WO2023166904A1 - Transparent thermoplastic polyurethane resin composition - Google Patents

Transparent thermoplastic polyurethane resin composition Download PDF

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Publication number
WO2023166904A1
WO2023166904A1 PCT/JP2023/003249 JP2023003249W WO2023166904A1 WO 2023166904 A1 WO2023166904 A1 WO 2023166904A1 JP 2023003249 W JP2023003249 W JP 2023003249W WO 2023166904 A1 WO2023166904 A1 WO 2023166904A1
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thermoplastic polyurethane
composition
polyurethane resin
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PCT/JP2023/003249
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French (fr)
Japanese (ja)
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元樹 倉上
秀行 初野
哲男 小林
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昭和化成工業株式会社
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Publication of WO2023166904A1 publication Critical patent/WO2023166904A1/en

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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
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • 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

Definitions

  • the present invention relates to a transparent thermoplastic polyurethane resin composition.
  • Patent Document 1 At least a terpolymer resin of methyl methacrylate/butadiene/styrene is added to 100 parts by weight of a transparent thermoplastic polyurethane single resin or mixed resin having a Shore A hardness of 90 or more.
  • a transparent polyurethane film obtained by calendering a thermoplastic polyurethane composition containing 5 to 20 parts by weight of the composition and having transparency with a total light transmittance of 85% or more is disclosed.
  • thermoplastic polyurethane resin composition having both excellent transparency and excellent releasability from the surfaces of kneaders and processing equipment. I've been to
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a transparent thermoplastic polyurethane resin composition having both excellent transparency and releasability.
  • a transparent thermoplastic polyurethane resin composition according to one embodiment of the present invention for solving the above problems has a Shore value measured immediately after pushing an indentation needle into a test piece in a method conforming to JIS K 6253-3:2012.
  • INDUSTRIAL APPLICABILITY According to the present invention, a transparent thermoplastic polyurethane resin composition having both excellent transparency and releasability is provided.
  • the transparent thermoplastic polyurethane resin composition may have a haze value of 19.0% or less as measured by a method conforming to JIS K 7136:2000. Further, the transparent thermoplastic polyurethane resin composition may have a tensile strength of 26 MPa or more as measured by a method conforming to JIS K 6251:2017. In addition, the transparent thermoplastic polyurethane resin composition may have cold resistance of -50°C or less as measured by a method conforming to JIS K 6723-1995. In addition, the transparent thermoplastic polyurethane resin composition has a melt flow rate of 29.0 g/10 min or less as measured under conditions of 190°C and a load of 10 kg by a method conforming to JIS K 7210-1:2014.
  • the transparent thermoplastic polyurethane resin composition after being melt-kneaded in a batch-type kneader, has a peelability in which the entire amount is peeled off from the kneader set at a temperature of 170° C. under its own weight. good too.
  • thermoplastic polyurethane resin composition having both excellent transparency and releasability is provided.
  • FIG. 2 is an explanatory diagram showing properties of thermoplastic polyurethane resins used in examples according to one embodiment of the present invention.
  • FIG. 2 is an explanatory diagram showing properties of a methyl methacrylate-butadiene-styrene copolymer resin used in examples according to one embodiment of the present invention.
  • FIG. 2 is an explanatory diagram showing part of the results of evaluation of properties of thermoplastic polyurethane resin compositions produced in examples according to one embodiment of the present invention.
  • FIG. 4 is an explanatory diagram showing another part of the results of evaluating the properties of the thermoplastic polyurethane resin composition produced in the examples according to one embodiment of the present invention.
  • thermoplastic polyurethane resin composition (hereinafter referred to as "this composition") according to one embodiment of the present invention will be described below. Note that the present invention is not limited to this embodiment.
  • the composition has a Shore A hardness (hereinafter referred to as "Shore A hardness (immediately after)”) measured immediately after the indenter is pushed into the test piece in accordance with JIS K 6253-3:2012.
  • a transparent thermoplastic polyurethane containing a methyl methacrylate-butadiene-styrene copolymer resin having a Shore D hardness measured immediately after being pushed hereinafter referred to as "Shore D hardness (immediately)" of 40 or more. It is a resin composition.
