WO2018180644A1 - 周面発光型の熱可塑性樹脂成形体 - Google Patents
周面発光型の熱可塑性樹脂成形体 Download PDFInfo
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- WO2018180644A1 WO2018180644A1 PCT/JP2018/010622 JP2018010622W WO2018180644A1 WO 2018180644 A1 WO2018180644 A1 WO 2018180644A1 JP 2018010622 W JP2018010622 W JP 2018010622W WO 2018180644 A1 WO2018180644 A1 WO 2018180644A1
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- cladding layer
- thermoplastic resin
- light
- core layer
- layer
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/036—Optical fibres with cladding with or without a coating core or cladding comprising multiple layers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S43/00—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights
- F21S43/20—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights characterised by refractors, transparent cover plates, light guides or filters
- F21S43/235—Light guides
- F21S43/236—Light guides characterised by the shape of the light guide
- F21S43/237—Light guides characterised by the shape of the light guide rod-shaped
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S43/00—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights
- F21S43/20—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights characterised by refractors, transparent cover plates, light guides or filters
- F21S43/235—Light guides
- F21S43/242—Light guides characterised by the emission area
- F21S43/245—Light guides characterised by the emission area emitting light from one or more of its major surfaces
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S43/00—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights
- F21S43/20—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights characterised by refractors, transparent cover plates, light guides or filters
- F21S43/235—Light guides
- F21S43/247—Light guides with a single light source being coupled into the light guide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S43/00—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights
- F21S43/20—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights characterised by refractors, transparent cover plates, light guides or filters
- F21S43/26—Refractors, transparent cover plates, light guides or filters not provided in groups F21S43/235 - F21S43/255
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0005—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being of the fibre type
- G02B6/001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being of the fibre type the light being emitted along at least a portion of the lateral surface of the fibre
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F13/00—Illuminated signs; Luminous advertising
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S8/00—Lighting devices intended for fixed installation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
- F21Y2101/00—Point-like light sources
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
Definitions
- the present invention is an improvement of a peripheral surface light emitting type thermoplastic resin molded body, and more specifically, it is flexibly bent along a shape of a decoration object or a decoration character or a decoration pattern formed in a linear shape.
- the present invention relates to a peripheral surface light emitting type thermoplastic resin molded article that can be used, has excellent light emitting performance, and suppresses yellowing of a light emission color at a site far from a light source.
- linear light emitters have been used in many light ornaments such as ornaments, illuminations, and electric signs, but neon lights that have been used for a long time as linear light emitters have a flexible body. Since it is composed of a poor glass tube, it is not possible to bend the linear light emitter along the curved portion of the wall surface or draw decorative characters or patterns.
- the present applicant has previously developed a soft light guide rod using an acrylic thermoplastic elastomer for the core layer and has filed a patent application, but in this soft light guide rod, further improvement of the light emitting performance has been made.
- a means for suppressing yellowing of the luminescent color (a phenomenon in which the luminescent color becomes yellowish as it becomes farther from the light source) is also required.
- the present invention has been made in view of the above problems, and its object is not only to bend flexibly in accordance with the method of light decoration and the object to be fixed, but also the overall emission luminance. It is another object of the present invention to provide a peripheral surface light emitting type thermoplastic resin molded body that can be improved in a continuous manner and that can also suppress yellowing of a light emission color at a site far from a light source.
- the present invention has at least a core layer 1 mainly composed of a thermoplastic elastomer and a first cladding layer 2 mainly composed of a thermoplastic resin having a refractive index smaller than that of the thermoplastic elastomer of the core layer 1.
- a light diffusing agent is added to each of the resin materials of the core layer 1 and the first cladding layer 2, and the total light transmittance of the first cladding layer 2 is less than 70%.
- a light diffusing agent in a ratio of 0.5 ppm to 10 ppm by weight with respect to the resin material of the core layer 1 in order to improve the light emitting performance.
- a bluing agent in order to suppress yellowing of the emission color, it is preferable to add a bluing agent to the resin material of the core layer 1 at a ratio of 0.1 ppm to 10 ppm by weight.
- the “blueing agent” means a blue or violet colorant that absorbs visible light in a yellow wavelength range.
- the thickness of the first cladding layer 2 is set to 0.1 to 0.3 mm in order to improve the light emission performance, and the light diffusing agent is added to the resin material of the first cladding layer 2 in a weight ratio of 0.05 to 1.5. It is preferable to add at a ratio of%.
- an acrylic thermoplastic elastomer is used as the main material of the core layer 1 and a main material of the first cladding layer 2 in order to obtain a thermoplastic resin molded article having excellent light emitting performance and impact resistance. It is preferable to use a fluororesin.
- titanium oxide or barium sulfate as a light diffusing agent to be added to the core layer 1 and the first cladding layer 2 in order to improve the light emitting performance.
- the same resin material as that of the first cladding layer 2 is used as a main material between the core layer 1 and the first cladding layer 2 in order to improve the light emission performance, and a light diffusing agent is added to the resin material. It is preferable to form a second cladding layer 3 that is not formed.
- the ratio of the thickness of the second cladding layer 3 to the first cladding layer 2 is set to 50% to 150% in order to further improve the light emission performance, and the first cladding layer 3
- the total thickness of 2 and the second clad layer 3 is 0.15 mm to 0.4 mm, and a light diffusing agent is added to the resin material of the first clad layer 2 at a ratio of 0.05 to 1.5% by weight.
