 parts of weight be 0 ℃ or the lower alkyl acrylate rubber as the collision reinforcing agent to plexiglass.
According to the method for preparing multi-layered sheet provided by the invention, wherein methyl methacrylate-acrylonitrile-butadiene-styrene resin is by the alkyl acrylate copolymer acquisition with the aryl ethylene compound of the rubber polymer of 8-30 part weight and 15-30 part weight, 15 parts of weight or vinyl cyanide compound still less and 40-60 part weight, and wherein rubber polymer is that particle diameter is that 0.2-0.4 micron and refractive index are polybutadiene or the Polybutadiene-styrene copolymer of 1.50-1.55.
According to the method for preparing multi-layered sheet provided by the invention, wherein total thickness of multi-layered sheet is the 0.8-15 millimeter, and the thickness of each outside plexiglass layer is the 0.1-1.5 millimeter.
The specific embodiment
The present invention sets forth in more detail with reference to the following examples.But these are to be used for illustrating of the present invention, and the present invention is not subjected to their restriction.
Embodiment 1
Design a Compound Extrusion machine, so that plexiglass thin plate layer and methyl methacrylate-acrylonitrile-butadiene-styrene resin thin plate layer becomes molten condition in independent extruder and by a die or stacked mutually after being divided into 3 a end of die.Methyl methacrylate-acrylonitrile-butadiene-styrene resin thin plate layer uses single extruder preparation of one 135 , temperature is set to 235 ℃ (feed hoppers), 240 ℃ (cylinder 1), 245 ℃ (cylinder 2), 245 ℃ (cylinder 3), 245 ℃ (cylinder 4) and 250 ℃ (die).The plexiglass thin plate layer uses single extruder preparation of one 55 , and temperature is set to 245 ℃ (feed hoppers), 255 ℃ (cylinder 1), 260 ℃ (cylinder 2), 260 ℃ (cylinder 3), 260 ℃ (cylinder 4) and 260 ℃ (die).And the temperature of roller is set to 90 ℃ (tops), 85 ℃ (middle part) and 80 ℃ (bottom).
Use complex extruder by above-mentioned preparation, rubber content is that 20% plexiglass (butyl acrylate-copolymer of methyl methacrylatestyrene) lower floor and upper thickness are controlled as 0.9mm, and rubber content be the THICKNESS CONTROL of methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS) internal layer of 15% at 4.2mm with preparation polymethyl methacrylate/methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) multiple field transparent thin board.
Embodiment 2
Methyl methacrylate/methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) multiple field transparent thin board adopts the method identical with embodiment 1 to prepare, just rubber content is that 20% plexiglass (butyl acrylate-copolymer of methyl methacrylatestyrene) lower floor and upper thickness are controlled as 0.45mm, and the THICKNESS CONTROL of methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS) internal layer is at 5.1mm.
Embodiment 3
Methyl methacrylate/methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) multiple field transparent thin board adopts the method preparation identical with embodiment 1, be rubber content be that 20% plexiglass lower floor and upper thickness are controlled as 0.2mm.
Embodiment 4
Methyl methacrylate/methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) multiple field transparent thin board adopts the method identical with embodiment 1 to prepare, just rubber content is that 20% plexiglass (butyl acrylate-copolymer of methyl methacrylatestyrene) lower floor and upper thickness are controlled as 0.1mm, and rubber content be the THICKNESS CONTROL of methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS) internal layer of 15% at 5.8mm, and methyl methacrylate-acrylonitrile-butadiene-styrene resin internal layer adds the Hisorb 770 (LG chemistry) of the Hisorb 327 (LG chemistry) of 0.15 part of weight and 0.15 part of weight as ultra-violet stabilizer.
Embodiment 5
Methyl methacrylate/methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) multiple field transparent thin board adopts the method identical with embodiment 1 to prepare, and is that pure plexiglass (methylmethacrylate polymer) lower floor and upper thickness are controlled as 0.2mm.
Embodiment 6
Methyl methacrylate/methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) multiple field transparent thin board adopts the method identical with embodiment 1 to prepare, just rubber content is that a certain layer thickness of 20% plexiglass layer is controlled as 0.45mm, and the THICKNESS CONTROL of methyl methacrylate-acrylonitrile-butadiene-styrene resin (MBS) internal layer is at 5.55mm.