  • the present composition employs a specific thermoplastic polyurethane resin (hereinafter referred to as "TPU") having a Shore A hardness (immediately) of 90 or more, and methyl methacrylate- As a butadiene-styrene copolymer resin (hereinafter referred to as "MBS resin”), a specific one having a Shore D hardness (immediately) of 40 or more is adopted, and further, 30 parts by weight per 100 parts by weight of the TPU It is a transparent thermoplastic polyurethane resin composition containing the MBS resin in an amount within a specific range of 190 parts by weight or less.
  • TPU thermoplastic polyurethane resin
  • MBS resin methyl methacrylate- As a butadiene-styrene copolymer resin
  • the TPU contained in this composition is a thermoplastic polyurethane resin synthesized by a chemical reaction between polyisocyanate and polyol.
  • the MBS resin contained in the composition is a terpolymer of methyl methacrylate, butadiene and styrene.
  • the content of the MBS resin in the present composition is, for example, preferably 35 parts by weight or more, more preferably 40 parts by weight or more, and further preferably 45 parts by weight or more with respect to 100 parts by weight of TPU. It is preferably 48 parts by weight or more, and particularly preferably 50 parts by weight or more.
  • the content of the MBS resin in the present composition is, for example, preferably 180 parts by weight or less, more preferably 170 parts by weight or less, and 160 parts by weight or less with respect to 100 parts by weight of TPU. is more preferably 150 parts by weight or less, more preferably 140 parts by weight or less, more preferably 130 parts by weight or less, further preferably 120 parts by weight or less, 110 parts by weight It is more preferably 100 parts by weight or less, further preferably 90 parts by weight or less, further preferably 80 parts by weight or less, and 70 parts by weight or less. More preferably, it is particularly preferably 60 parts by weight or less.
  • the content of the MBS resin in the present composition may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the Shore A hardness (immediately) of TPU is not particularly limited as long as it is 90 or more and the effect of the present invention can be obtained, but for example, 91 or more is particularly preferable. Further, the Shore A hardness (immediately) of the TPU may be, for example, 100 or less, 97 or less, 95 or less, 93 or less, or 92 or less. There may be. The Shore A hardness (immediate) of the TPU may be specified by any combination of any of the above lower limits and any of the above upper limits. The higher the Shore A hardness (immediately) of the TPU, the higher the elasticity of the composition. improves. However, if the Shore A hardness (immediately after) of the TPU is too high, the composition becomes difficult to melt during processing, resulting in poor workability.
  • the refractive index measured by a method conforming to JIS K 7142:2014 for TPU is Although not particularly limited, for example, it may be 1.520 or more, preferably 1.525 or more, more preferably 1.530 or more, further preferably 1.535 or more, 1.537 or more is particularly preferable.
  • the refractive index of the TPU may be, for example, 1.560 or less, preferably 1.555 or less, more preferably 1.550 or less, and further preferably 1.545 or less. It is preferably 1.542 or less, and particularly preferably 1.542 or less.
  • the refractive index of the TPU may be specified by any combination of any of the above lower limits and any of the above upper limits.
  • the solubility parameter (hereinafter referred to as "SP value") of TPU is not particularly limited as long as the effect of the present invention can be obtained, but for example, 10.0 (cal/cm 3 ) 0.5 or more. 10.2 (cal/cm 3 ) 0.5 or more is preferable, 10.4 (cal/cm 3 ) 0.5 or more is more preferable, and 10.5 (cal/cm 3 ) is more preferable.
  • cm 3 ) is particularly preferably 0.5 or more.
  • the SP value of TPU may be, for example, 11.0 (cal/cm 3 ) 0.5 or less, 10.8 (cal/cm 3 ) 0.5 or less, or 10.8 (cal/cm 3 ) 0.5 or less. 7 (cal/cm 3 ) It may be 0.5 or less.
  • the SP value of the TPU may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • total light transmittance (hereinafter referred to as "total light transmittance") (%) measured by a method conforming to JIS K 7136:2000 for TPU is not particularly limited as long as the effects of the present invention can be obtained.
  • it may be 80.0% or more, preferably 85.0% or more, more preferably 88.0% or more, further preferably 89.0% or more, and 90.0% or more. 0% or more is particularly preferable.
  • the total light transmittance of TPU may be, for example, 99.0% or less, or 95.0% or less.