- a soft light guide bar in the peripheral surface light emitting type thermoplastic resin molded article, can be formed by using an acrylic thermoplastic elastomer as the material of the core layer. It can be bent and fixed to an object to be decorated, or a decorative character or pattern can be formed. This makes it possible to use the light guide bar even in applications that could not be used conventionally.
- thermoplastic resin molded body of the present invention is configured by adding a light diffusing agent to the resin material of the core layer and the clad layer, respectively, thereby making it possible to improve the overall light emission luminance of the light guide rod.
- a light diffusing agent to the resin material of the core layer and the clad layer, respectively.
- the present invention not only can the problem of flexibility of the conventional peripheral light emitting type light guide rod be solved, but also the light emission performance and color unevenness can be obtained by utilizing the action of the light diffusing agent added to the core layer and the clad layer. Since the peripheral surface light emitting type thermoplastic resin molded article suitable for decoration use or display use can be provided, the practical utility value of the present invention is very high.
- thermoplastic resin molding of 1st embodiment of this invention It is a whole perspective view showing the thermoplastic resin molded object of 1st embodiment of this invention. It is process explanatory drawing showing the manufacturing method of the thermoplastic resin molding of 1st embodiment of this invention. It is an expanded end view showing the thermoplastic resin molding of the second embodiment of the present invention. It is a graph which shows the result of the light-emitting luminance test of the thermoplastic resin molding of this invention. It is a graph which shows the result of the chromaticity change test of the luminescent color of the thermoplastic resin molding of this invention. It is the graph which put together the test result of the impact resistance of the thermoplastic resin molding of this invention for every sample unit. It is the graph which put together the test result of the impact resistance of the thermoplastic resin molding of this invention in a temperature condition unit.
- thermoplastic resin molding [1] Basic structure of thermoplastic resin molded body First, the basic structure of the thermoplastic resin molded body will be described.
- a first cladding layer 2 mainly composed of a thermoplastic resin having a refractive index smaller than that of the thermoplastic elastomer is disposed around the core layer 1 mainly composed of a thermoplastic elastomer.
- a soft light guide rod type thermoplastic resin molded body F To form a soft light guide rod type thermoplastic resin molded body F.
- a predetermined amount of light diffusing agent is added to each resin material of the core layer 1 and the first cladding layer 2, and the addition of the light diffusing agent to the first cladding layer 2 causes the total light transmission of the first cladding layer 2. This is done so that the rate is less than 70%.
- thermoplastic resin molded body F As for the thermoplastic resin molded body F, as shown in FIG. 1, a light source is arranged at one or both ends of the thermoplastic resin molded body F so that light is incident on the end surface. By doing so, the peripheral surface of the thermoplastic resin molded body F is made to emit light and used. In the thermoplastic resin molded body F of the present embodiment, since a predetermined amount of light diffusing agent is added to the core layer 1 and the first cladding layer 2, light emission unevenness and Light can be emitted in a state where yellowing of the emission color is suppressed.
- an acrylic thermoplastic elastomer is used in the present embodiment.
- an acrylic thermoplastic elastomer a structure in which a polymer block (a1) mainly composed of a methacrylic ester unit is bonded to both ends of a polymer block (a2) mainly composed of an acrylate unit, That is, it is preferable to use an acrylic block copolymer having at least the structure of (a1)-(a2)-(a1) (“-” in the structure indicates a chemical bond).
- the molecular weight and composition of (a1) at both ends of (a2) may be the same or different from each other. Further, it may further contain a diblock body represented by (a1)-(a2).
- methacrylic acid ester used as the said methacrylic acid ester unit methyl methacrylate etc. can be mentioned, for example, Even if comprised from 1 type of these methacrylic acid esters, it may be comprised from 2 or more types. Good.
- the acrylate ester serving as the acrylate ester unit examples include methyl acrylate, n-butyl acrylate, and benzyl acrylate.
- the acrylate ester unit is composed of one of these acrylate esters. Also, it may be composed of two or more kinds, and is preferably composed of n-butyl acrylate, benzyl acrylate, or n-butyl acrylate and benzyl acrylate.
- the mass ratio (n-butyl acrylate / benzyl acrylate) is preferably in the range of 50/50 to 90/10. More preferably, it is in the range of 40-80 / 20.
- MMA-BA block copolymer As a material for the core layer, among them, a block copolymer of methyl methacrylate and butyl acrylate (hereinafter referred to as MMA-BA block copolymer) having a flexural modulus (ASTM D790) of 50 to 500 MPa, in particular.
- MMA-BA block copolymer having a flexural modulus (ASTM D790) of 50 to 500 MPa, in particular.
- ASTM D790 flexural modulus
- the first cladding layer With respect to the material of the first cladding layer 2, it is preferable to use a fluorine-based resin having a refractive index smaller than that of the core layer 1.
- ETFE copolymerization of ethylene and tetrafluoroethylene is used.
- EFEP a copolymer of hexafluoropropylene, tetrafluoroethylene, and ethylene.
- fluorine resins such as PVDF (polyvinylidene fluoride) and other resins can also be used.
- a resin having a melting point of 230 ° C. or less as the main material of the first cladding layer 2.
- the core layer 1 is highly compatible with the acrylic thermoplastic elastomer, so that the first clad layer 2 and the core layer 1 are less likely to be peeled off during use.