Embodiment 7
Methyl methacrylate/methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) multiple field transparent thin board adopts the method identical with embodiment 1 to prepare, just rubber content is that a certain layer thickness of 20% plexiglass layer is controlled as 0.2mm, and rubber content is that the THICKNESS CONTROL of methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS) internal layer of 15% is at 2.8mm.
The comparative example 1
Preparation monomethyl methyl acrylate-acrylonitrile-butadiene-styrene resin thin plate, do not have the plexiglass layer, and only use methyl methacrylate-acrylonitrile-butadiene-styrene resin layer, use its thickness of extrusion device control to 6mm.
The comparative example 2
Used thickness is the commerce of a 6mm Merlon thin plate.
The comparative example 3
Used thickness is the Merlon thin plate that the hard conating of ultraviolet protection of the commerce usefulness of 6mm is handled.
The comparative example 4
Used thickness is the Merlon thin plate of ultraviolet protection of the commerce usefulness of 6mm.
The comparative example 5
Used thickness is the pure polymethyl methacrylate thin plate of the commerce usefulness of 6mm.
Test
For the polymethyl methacrylate/methyl methacrylate for preparing among embodiment 1-7 and the comparative example 1-5-acrylonitrile-butadiene-styrene (ABS) multiple field transparent thin board, assess be considered to very important physical property in transparent sound barrier, the result is shown in table 1 and table.
A) impact strength one cutting thin plate prepares sample, and measures the IZOD impact strength according to the ASTM D256 of ASTM.
B) durability-continuing test after 200 hours is used a durability measuring instrument (Q-UV panel) that the UVB lamp is housed, and at illumination condition: 8 hours * optically focused: 4 hours as 1 circulation, measures the change color (Δ E) before and after the thin plate test.
C) light transmission-with the wavelength is that the visible light of 600nm is measured.
D) marresistance-employing KSD3502 measuring method is measured pencil hardness.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | ||
| PMMA resin (skin) | Component | BA-MMA- ST | BA-MMA- ST | BA-MMA- ST | BA-MMA- ST | MMA | BA-MMA- ST | BA-MMA- ST |
| Rubber content | 20％ | 20％ | 20％ | 20％ | - | 20％ | 20％ | |
| Upper thickness | 0.9mm | 0.45mm | 0.2mm | 0.1mm | 0.2mm | 0.45mm | 0.2mm | |
| Lower thickness | 0.9mm | 0.45mm | 0.2mm | 0.1mm | 0.2mm | - | - | |
| Refraction index | 1.490 | 1.490 | 1.490 | 1.490 | 1.490 | 1.490 | 1.490 | |
| Transparent ABS resin (internal layer) | Component | MMA-AN- BD-ST | MMA-AN- BD-ST | MMA-AN- BD-ST | MMA-AN- BD-ST | MMA-AN- BD-ST | MMA-AN- BD-ST | MMA-BD- ST |
| Rubber content | 15％ | 22％ | 15％ | 15％ | 15％ | - | 15％ | |
| Thickness | 4.2mm | 5.1mm | 5.6mm | 5.8mm | 5.6mm | 5.55mm | 2.8mm | |
| Hisorb 327 | - | - | - | 0.15 | - | - | - | |
| Hisorb 770 | - | - | - | 0.15 | - | - | - | |
| Refraction index | 1.517 | 1.516 | 1.517 | 1.517 | 1.517 | 1.530 | 1.517 | |
| Impact strength | 9 | 12 | 13 | 14 | 12 | 14 | 12 | |
| Durability | 0.6 | 0.9 | 1.5 | 1.6 | 1.7 | 0.9 | 1.4 | |
| Transparency | 86 | 85 | 85 | 85 | 85 | 83 | 83 | |
| Marresistance | H | H | H | H | 2H | H | H | |
| Surface condition after the installation (surface plate) | Good | Good | Good | Good | Good | Good | Good | |
| Surface condition after the installation (curved panel) | Good | Good | Good | Good | Minute crack | Good | Good | |
| BA-MMA-ST (butyl acrylate-methyl methacrylate-styrene) copolymer: make MMA (methyl methacrylate) copolymer: make MMA-AN-BD-ST (methyl methacrylate-acrylonitrile-butadiene-styrene (ABS)) copolymer by LGMMA: Japanese electrochemistry by LGMMA. transparent ABS naval stores light stabilizer: Hisorb 327 (LG chemistry, benzotriazole light stabilizer), Hisorb 770 (LG chemistry, HALS light stabilizer) | ||||||||
Table 2
| The comparative example 1 | The comparative example 2 | The comparative example 3 | The comparative example 4 | The comparative example 5 | ||