  • the total light transmittance of the TPU may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the total light transmittance of the TPU, the better the translucency of the present composition.
  • the parallel light transmittance (hereinafter referred to as "parallel light transmittance") (%) measured by a method conforming to JIS K 7136:2000 for TPU is not particularly limited as long as the effect of the present invention is obtained.
  • it may be 75.0% or more, preferably 80.0% or more, more preferably 84.0% or more, further preferably 85.0% or more, and 86.0% or more. 0% or more is particularly preferred.
  • the parallel light transmittance of TPU may be, for example, 99.0% or less, or may be 95.0% or less.
  • the parallel light transmittance of the TPU may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The greater the parallel light transmittance of the TPU, the more excellent the translucency of the present composition.
  • the diffuse light transmittance (hereinafter referred to as "diffuse light transmittance") (%) measured by a method conforming to JIS K 7136:2000 for TPU is not particularly limited as long as the effects of the present invention can be obtained.
  • it may be 1.5% or more, preferably 2.0% or more, more preferably 2.5% or more, further preferably 3.0% or more. 5% or more is particularly preferable.
  • the diffuse light transmittance of the TPU may be, for example, 15.0% or less, 10.0% or less, or 5.0% or less.
  • the diffuse light transmittance of the TPU may be specified by any combination of any of the above lower limits and any of the above upper limits. The higher the diffuse light transmittance of the TPU, the better the translucency of the composition.
  • the haze value (hereinafter referred to as "haze value”) (%) measured by a method conforming to JIS K 7136:2000 for TPU is not particularly limited as long as the effects of the present invention can be obtained. It may be 0% or less, preferably 7.0% or less, and particularly preferably 5.0% or less. Further, the haze value of TPU may be, for example, 1.0% or more.
  • the type of TPU contained in the present composition is not particularly limited as long as the effect of the present invention can be obtained, and for example, one or more selected from the group consisting of ether-based TPU, ester-based TPU, and polycarbonate-based TPU is preferably used.
  • ether type TPU is particularly preferably used. That is, ester-based TPUs are susceptible to hydrolysis due to, for example, heat and light, which may reduce tensile properties.
  • polycarbonate-based TPU for example, is relatively expensive, and thus has an aspect of inferior versatility.
  • the ether-based TPU has relatively high durability against heat and light, and is relatively inexpensive, so it is also excellent in versatility.
  • the ratio (%) of the weight of the ether-based TPU contained in the composition with respect to the total weight of the TPU contained in the composition is, for example, preferably 50% by weight or more, and preferably 60% by weight or more. More preferably, 70% by weight or more, still more preferably 80% by weight or more, still more preferably 90% by weight or more, further preferably 95% by weight or more, 100% by weight is particularly preferred.
  • the MBS resin contained in this composition has a Shore D hardness (immediately) of 40 or more.
  • the Shore D hardness (immediately) of the MBS resin is preferably 42 or more, more preferably 45 or more, still more preferably 48 or more, further preferably 50 or more, and 51 or more. It is more preferable to be 1, and 52 or more is particularly preferable.
  • the Shore D hardness (immediately after) of the MBS resin may be, for example, 70 or less, preferably 67 or less, more preferably 64 or less, and even more preferably 62 or less. It is more preferably 60 or less, more preferably 58 or less, even more preferably 56 or less, and particularly preferably 54 or less.
  • the Shore D hardness (immediately) of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the Shore D hardness (immediate) of the MBS resin, the better the tensile strength of the composition. However, if the Shore D hardness (immediately) is too high, the specific gravity of the present composition increases, resulting in poor lightweight properties.
  • Shore D hardness (hereinafter referred to as "Shore D hardness (after 10 seconds)") measured 10 seconds after the indenter is pushed into the test piece in accordance with MBS resin JIS K 6253-3:2012. ) is not particularly limited as long as the effect of the present invention can be obtained, but for example, it may be 30 or more, preferably 35 or more, more preferably 40 or more, and 43 or more It is more preferably 45 or more, and particularly preferably 47 or more.
  • the Shore D hardness (after 10 seconds) of the MBS resin may be, for example, 65 or less, preferably 59 or less, more preferably 55 or less, and further preferably 53 or less. It is preferably 50 or less, and particularly preferably 50 or less.