- ETFE is used as the fluororesin
- the elongation of ETFE 350 to 450%) is larger than that of PVDF (200 to 300%)
- the flexural modulus of ETFE 800 ( ⁇ 1000 MPa) is smaller than the bending elastic modulus (1400 to 1800 MPa) of PVDF, so that the clad layer is less likely to be wrinkled when the thermoplastic resin molded body F is bent.
- ETFE has a higher visible light transmittance than PVDF, the attenuation factor of light emission luminance can be kept low.
- Each numerical value of the elongation is a measured value according to ASTM D638, and each numerical value of the flexural modulus is a measured value according to ASTM D790.
- the light diffusing agent With respect to the light diffusing agent added to the core layer 1 and the first cladding layer 2, although powdered titanium oxide is used in this embodiment, barium sulfate can also be used. .
- the addition amount of the light diffusing agent it is preferable to add the light diffusing agent to the resin material of the core layer 1 so that the ratio by weight is 0.5 ppm to 10 ppm.
- the thickness of the first cladding layer 2 is 0.1 to 0.3 mm (preferably 0.2 mm to 0.3 mm)
- the light diffusing agent is 0.05 to 1.5% by weight with respect to the resin material of the first cladding layer 2. It is preferable to add so that it may become a ratio.
- the blueing agent yellowing of the emission color of the thermoplastic resin molded body F is suppressed by adding a blueing agent (blue pigment or purple pigment) to the core layer 1. Yes.
- the amount of the bluing agent is preferably added so that the weight ratio of the bluing agent to the resin material of the core layer 1 is 0.1 ppm to 10 ppm.
- thermoplastic resin molded body F has a round bar shape, but may be molded into a bar shape having a square cross section or a complicated cross section. Further, the shape of the thermoplastic resin molded body F includes a plate-like shape having a large aspect ratio of the cross-sectional shape.
- thermoplastic resin molding Next, the manufacturing method of the said thermoplastic resin molded object F is demonstrated.
- the core layer and the clad layer are simultaneously extruded from the mold of the extrusion molding machine, and after cooling and shaping in an integrated state, they are cut into a predetermined length for production.
- an acrylic thermoplastic elastomer with an MFR of 2 to 10 g / 10 min under the test conditions of a temperature of 190 ° C and a load of 5 kg is used as the main material of the core layer, and a melting point of 230 ° C or less is used as the main material of the cladding layer.
- the reference numeral 3 indicates the second cladding layer.
- the second clad layer 3 is formed between the core layer 1 and the first clad layer 2 to constitute a soft light guide rod type thermoplastic resin molded body F.
- a light diffusing agent is added to each resin material of the core layer 1 and the outer first cladding layer 2.
- the main material of the second cladding layer 3 is the same resin material as that of the first cladding layer 2 and is used without adding a light diffusing agent to the resin material.
- the conditions of the resin material that is the main material of the core layer 1 and the resin material that is the main material of the first cladding layer 2 are the same as those in the first embodiment. .
- the conditions of the light diffusing agent material, the amount of the light diffusing agent added to the resin material of the core layer 1, the manufacturing method, and the like are the same as in the first embodiment.
- the thickness of the cladding layer the ratio of the thickness of the second cladding layer 3 to the first cladding layer 2 is 50% to 150%, and the first cladding
- the total thickness of the layer 2 and the second cladding layer 3 is preferably 0.15 mm to 0.4 mm.
- the light diffusing agent is preferably added in a weight ratio of 0.05 to 1.5% with respect to the resin material of the first cladding layer 2 formed with this thickness. Also in this embodiment, the light diffusing agent is added to the first cladding layer 2 so that the total light transmittance of the two layers of the first cladding layer 2 and the second cladding layer 3 is less than 70%. preferable.
- Comparative Example 1 In Comparative Example 1, a round bar-shaped thermoplastic resin molded body was composed of a core layer and a first cladding layer having a thickness of 0.24 mm.
- the main material of the core layer is MMA-BA block copolymer with MFR 3.1g / 10min and flexural modulus 400MPa under the test conditions of temperature 190 °C and load 2.16kg.
- the main material is ETFE with a melting point of 192 ° C, elongation of 417%, flexural modulus of 959MPa, temperature of 297 ° C, load of 5kg and MFR of 78.6g / 10min. Made by extrusion.
- the total light transmittance of the first cladding layer was 65.2%.
- Comparative Example 2 In Comparative Example 2, a round bar-shaped thermoplastic resin molded body was composed of a core layer, a second cladding layer having a thickness of 0.1 mm, and a first cladding layer having a thickness of 0.11 mm. Further, the same MMA-BA block copolymer as that of Comparative Example 1 is used as the main material of the core layer, and the first cladding layer of Comparative Example 1 is used as the main material of the second cladding layer and the first cladding layer. Using the same ETFE, a thermoplastic resin molding was produced by coextrusion molding.
- the light diffusing agent is not added to the core layer, but the light diffusing agent is added only to the first cladding layer so that the weight ratio of the light diffusing agent to the resin material of the first cladding layer 2 is 1.3%. did.
- the total light transmittance of the two layers of the first cladding layer and the second cladding layer was 24.5%.