| The PMMA resin | Component | - | - | - | - | MMA |
| Thickness | - | - | - | - | 6mm | |
| The transparent ABS resin | Component | MMA-AN-BD-ST | - | - | - | - |
| Thickness | 6mm | - | - | - | - | |
| The PC resin | Thickness | - | 6mm | 6mm | 6mm | - |
| Surface treatment | - | - | The UV protection, gel coating is handled | The UV protection, coating is handled | - | |
| Impact strength | 15 | 18 | 18 | 18 | 1.2 | |
| Durability | 10 | 10 | 1.8 | 1.8 | 0.6 | |
| Marresistance | 3B | 5B | 3H | 5NB | 2H | |
| Transparency | 76 | 85 | 85 | 85 | 92 | |
| Surface after the installation (surface plate) | Fade | Fade | Coating shedding | Good | Good | |
| Surface after the installation (curved panel) | Fade | Fade | Coating shedding | Good | The crack | |
From table 1 and table 2, can prove among the embodiment of the invention 1-7 to include plexiglass outer and comprise surface condition after impact strength, durability, marresistance, transparency and the installation that the methyl methacrylate-thin plate of acrylonitrile-butadiene-styrene resin internal layer has the thin plate that is better than comparative example 1-5.
As set forth, outdoor multiple field transparent thin board of the present invention has the good shock-resistant of the excellent durability of plexiglass and marresistance and methyl methacrylate-acrylonitrile-butadiene-styrene resin simultaneously, and have a manufacturing expense lower than Merlon thin plate, they do not need independent processing to handle to improve marresistance, and product quality can not degenerate as time goes by.In addition, because they have the impact strength higher than plexiglass, they are well suited for the outdoor transparent thin board that requires impact strength, durability and marresistance simultaneously, therefore, they are suitable for the construction material of requirement transparency, for example are used for transparent sound barrier, and it is fluffy etc.In addition, plexiglass in the multiple field transparent thin board of the present invention has identical methyl methacrylate composition with methyl methacrylate-acrylonitrile-butadiene-styrene resin, therefore this multiple field transparent thin board has superior compatibility, and remove after the methyl methacrylate composition, its total amount energy recycle applications is in opaque acrylonitrile-butadiene-styrene (ABS).
Claims (6)
1. method that is used to prepare multi-layered sheet, its step comprises:
A) use the extruder preparation to include the skin of polymethyl methacrylate (PMMA) resin;
B) use the extruder preparation to include the internal layer of methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) (MABS) resin; And
C) hot melt coextruded multilayer thin plate, it has the double-decker that is made of outer and internal layer, or the three-decker that is made of two skins and the internal layer between them.
2. the method for preparing multi-layered sheet as claimed in claim 1, it is characterized in that, described plexiglass is the Polymerization of Methyl thing, methyl methacrylate and cinnamic copolymer, or the copolymer of methyl methacrylate and cyclohexyl maleimide.
3. the method for preparing multi-layered sheet as claimed in claim 1 is characterized in that, it is 0 ℃ or the lower alkyl acrylate rubber as the collision reinforcing agent that described plexiglass comprises the glass transition temperature that surpasses 60 parts of weight.
4. the method for preparing multi-layered sheet as claimed in claim 1, it is characterized in that described methyl methacrylate-acrylonitrile-butadiene-styrene resin is by the alkyl acrylate copolymer acquisition with the aryl ethylene compound of the rubber polymer of 8-30 part weight and 15-30 part weight, 15 parts of weight or vinyl cyanide compound still less and 40-60 part weight.
5. the method for preparing multi-layered sheet as claimed in claim 5 is characterized in that, described rubber polymer is that particle diameter is that 0.2-0.4 micron and refractive index are polybutadiene or the Polybutadiene-styrene copolymer of 1.50-1.55.