  • the Shore D hardness (after 10 seconds) of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the Shore D hardness (after 10 seconds) of the MBS resin, the better the tensile strength of the composition. However, if the Shore D hardness (after 10 seconds) is too high, the specific gravity of the present composition increases, resulting in poor lightweight properties.
  • the Shore A hardness (hereinafter referred to as "Shore A hardness (immediately)”) measured immediately after the indenter is pushed into the test piece in a method conforming to JIS K 6253-3:2012 of MBS resin is Although not particularly limited as long as the effect of the invention can be obtained, for example, it may be 85 or more, preferably 90 or more, more preferably 93 or more, and particularly preferably 95 or more.
  • the Shore A hardness (immediately after) of the MBS resin may be, for example, 99 or less, preferably 98 or less, and particularly preferably 97 or less.
  • the Shore A hardness (immediately after) of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the Shore A hardness (immediately) of the MBS resin, the better the tensile strength of the composition. However, if the Shore A hardness (immediately after) is too high, the specific gravity of the composition increases, resulting in poor lightweight properties.
  • Shore A hardness (hereinafter referred to as "Shore A hardness (after 10 seconds)" measured 10 seconds after the indenter is pushed into the test piece in accordance with MBS resin JIS K 6253-3:2012. ) is not particularly limited as long as the effect of the present invention can be obtained, but for example, it may be 85 or more, preferably 91 or more, more preferably 93 or more, and 95 or more More preferably, it is particularly preferably 96 or more.
  • the Shore A hardness (after 10 seconds) of the MBS resin may be, for example, 99 or less, preferably 98 or less, and particularly preferably 97 or less.
  • the Shore A hardness (after 10 seconds) of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the Shore A hardness (after 10 seconds) of the MBS resin, the better the tensile strength of the composition. However, if the Shore A hardness (after 10 seconds) is too high, the specific gravity of the present composition increases, resulting in poor lightweight properties.
  • Tensile strength of MBS resin measured by a method conforming to JIS K 6251:2017 value obtained by dividing the maximum tensile force recorded when the test piece is pulled until it breaks by the initial cross-sectional area of the test piece
  • tensile strength is not particularly limited as long as the effect of the present invention can be obtained, but for example, it may be 10 MPa or more, preferably 12 MPa or more, and 14 MPa or more. is more preferable, and 15 MPa or more is particularly preferable.
  • the tensile strength of the MBS resin may be, for example, 30 MPa or less, 25 MPa or less, 21 MPa or less, or 20 MPa or less.
  • the tensile strength of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the tensile strength, the better the mechanical strength. However, if the tensile strength is too high, the flexibility will be poor.
  • Elongation at break measured by a method conforming to JIS K 6251:2017 of MBS resin (value expressed as a ratio (%) of the elongation at the time the test piece is cut to the initial length) (hereinafter referred to as "elongation at break” (%) is not particularly limited as long as the effect of the present invention can be obtained, but for example, it may be 140% or more, preferably 150% or more, and more preferably 160% or more. It is preferably 170% or more, more preferably 180% or more, further preferably 190% or more, further preferably 200% or more, further preferably 210% or more. It is preferably 220% or more, more preferably 230% or more, and particularly preferably 240% or more.
  • the elongation at break of the MBS resin may be, for example, 400% or less, 350% or less, 300% or less, 280% or less, or 260%. It may be below.
  • the elongation at break of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The greater the elongation at break, the more excellent the extensibility. However, if the elongation at break is too large, the mechanical strength will be poor.
  • 100% modulus of MBS resin measured by a method conforming to JIS K 6251:2017 (the value obtained by dividing the tensile stress when 100% elongation is applied to the test piece by the initial cross-sectional area of the test piece) (hereinafter referred to as “ (referred to as "100% modulus”) (MPa) is not particularly limited as long as the effects of the present invention can be obtained, but may be, for example, 25.0 MPa or less, preferably 20.0 MPa or less. It is more preferably 0 MPa or less, further preferably 15.0 MPa or less, even more preferably 13.0 MPa or less, and particularly preferably 12.0 MPa or less.