- Comparative Example 3 In Comparative Example 3, blue pigments and purple pigments, which are bluing agents, were added so that each pigment had a weight ratio of 1 ppm with respect to the resin material of the core layer, and an antioxidant was added to the core layer. An antioxidant was added to the resin material at a weight ratio of 0.1%. The total light transmittance of the two layers of the first cladding layer and the second cladding layer is 24.5%, and the other conditions are the same as in Comparative Example 2.
- Example 1 In Example 1, a round bar-shaped thermoplastic resin molded body was composed of a core layer and a first cladding layer having a thickness of 0.24 mm.
- the main material of the core layer is MMA-BA block copolymer with MFR 3.1g / 10min and flexural modulus 400MPa under the test conditions of temperature 190 °C and load 2.16kg.
- the main material is ETFE with a melting point of 192 ° C, elongation of 417%, flexural modulus of 959MPa, temperature of 297 ° C, load of 5kg and MFR of 78.6g / 10min. Made by extrusion.
- a light diffusing agent was added to the core layer so that the weight ratio of the light diffusing agent to the resin material of the core layer was 1 ppm.
- the light diffusing agent was added to the first cladding layer so that the weight ratio of the light diffusing agent to the resin material of the first cladding layer was 0.065%.
- a blue pigment and a purple pigment which are blueing agents, are added to the core layer so that each pigment has a weight ratio of 1 ppm to the resin material of the core layer, and an antioxidant is added to the core layer.
- the antioxidant was added to the resin material so that the ratio by weight was 0.1%.
- the total light transmittance of the first cladding layer was 65.2%.
- Example 2 In Example 2, a round rod-shaped thermoplastic resin molding was formed by forming a core layer, a second cladding layer having a thickness of 0.1 mm, and a first cladding layer having a thickness of 0.12 mm.
- the main material of the core layer is the same MMA-BA block copolymer as in Example 1, and the main material of the second cladding layer and the first cladding layer is the first cladding layer of Example 1.
- a thermoplastic resin molding was produced by coextrusion molding.
- the light diffusing agent was added to the core layer so that the weight ratio of the light diffusing agent to the resin material of the core layer was 0.5 ppm.
- the light diffusing agent is not added to the second cladding layer, the light diffusing agent is added only to the first cladding layer, and the light diffusing agent is 1.3% by weight with respect to the resin material of the first cladding layer.
- a blue pigment and a purple pigment which are blueing agents, are added to the core layer so that each pigment has a weight ratio of 1 ppm to the resin material of the core layer, and an antioxidant is added to the core layer. The antioxidant was added to the resin material so that the ratio by weight was 0.1%.
- the total light transmittance of the two layers of the first cladding layer and the second cladding layer was 18.2%.
- Example 3 In Example 3, the light diffusing agent was added to the core layer so that the weight ratio of the light diffusing agent to the resin material of the core layer was 0.8 ppm. The other conditions are the same as in Example 2.
- Example 4 In Example 4, a light diffusing agent was added to the core layer so that the weight ratio of the light diffusing agent to the resin material of the core layer was 1 ppm. The other conditions are the same as in Example 2.
- Example 5" In Example 5, a light diffusing agent was added to the core layer so that the light diffusing agent was 3 ppm by weight with respect to the resin material of the core layer. The other conditions are the same as in Example 2.
- thermoplastic resin molded body of Example 1 is more preferable than the thermoplastic resin molded body of Comparative Example 1 in the form of a single clad layer. It was also confirmed that the emission luminance was increased overall. Even in the case where the clad layer is composed of two layers, the thermoplastic resin molded bodies of Examples 2 to 5 may have a larger overall luminance than the thermoplastic resin molded bodies of Comparative Examples 2 and 3. It could be confirmed.
- the following table shows the detailed data of emission luminance and attenuation rate (unit of luminance is cd / m 2 ).
- the evaluation of the chromaticity change of the emission color is performed by measuring the emission color of the part 100 to 900 mm away from the light source using the CIE chromaticity diagram at 100 mm intervals, and the minimum x value and y value (close to blue) This was done by comparing the magnitude of the change from the coordinates) to the maximum x and y values (yellowish coordinates).
- Detailed data on the amount of change in chromaticity is shown below. As can be seen from the table below, except for Example 5, the x value and y value of the part close to the light source are minimum, and the x value and y value of the part far from the light source are maximum.
- Comparative Example 4 a peripheral surface light emitting type thermoplastic resin molded body was formed into a round bar shape having an outer diameter of 3.5 mm composed of a core layer and a first cladding layer.
- the material for the core layer polyoxypropylene triol and polyoxypropylene diol were used as the polymer polyol, and hexamethylene diisocyanate was used as the hydroxy group-reactive polyfunctional compound.
- Tetrafluoroethylene / hexafluoropropylene copolymer (FEP) was used as the material for the first cladding layer.
- FEP Tetrafluoroethylene / hexafluoropropylene copolymer
- the tube which comprises a 1st clad layer was filled with the material of the core layer in the mixed state, and it heat-hardened, and produced the surface emitting type thermoplastic resin molding.
- Comparative Example 5 the peripheral surface light emitting type thermoplastic resin molded body was formed into a round bar shape having an outer diameter of 3.0 mm composed of a core layer and a first cladding layer.
- the core layer is made of a polymerizable monomer (100: 1 by weight, a mixture of n-butyl methacrylate and triethylene glycol dimethacrylate) and bis (4-t-butylcyclohexyl) as a polymerization initiator. What added peroxydicarbonate was used. A tetrafluoroethylene-hexafluoropropylene copolymer was used as the material for the first cladding layer.