6. the method for preparing multi-layered sheet as claimed in claim 1 is characterized in that, total thickness of described multi-layered sheet is the 0.8-15 millimeter, and the thickness of each outside plexiglass layer is the 0.1-1.5 millimeter.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2002-0010894A KR100428639B1 (en) | 2002-02-28 | 2002-02-28 | Multi-layered transparent sheet for exterior |
| KR20020010894 | 2002-02-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1440872A CN1440872A (en) | 2003-09-10 |
| CN1320998C true CN1320998C (en) | 2007-06-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021321787A Expired - Fee Related CN1320998C (en) | 2002-02-28 | 2002-08-28 | Multilayer type thin plate |
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| KR (1) | KR100428639B1 (en) |
| CN (1) | CN1320998C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20040019204A (en) * | 2002-08-27 | 2004-03-05 | 주식회사에버그로스 | Multi sheet with excellent UV resistance and impact resistance and Manufacturing thereof |
| CN101111529B (en) * | 2005-08-19 | 2010-07-28 | Lg化学株式会社 | Impact strength modifiers for polyvinyl chloride resin and method of preparing them |
| CN102089685B (en) * | 2008-07-16 | 2013-07-24 | 3M创新有限公司 | Multilayer optical film layer comprising blend of methyl methacrylate polymer and styrene acrylonitrile polymer |
| CN101672091B (en) * | 2008-09-09 | 2011-06-15 | 阿波罗（中国）有限公司 | Nano-titanium dioxide modified composite board |
| CN101670696B (en) * | 2009-06-19 | 2012-04-25 | 常州博双塑料有限公司 | Extruded acryl composite foam board and preparation method thereof |
| CN104812564B (en) * | 2012-11-28 | 2017-04-12 | 理研科技株式会社 | Article having glass-like design |
| JP6711065B2 (en) * | 2016-03-25 | 2020-06-17 | 日本ゼオン株式会社 | Optical film, polarizing plate, and display device |
| WO2019113809A1 (en) * | 2017-12-12 | 2019-06-20 | 陈斌 | Method for manufacturing flame-resistant composite board with convenient processing and decoration, and structure thereof |
| KR102179950B1 (en) * | 2018-09-03 | 2020-11-17 | 하현대 | Weatherproof two-layer resin sheet |
| CN111941973A (en) * | 2019-05-17 | 2020-11-17 | 洛阳尖端技术研究院 | Tear-resistant light-transmitting composite film, light-reflecting film, preparation method and application thereof |
| KR102117524B1 (en) * | 2020-05-06 | 2020-06-02 | 하현대 | Sheet comprising inline-laminated plastic film and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1007500B (en) * | 1985-11-14 | 1990-04-11 | 塞洛普拉斯特·克莱普施公司 | Method of producing composite boards or laminates |
| JP2000272056A (en) * | 1999-03-29 | 2000-10-03 | Shin Kobe Electric Mach Co Ltd | Multilayered sheet made of thermoplastic resin |
| WO2001096469A1 (en) * | 2000-06-14 | 2001-12-20 | General Electric Company | Transparent rubber modified styrenics compositions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59152854A (en) * | 1983-02-22 | 1984-08-31 | 旭化成株式会社 | Solid multilayer acryl sheet |
| DE4436381A1 (en) * | 1994-10-12 | 1996-04-18 | Roehm Gmbh | Composites of thermoplastic layers for sanitary articles |
| KR100228031B1 (en) * | 1997-06-18 | 1999-12-01 | 성재갑 | Acrylic transparent sheets having shock resistance and method for making same |
| KR200183252Y1 (en) * | 1999-12-27 | 2000-05-15 | 주식회사케이.피 | Two Layer Sheets of A.B.S & SAN. Two Layer Sheets of A.B.S & PMMA. |
-
2002
- 2002-02-28 KR KR10-2002-0010894A patent/KR100428639B1/en not_active IP Right Cessation
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1007500B (en) * | 1985-11-14 | 1990-04-11 | 塞洛普拉斯特·克莱普施公司 | Method of producing composite boards or laminates |
| JP2000272056A (en) * | 1999-03-29 | 2000-10-03 | Shin Kobe Electric Mach Co Ltd | Multilayered sheet made of thermoplastic resin |
| WO2001096469A1 (en) * | 2000-06-14 | 2001-12-20 | General Electric Company | Transparent rubber modified styrenics compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100428639B1 (en) | 2004-04-28 |
| CN1440872A (en) | 2003-09-10 |
| KR20030071266A (en) | 2003-09-03 |
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