  • the 100% modulus of the MBS resin may be, for example, 3.0 MPa or less, preferably 5.0 MPa or less, more preferably 6.0 MPa or less, and 7.0 MPa or less. is more preferable, 8.0 MPa or less is more preferable, and 9.0 MPa or less is particularly preferable.
  • the 100% modulus of the MBS resin may be specified by any combination of any of the above lower limits and any of the above upper limits. The smaller the 100% modulus, the better the flexibility. However, if the 100% modulus is too large, the mechanical strength will be poor.
  • Cold resistance (hereinafter referred to as "cold resistance") measured by a method conforming to JIS K 6723-1995 of MBS resin is not particularly limited as long as the effect of the present invention can be obtained.
  • ° C. or lower preferably -10 ° C. or lower, more preferably -20 ° C. or lower, even more preferably -25 ° C. or lower, and particularly preferably -30 ° C. or lower.
  • the refractive index of the MBS resin is not particularly limited as long as the effects of the present invention can be obtained. is more preferable, and 1.532 or more is particularly preferable.
  • the refractive index of the MBS resin may be, for example, 1.560 or less, preferably 1.555 or less, more preferably 1.550 or less, and preferably 1.545 or less. It is more preferably 1.540 or less, and particularly preferably 1.538 or less.
  • the refractive index of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the absolute value of the difference between the refractive index of the MBS resin contained in the present composition and the refractive index of the TPU contained in the present composition is not particularly limited as long as the effects of the present invention can be obtained, but for example 0.020. or less, preferably 0.015 or less, more preferably 0.010 or less, further preferably 0.007 or less, further preferably 0.006 or less, 0.005 or less is particularly preferable.
  • the SP value of the MBS resin is not particularly limited as long as the effects of the present invention can be obtained .
  • ) is preferably 0.5 or more, more preferably 9.4 (cal/cm 3 ) 0.5 or more, and even more preferably 9.5 (cal/cm 3 ) 0.5 or more , 9.6 (cal/cm 3 ) 0.5 or more is particularly preferable.
  • the SP value of the MBS resin may be, for example, 11.0 (cal/cm 3 ) 0.5 or less, 10.5 (cal/cm 3 ) 0.5 or less, or 10 .2 (cal/cm 3 ) 0.5 or less, 10.0 (cal/cm 3 ) 0.5 or less, or 9.8 (cal/cm 3 ) 0.5 or less may be
  • the SP value of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
  • the absolute value of the difference between the SP value of the MBS resin contained in the present composition and the SP value of the TPU contained in the present composition is not particularly limited as long as the effects of the present invention can be obtained, but is, for example, 1.5. or less, preferably 1.4 or less, more preferably 1.3 or less, further preferably 1.2 or less, further preferably 1.1 or less, 1.0 or less is particularly preferable.
  • the smaller the difference between the SP value of the MBS resin and the SP value of the TPU the better the compatibility between the MBS resin and the TPU in the present composition. As a result, for example, the transparency of the present composition is improved, and/or improved mechanical strength.
  • the specific gravity of MBS resin measured by a method conforming to JIS K 7112:1999 is not particularly limited as long as the effects of the present invention can be obtained, but is, for example, 1.05 or less. It is preferably 1.04 or less, more preferably 1.03 or less, even more preferably 1.02 or less, and particularly preferably 1.01 or less.
  • the specific gravity of the MBS resin may be, for example, 0.95 or more, 0.96 or more, 0.97 or more, or 0.98 or more. It may be 0.99 or more.
  • the specific gravity of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. As the specific gravity is smaller, the lightness is improved.
  • the Shore A hardness (immediately after) of the present composition is not particularly limited as long as the effects of the present invention can be obtained, but for example, it may be 85 or more, preferably 90 or more, and 91 or more. is more preferably 92 or more, more preferably 93 or more, and particularly preferably 94 or more.
  • the Shore A hardness (immediately after) of the present composition may be, for example, 99 or less, preferably 98 or less, more preferably 97 or less, and particularly preferably 96 or less.
  • the Shore A hardness (immediately) of the present composition may be specified by any combination of any of the above lower limits and any of the above upper limits. The higher the Shore A hardness (immediately), the better the tensile strength of the composition. However, if the Shore A hardness (immediately after) is too high, the specific gravity of the composition increases, resulting in poor lightweight properties of the composition.