- the first clad layer formed into a tube shape with an extruder was pressurized and filled with a core-forming material to produce a peripheral surface light emitting type thermoplastic resin molded body.
- Example 6 the peripheral surface light emitting type thermoplastic resin molded body was formed into a round bar shape having an outer diameter of 3.5 mm composed of a core layer and a first cladding layer.
- the main material of the core layer is MMA-BA block copolymer with MFR 3.1g / 10min and flexural modulus 400MPa under the test conditions of temperature 190 °C and load 2.16kg.
- the main material is ETFE with a melting point of 192 ° C, elongation of 417%, flexural modulus of 959MPa, temperature of 297 ° C, load of 5kg and MFR of 78.6g / 10min. Made by extrusion.
- Example 6 manufactured by coextrusion molding using an acrylic thermoplastic elastomer as the main material of the core layer and using a fluorine resin as the main material of the first cladding layer It was confirmed that the sample No. 1 was less susceptible to deterioration in appearance and light emission performance due to impact than the samples of Comparative Examples 4 and 5 employing other materials and production methods.
- thermoplastic resin molded article of the present invention can be used by flexibly bending it according to the method of light decoration and the object to be fixed, as well as improving the overall emission luminance, and is far from the light source. Since yellowing of the luminescent color at the part can also be suppressed, it can be suitably used as a peripheral surface light emitting type thermoplastic resin molded article excellent in light emitting performance and impact resistance, particularly as a light guide rod.
- Such a light guide rod can be used as a lighting device for automobile interiors, specifically, auxiliary lighting installed around a vehicle instrument panel, around a car audio car navigation, a door panel, a console box, and a pillar. In addition, it can also be applied to courtesy lamps, map lamps, room lamps, floor lamps, foot lamps, ceiling lamps, and door lamps.
- automotive exterior lighting devices such as automotive headlamps, tail lamps, brake lamps, side marker lamps, and license plate lamps.
- transmission of sunlight optical signal transmission such as in-vehicle wiring, mobile wiring, and FA equipment wiring
- optical sensors such as liquid level sensors and pressure sensors, image guides for endoscopes, and light guides for optical equipment It can also be applied to.
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Abstract
Description
次に、本発明の第一実施形態について図1及び図2に基づいて説明する。なお図中、符号Fで指示するのものは、周面発光型の熱可塑性樹脂成形体であり、符号1で指示するものは、コア層である。また符号2で指示するものは、第一クラッド層である。
[1]熱可塑性樹脂成形体の基本構成について
まず熱可塑性樹脂成形体の基本構成について説明する。本実施形態では、図1に示すように、熱可塑性エラストマーを主材料とするコア層1の周囲に、この熱可塑性エラストマーよりも屈折率の小さい熱可塑性樹脂を主材料とする第一クラッド層2を形成して軟質導光棒型の熱可塑性樹脂成形体Fを構成している。またコア層1と第一クラッド層2の各樹脂材料にはそれぞれ所定量の光拡散剤を添加すると共に、第一クラッド層2に対する光拡散剤の添加は、第一クラッド層2の全光線透過率が70%未満となるように行っている。
また上記熱可塑性樹脂成形体Fについては、図1に示すように熱可塑性樹脂成形体Fの一端若しくは両端に光源を配置して端面に光を入射することにより、熱可塑性樹脂成形体Fの周面を発光させて使用する。なお本実施形態の熱可塑性樹脂成形体Fは、コア層1と第一クラッド層2に所定量の光拡散剤を添加しているため、光拡散剤が添加されていないものよりも発光ムラや発光色の黄変を抑えた状態で発光させることができる。
次に上記熱可塑性樹脂成形体Fの各構成要素について説明する。まず上記コア層1の材料に関しては、本実施形態ではアクリル系熱可塑性エラストマーを使用している。具体的には、アクリル系熱可塑性エラストマーとして、アクリル酸エステル単位を主体とする重合体ブロック(a2)の両末端にそれぞれメタクリル酸エステル単位を主体とする重合体ブロック(a1)が結合した構造、すなわち、(a1)-(a2)-(a1)の構造(構造中の「-」は、化学結合を示す)を少なくとも有する、アクリル系ブロック共重合体の使用が好ましい。ここで、(a2)の両端の(a1)の分子量、組成などは同じであってもよいし、相互に異なっていてもよい。また(a1)-(a2)で表されるジブロック体を更に含んでいてもよい。
上記第一クラッド層2の材料に関しては、屈折率がコア層1よりも小さいフッ素系樹脂の使用が好ましく、本実施形態ではETFE(エチレンとテトラフルオロエチレンの共重合体)やEFEP(ヘキサフルオロプロピレンとテトラフルオロエチレンとエチレンの共重合体)を使用している。但し、PVDF(ポリフッ化ビニリデン)等のフッ素系樹脂やその他の樹脂を使用することもできる。また第一クラッド層2の主材料には、コア層1との共押出成形を考慮して、融点が230℃以下の樹脂を使用するのが好ましい。
上記コア層1及び第一クラッド層2に添加する光拡散剤に関しては、本実施形態では粉末状の酸化チタンを使用しているが、硫酸バリウムを使用することもできる。また光拡散剤の添加量に関しては、コア層1の樹脂材料に対し光拡散剤が重量比で0.5ppm~10ppmの割合となるように添加するのが好ましい。また第一クラッド層2の厚みを0.1~0.3mm(好ましくは0.2mm~0.3mm)とする場合には、第一クラッド層2の樹脂材料に対し光拡散剤が重量比で0.05~1.5%の割合となるように添加するのが好ましい。
また本実施形態では、上記コア層1に対しブルーイング剤(青色顔料や紫色顔料)を添加することによって熱可塑性樹脂成形体Fの発光色の黄変を抑制している。なおブルーイング剤の添加量については、コア層1の樹脂材料に対しブルーイング剤が重量比で0.1ppm~10ppmの割合となるように添加することが好ましい。
また本実施形態では、熱可塑性樹脂成形体Fを丸棒型の形状としているが、角形断面や複雑な断面形状の棒状に成形することもできる。また熱可塑性樹脂成形体Fの形状には、断面形状の縦横比が大きい板状のものも含まれる。
次に上記熱可塑性樹脂成形体Fの製造方法について説明する。まず図2に示すように押出成形機の金型からコア層とクラッド層を同時に押出し、これらを一体化させた状態で冷却賦形を行った後、所定長さに切断して製造を行う。なお製造に際しては、コア層の主材に温度190℃・荷重5kgの試験条件下におけるMFRが2~10g/10minのアクリル系熱可塑性エラストマーを使用し、クラッド層の主材に融点が230℃以下のフッ素系樹脂を使用して、270℃以下の成形温度で共押出成形を行うのが好ましい。
「熱可塑性樹脂成形体の構成」
[1]導光棒の基本構成について
次に本発明の第二実施形態について図3に基づいて以下に説明する。なお図中、符号3で指示するのものは、第二クラッド層である。本実施形態では、コア層1と第一クラッド層2の間に第二クラッド層3を形成して軟質導光棒型の熱可塑性樹脂成形体Fを構成している。そしてコア層1と外側の第一クラッド層2の各樹脂材料にそれぞれ光拡散剤を添加している。また第二クラッド層3の主材料には、第一クラッド層2と同じ樹脂材料を使用し、樹脂材料に光拡散剤を添加せずに使用している。このような構成を採用することで熱可塑性樹脂成形体Fの均一発光性を向上させることができる。
一方、クラッド層の厚みに関しては、第一クラッド層2に対する第二クラッド層3の厚みの比率を50%~150%とし、第一クラッド層2と第二クラッド層3の合計厚みが0.15mm~0.4mmとなるようにするのが好ましい。そして、この厚みで形成される第一クラッド層2の樹脂材料に対し光拡散剤を重量比で0.05~1.5%の割合となるように添加するのが好ましい。なお本実施形態においても、第一クラッド層2に対する光拡散剤の添加は、第一クラッド層2と第二クラッド層3の二層の全光線透過率が70%未満となるように行うのが好ましい。
次に本発明の効果の実証試験(i)について説明する。まず本試験では、製造条件(コア層への光拡散剤及びブルーイング剤の添加、光拡散剤の添加量、クラッド層の構成)の異なる複数のサンプル(下記比較例1~3並びに実施例1~5)を作製し、これらの各サンプルについて、発光性能(発光輝度及び減衰率)、発光色の色度変化の評価を行った。なお本試験では、光拡散剤として粉末状の酸化チタンを使用した。以下に比較例1~3並びに実施例1~5の各サンプルの製造条件について記載する。
この比較例1では、丸棒状の熱可塑性樹脂成形体を、コア層と厚み0.24mmの第一クラッド層から構成した。またコア層の主材料には、温度190℃・荷重2.16kgの試験条件下におけるMFRが3.1g/10min、曲げ弾性率が400MPaのMMA-BAブロック共重合体を使用し、第一クラッド層の主材料には、融点192℃、伸度417%、曲げ弾性率959MPa、温度297℃・荷重5kgの試験条件下におけるMFRが78.6g/10minのETFEを使用して、熱可塑性樹脂成形体を共押出成形により作製した。またコア層には光拡散剤を添加せず、第一クラッド層にのみ光拡散剤を、第一クラッド層の樹脂材料に対し光拡散剤が重量比で0.065%の割合となるように添加した。なお第一クラッド層の全光線透過率は65.2%であった。