  • the Shore A hardness (after 10 seconds) of the present composition is not particularly limited as long as the effects of the present invention can be obtained. It is more preferably 1, more preferably 92 or more, and particularly preferably 93 or more.
  • the Shore A hardness (after 10 seconds) of the present composition may be, for example, 99 or less, preferably 98 or less, more preferably 97 or less, and 96 or less. More preferably, it is particularly preferably 95 or less.
  • the Shore A hardness (after 10 seconds) of the present composition may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the Shore A hardness (after 10 seconds) of the composition, the better the tensile strength. However, if the Shore A hardness (after 10 seconds) is too high, the composition will have a high specific gravity and will be inferior in lightness.
  • the tensile strength of the present composition is not particularly limited as long as the effects of the present invention can be obtained. It is more preferably 23 MPa or more, more preferably 24 MPa or more, further preferably 25 MPa or more, further preferably 26 MPa or more, further preferably 27 MPa or more, and 28 MPa or more. is more preferably 29 MPa or more, more preferably 30 MPa or more, further preferably 31 MPa or more, still more preferably 32 MPa or more, further preferably 33 MPa or more, and 34 MPa It is more preferably 35 MPa or more, and particularly preferably 35 MPa or more.
  • the tensile strength of the present composition may be, for example, 50 MPa or less, 45 MPa or less, 40 MPa or less, 39 MPa or less, or 38 MPa or less. may be 37 MPa or less.
  • the tensile strength of the present composition may be specified by any combination of any of the above lower limits and any of the above upper limits. The higher the tensile strength, the better the mechanical strength. However, if the tensile strength is too high, the flexibility will be poor.
  • the elongation at break of the present composition is not particularly limited as long as the effects of the present invention can be obtained, but for example, it may be 300% or more, preferably 350% or more, and 380% or more. It is preferably 400% or more, more preferably 410% or more, still more preferably 420% or more, still more preferably 425% or more, and further preferably 430% or more. It is preferably 435% or more, more preferably 440% or more, further preferably 445% or more, further preferably 450% or more, further preferably 455% or more. It is preferably 460% or more, and particularly preferably 460% or more.
  • the elongation at break of the present composition may be, for example, 600% or less, 550% or less, 500% or less, 490% or less, or 480% or less. % or less, or 470% or less.
  • the elongation at break of the present composition may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The greater the elongation at break, the more excellent the extensibility. However, if the elongation at break is too large, the mechanical strength will be poor.
  • the 100% modulus of the present composition measured by a method conforming to JIS K 6251:2017 is not particularly limited as long as the effects of the present invention can be obtained. It is preferably 0 MPa or less, more preferably 17.0 MPa or less, even more preferably 15.0 MPa or less, further preferably 13.0 MPa or less, and further preferably 12.0 MPa or less. It is preferably 11.0 MPa or less, more preferably 10.0 MPa or less.
  • the 100% modulus of the present composition may be, for example, 3.0 MPa or less, preferably 5.0 MPa or less, more preferably 6.0 MPa or less, and 7.0 MPa or less. is more preferably 8.0 MPa or less, and particularly preferably 9.0 MPa or less.
  • the 100% modulus of the composition may be specified by any combination of any of the above lower limits and any of the above upper limits. The smaller the 100% modulus, the better the flexibility. However, if the 100% modulus is too large, the mechanical strength will be poor.
  • MFR Melt Flow Rate
  • preferably 8.0 g/10 min or more more preferably 8.5 g/10 min or more, even more preferably 9.0 g/10 min or more, 9.5 g/10 min more preferably 10.0 g/10 min or more, more preferably 10.5 g/10 min or more, even more preferably 11.0 g/10 min or more, and 11.5 g /10 min or more, more preferably 12.0 g/10 min or more, more preferably 12.5 g/10 min or more, further preferably 13.0 g/10 min or more, 13 It is more preferably 0.5 g/10 min or more, further preferably 14.0 g/10 min or more, still more preferably 14.5 g/10 min or more, and particularly preferably 15.0 g/10 min or more. .
  • the MFR of the present composition may be, for example, 35.0 g/10 min or less, preferably 30.0 g/10 min or less, more preferably 25.0 g/10 min or less. It is more preferably 0 g/10 min or less, further preferably 18.0 g/10 min or less, still more preferably 17.0 g/10 min or less, and particularly preferably 16.0 g/10 min or less.