この比較例2では、丸棒状の熱可塑性樹脂成形体を、コア層と厚み0.1mmの第二クラッド層及び厚み0.11mmの第一クラッド層から構成した。またコア層の主材料には、比較例1と同じMMA-BAブロック共重合体を使用し、また第二クラッド層と第一クラッド層の主材料には、比較例1の第一クラッド層と同じETFEを使用して、熱可塑性樹脂成形体を共押出成形により作製した。またコア層には光拡散剤を添加せず、第一クラッド層にのみ光拡散剤を、第一クラッド層2の樹脂材料に対し光拡散剤が重量比で1.3%の割合となるように添加した。なお第一クラッド層と第二クラッド層の二層の全光線透過率は24.5%であった。
この比較例3では、ブルーイング剤である青色顔料及び紫色顔料を、コア層の樹脂材料に対し各顔料が重量比で1ppmの割合となるようにそれぞれ添加し、また酸化防止剤を、コア層の樹脂材料に対し酸化防止剤が重量比で0.1%の割合となるように添加した。なお第一クラッド層と第二クラッド層の二層の全光線透過率は24.5%であり、その他の条件は比較例2と同様である。
この実施例1では、丸棒状の熱可塑性樹脂成形体を、コア層と厚み0.24mmの第一クラッド層から構成した。またコア層の主材料には、温度190℃・荷重2.16kgの試験条件下におけるMFRが3.1g/10min、曲げ弾性率が400MPaのMMA-BAブロック共重合体を使用し、第一クラッド層の主材料には、融点192℃、伸度417%、曲げ弾性率959MPa、温度297℃・荷重5kgの試験条件下におけるMFRが78.6g/10minのETFEを使用して、熱可塑性樹脂成形体を共押出成形により作製した。
この実施例2では、丸棒状の熱可塑性樹脂成形体を、コア層と厚み0.1mmの第二クラッド層及び厚み0.12mmの第一クラッド層を形成して構成した。またコア層の主材料には、実施例1と同じMMA-BAブロック共重合体を使用し、また第二クラッド層と第一クラッド層の主材料には、実施例1の第一クラッド層と同じETFEを使用して、熱可塑性樹脂成形体を共押出成形により作製した。またコア層には、光拡散剤をコア層の樹脂材料に対し光拡散剤が重量比で0.5ppmの割合となるように添加した。
この実施例3においては、コア層に光拡散剤を、コア層の樹脂材料に対し光拡散剤が重量比で0.8ppmの割合となるように添加した。なおその他の条件は実施例2と同様である。
「実施例4」
この実施例4においては、コア層に光拡散剤を、コア層の樹脂材料に対し光拡散剤が重量比で1ppmの割合となるように添加した。なおその他の条件は実施例2と同様である。
「実施例5」
この実施例5においては、コア層に光拡散剤を、コア層の樹脂材料に対し光拡散剤が重量比で3ppmの割合となるように添加した。なおその他の条件は実施例2と同様である。
次に上記比較例1~3並びに実施例1~5のサンプルについて、寸法を長さ1000mm、直径6.3mmとして、光源からの距離が100~900mmの部位の発光輝度を100mm間隔で測定した。なお本試験では、発光輝度の測定を、サンプルの被測定部位から垂直方向に600mm離れた位置に分光放射輝度計(CS-2000コニカミノルタ製)を配置して行った。また光源には、駆動電流20mA、輝度25cd/m2、指向特性30°のものを使用した。測定条件をまとめた表を以下に示す。
次に上記比較例1~3並びに実施例1~5のサンプルについて、光源から近い側から遠い側にかけての発光色の色度変化を調べたところ、図5に示すようにクラッド層が一層から成る形態において、実施例1の熱可塑性樹脂成形体の方が比較例1の熱可塑性樹脂成形体よりも発光色の黄変が抑制されていることが確認できた。またクラッド層が二層から成る形態においても、実施例2~5の熱可塑性樹脂成形体の方が比較例2及び3の熱可塑性樹脂成形体よりも発光色の黄変が抑制されていることが確認できた。
次に本発明の効果の実証試験(ii)について説明する。本試験では、コア層とクラッド層に使用する材料、及び製法が異なる複数のサンプル(下記比較例4・5並びに実施例6)を作製し、これらの各サンプルについて、落球試験を行って試験後における各サンプルの発光性能(発光輝度)の評価を行った。なお本試験では、光拡散剤として粉末状の酸化チタンを使用した。以下に比較例4・5並びに実施例6の各サンプルの製造条件について説明する。
この比較例4では、周面発光型の熱可塑性樹脂成形体を、コア層と第一クラッド層から成る外径3.5mmの丸棒状に構成した。またコア層の材料には、ポリマーポリオールとしてポリオキシプロピレントリオールとポリオキシプロピレンジオールを使用し、ヒドロキシ基反応性多官能化合物としてヘキサメチレンジイソシアネートを使用した。また第一クラッド層の材料には、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体(FEP)を使用した。そして第一クラッド層を構成するチューブ内に、コア層の材料を混合した状態で充填して加熱硬化させることにより、周面発光型の熱可塑性樹脂成形体を作製した。
この比較例5では、周面発光型の熱可塑性樹脂成形体を、コア層と第一クラッド層から成る外径3.0mmの丸棒状に構成した。またコア層の材料には、重合性モノマー(重量比で100:1の、n-ブチルメタクリレートとトリエチレングリコールジメタクリレートとの混合液)に、重合開始剤としてビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネートを加えたものを使用した。また第一クラッド層の材料には、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体を使用した。そして押出し機でチューブ状に成形した第一クラッド層内に、コア形成材料を加圧充填して重合させることにより、周面発光型の熱可塑性樹脂成形体を作製した。
この実施例6では、周面発光型の熱可塑性樹脂成形体を、コア層と第一クラッド層から成る外径3.5mmの丸棒状に構成した。またコア層の主材料には、温度190℃・荷重2.16kgの試験条件下におけるMFRが3.1g/10min、曲げ弾性率が400MPaのMMA-BAブロック共重合体を使用し、第一クラッド層の主材料には、融点192℃、伸度417%、曲げ弾性率959MPa、温度297℃・荷重5kgの試験条件下におけるMFRが78.6g/10minのETFEを使用して、熱可塑性樹脂成形体を共押出成形により作製した。