  • the MFR of the present composition may be specified by any combination of any of the above lower limits and any of the above upper limits. If the MFR is too small, the fluidity will be poor and the workability will be poor. If the MFR is too large, the shape maintenance after processing will be poor.
  • the cold resistance of the present composition is not particularly limited as long as the effects of the present invention can be obtained, but for example, it may be 0 ° C. or lower, preferably -10 ° C. or lower, and -20 ° C. or lower. is more preferably -30°C or lower, more preferably -40°C or lower, even more preferably -50°C or lower, further preferably -55°C or lower, and -60°C. ° C. or less is more preferable, and -65° C. or less is particularly preferable.
  • the lower the cold resistance the better the cold resistance.
  • the total light transmittance (%) of the present composition is not particularly limited as long as the effect of the present invention is obtained, but may be, for example, 80.0% or more, preferably 81.0% or more. , is more preferably 82.0% or more, still more preferably 82.5% or more, and particularly preferably 83.0% or more. Moreover, the total light transmittance of the present composition may be, for example, 99.0% or less, or 95.0% or less. The total light transmittance of the present composition may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the total light transmittance, the better the translucency.
  • the haze value (%) of the present composition is not particularly limited as long as the effects of the present invention can be obtained. 0% or less, more preferably 18.5% or less, even more preferably 18.0% or less, even more preferably 17.5% or less, and 17.0% % or less is particularly preferred. Moreover, the haze value of the present composition may be, for example, 1.0% or more. The smaller the haze value, the less fogging and the better the transparency.
  • the specific gravity of the present composition is not particularly limited as long as the effects of the present invention can be obtained, but for example, it may be 1.15 or less, preferably 1.12 or less, and 1.10 or less. is more preferably 1.09 or less, and particularly preferably 1.08 or less.
  • the specific gravity of the present composition may be, for example, 0.95 or more, 1.00 or more, 1.02 or more, or 1.04 or more. , may be 1.05 or more, or may be 1.06 or more.
  • the specific gravity of the present composition may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The smaller the specific gravity, the more excellent the lightness.
  • the composition may further contain other components in addition to TPU and MBS resin.
  • Other components that the present composition may contain are not particularly limited as long as the effect of the present invention can be obtained.
  • the present composition mainly contains TPU and MBS resin. That is, the total of the parts by weight of the TPU and the parts by weight of the MBS resin with respect to 100 parts by weight of the present composition is, for example, preferably 50 parts by weight or more, more preferably 60 parts by weight or more, and 70 parts by weight. parts by weight or more, more preferably 80 parts by weight or more, more preferably 90 parts by weight or more, still more preferably 95 parts by weight or more, and preferably 96 parts by weight or more. It is more preferably 97 parts by weight or more, still more preferably 98 parts by weight or more, and particularly preferably 99 parts by weight or more.
  • the method for producing the present composition is not particularly limited as long as the present composition having the properties described above can be obtained. It is preferable to melt-knead 30 parts by weight or more and 190 parts by weight or less of an MBS resin having a Shore D hardness (immediately) of 40 or more with respect to 100 parts by weight of the TPU.
  • the temperature at which the TPU and the MBS resin are melt-kneaded is not particularly limited as long as the effects of the present invention can be obtained. C. or less, more preferably 150.degree. C. to 200.degree. C., and particularly preferably 160.degree. C. to 190.degree.
  • the batch type kneader is not particularly limited as long as the effects of the present invention can be obtained.
  • it may be a kneader with blades or a kneader without blades.
  • a batch type kneader for example, a pressure kneader or a Banbury mixer is preferably used.
  • the composition After being melt-kneaded in a batch-type kneader, the composition has a peeling property whereby the entire amount is peeled off from the kneader set at a temperature of 170°C by its own weight. That is, for example, when the present composition is produced by melt-kneading the TPU and the MBS resin in a batch kneader, When the kneader is set at a temperature of 170°C, the composition is separated from the inner surface of the kneader by its own weight and falls, and the entire amount can be recovered from the outlet. .
  • the present composition has excellent releasability in addition to excellent transparency. Therefore, the present composition has, for example, excellent releasability against processing equipment and excellent processability.