次に上記落球試験の方法について説明する。本試験では、200mmに切断した各サンプルを、任意の温度(常温・-30℃・80℃)に約3時間放置した後、このサンプルの中央部に、質量約1040gの鋼球(サイズ2 1/2インチ)を306mmの高さから落下させて衝撃を与えた。なお試験は、厚さ約30mmの鉄板上に試料を設置して行った。
次に発光性能の評価方法について説明する。上記落球試験を行った各サンプルにおける落下点前、落下点、落下点後の部位の発光輝度を測定した。なお本試験では、発光輝度の測定を、サンプルの被測定部位から垂直方向に600mm離れた位置に分光放射輝度計(CS-2000コニカミノルタ製)を配置して行った。また光源には、駆動電流20mA、輝度25cd/m2、指向特性30°のものを使用した。
2 第一クラッド層
3 第二クラッド層
F 熱可塑性樹脂成形体
Claims (8)
- 熱可塑性エラストマーを主材料とするコア層(1)と、このコア層(1)の熱可塑性エラストマーよりも屈折率の小さい熱可塑性樹脂を主材料とする第一クラッド層(2)を少なくとも有し、かつ、これらコア層(1)と第一クラッド層(2)の各樹脂材料にそれぞれ光拡散剤が添加されており、第一クラッド層(2)の全光線透過率が70%未満であることを特徴とする周面発光型の熱可塑性樹脂成形体。
- コア層(1)の樹脂材料に対し光拡散剤が重量比で0.5ppm~10ppmの割合で添加されていることを特徴とする請求項1記載の周面発光型の熱可塑性樹脂成形体。
- コア層(1)の樹脂材料に対しブルーイング剤が重量比で0.1ppm~10ppmの割合で添加されていることを特徴とする請求項1または2に記載の周面発光型の熱可塑性樹脂成形体。
- 第一クラッド層(2)の厚みが0.1~0.3mmであり、かつ、この第一クラッド層(2)の樹脂材料に対し光拡散剤が重量比で0.05~1.5%の割合で添加されていることを特徴とする請求項1~3の何れか一つに記載の周面発光型の熱可塑性樹脂成形体。
- コア層(1)の主材料がアクリル系熱可塑性エラストマーであり、第一クラッド層(2)の主材料がフッ素系樹脂であることを特徴とする請求項1~4の何れか一つに記載の周面発光型の熱可塑性樹脂成形体。
- コア層(1)及び第一クラッド層(2)に添加される光拡散剤として酸化チタンまたは硫酸バリウムが使用されていることを特徴とする請求項1~5の何れか一つに記載の周面発光型の熱可塑性樹脂成形体。
- コア層(1)と第一クラッド層(2)の間に、第一クラッド層(2)と同じ樹脂材料を主材料とし、かつ、樹脂材料に光拡散剤が添加されていない第二クラッド層(3)が形成されていることを特徴とする請求項1~6の何れか一つに記載の周面発光型の熱可塑性樹脂成形体。
- 第一クラッド層(2)に対する第二クラッド層(3)の厚みの比率が50%~150%であり、かつ、第一クラッド層(2)と第二クラッド層(3)の合計厚みが0.15mm~0.4mmであって、第一クラッド層(2)の樹脂材料に対し光拡散剤が重量比で0.05~1.5%の割合で添加されていることを特徴とする請求項7記載の周面発光型の熱可塑性樹脂成形体。
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CA3058090A CA3058090C (en) | 2017-03-31 | 2018-03-16 | A circumferentially light-emitting type thermoplastic resin molded body |
CN201880016018.7A CN110383125A (zh) | 2017-03-31 | 2018-03-16 | 周面发光型的热塑性树脂成型体 |
EP18776795.9A EP3605170B1 (en) | 2017-03-31 | 2018-03-16 | Thermoplastic resin molding of peripheral surface light-emitting type |
ES18776795T ES2937909T3 (es) | 2017-03-31 | 2018-03-16 | Moldeado de resina termoplástica de tipo que emite luz superficial periféricamente |
JP2019509312A JP7083336B2 (ja) | 2017-03-31 | 2018-03-16 | 周面発光型の熱可塑性樹脂成形体 |
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JP2020112616A (ja) * | 2019-01-09 | 2020-07-27 | フクビ化学工業株式会社 | 周面発光型導光棒 |
JP2020112617A (ja) * | 2019-01-09 | 2020-07-27 | フクビ化学工業株式会社 | 周面発光型導光棒 |
JP2020166067A (ja) * | 2019-03-28 | 2020-10-08 | フクビ化学工業株式会社 | 周面発光型導光棒 |
JP7468302B2 (ja) | 2020-11-05 | 2024-04-16 | 東レ株式会社 | 照光プラスチック光ファイバおよび照光プラスチック光ファイバコード |
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KR20190129037A (ko) | 2019-11-19 |
EP3605170A1 (en) | 2020-02-05 |
CA3058090C (en) | 2023-01-03 |
JPWO2018180644A1 (ja) | 2020-02-06 |
US11086062B2 (en) | 2021-08-10 |
CA3058090A1 (en) | 2018-10-04 |
EP3605170B1 (en) | 2022-12-28 |
ES2937909T3 (es) | 2023-04-03 |
JP7083336B2 (ja) | 2022-06-10 |
EP3605170A4 (en) | 2020-06-03 |
CN110383125A (zh) | 2019-10-25 |
US20200018884A1 (en) | 2020-01-16 |
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