  • TPU #1 to #5 Five types of TPU (TPU #1 to #5) shown in FIG. 1A were used as the TPU.
  • MBS resins five types of MBS resins (MBS #1 to #5) shown in FIG. 1B were used.
  • a fatty acid amide was used as a lubricant, and a phosphorus-based stabilizer was used as a stabilizer.
  • the SP values shown in FIGS. 1A and 1B are obtained by using the turbidity titration method, document 1 (K. W. Suh, D. H. Clarke: J. Polymer Sci., A-1, 5 1671 (1967)) and document 2 ( K. W. Suh, J. M. Corbett: J. Appl.
  • thermoplastic polyurethane resin composition 100 parts by weight of any one of the above five types of TPU and a predetermined weight part of any one of the above five types of MBS resin are placed in a batch-type kneader kneader having a blade (volume of 3 L), A thermoplastic polyurethane resin composition was produced by adding 1 part by weight of a lubricant and 0.1 part by weight of a stabilizer and melt-kneading them at about 160° C. for 10 minutes.
  • acrylonitrile-styrene (AS) resin In place of MBS resin, acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, polymethyl methacrylate (PMMA) resin, core-shell type acrylic rubber (AR#1), transparent acrylic rubber (AR Compositions using #2) or silicone-acrylic rubber (SAR) were also prepared in the same manner.
  • a composition without MBS resin and a composition without TPU were also prepared in the same manner.
  • [result] 2A and 2B show the results of evaluating the properties of the composition.
  • the " ⁇ " mark indicates that the entire amount of the composition was detached and recovered from the inner surface of the kneader kneader by its own weight (that is, the releasability was excellent).
  • the "x" mark indicates that part or all of the composition adhered to the inner surface of the kneader kneader and was not peeled off (that is, the peelability was poor).
  • the "x" mark in the MFR column of FIG. 2 indicates that the composition did not flow even when a load was applied, and the MFR could not be measured.
  • compositions of Examples 1 to 3 containing 50 to 100 parts by weight of MBS#1 to 100 parts by weight of TPU#1 have high transparency (total light transmittance of 83.2% or more, haze value of 16.8% or less) and excellent peelability.
  • compositions of Examples C6 to C8 containing 5 to 20 parts by weight of MBS#1 to 100 parts by weight of TPU#1 had poor release properties, and the entire amount could be could not be recovered from Also, the compositions of Examples C6 to C8 had a large MFR of 30 g/10 min or more. Also, the composition of Example C8, which contained 20 parts by weight of MBS #1, had a higher haze value of 19.6%. Also, the composition of Example C9, which contained 200 parts by weight of MBS#1 to 100 parts by weight of TPU#1, had poor release properties and did not flow as measured by MFR.
  • Example C1 containing TPU#1 and not containing MBS resin had poor release properties, a large MFR of 37 g/10 min, and a high haze value of 19.7%.
  • the compositions of Examples C2-C5 containing any of the other four TPUs #2-#5 but no MBS resin also have satisfactory properties in terms of release, MFR or haze. I didn't.
  • the composition of Example C10, which contained MBS#1 but did not contain TPU showed no fluidity in MFR measurements and had poor mechanical strength in terms of tensile strength and elongation at break.
  • Example C11 which contained 100 parts by weight of TPU#1 and 20 parts by weight of MBS#2, had poor kneader releasability and a large MFR of 48 g/10 min.
  • the compositions of Examples C12 and 13 containing 50 or 80 parts MBS#2 to 100 parts TPU#1 have poor mechanical strength in terms of tensile strength and elongation at break, and poor cold resistance. It was inferior (about -45°C).
  • compositions of Examples C23 to C30 which contain 50 or 80 parts by weight of MBS#1 for 100 parts by weight of four TPUs #2 to #5 other than TPU#1, also have high haze values, It lacked transparency.

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Abstract

Provided is a transparent thermoplastic polyurethane resin composition combining excellent transparency with excellent releasability. The transparent thermoplastic polyurethane resin composition comprises a thermoplastic polyurethane resin having a Shore A hardness, as measured immediately after insertion of an indenter point into a test piece by a method in accordance with JIS K 6253-3:2012, of 90 or greater and a methyl methacrylate/butadiene/styrene copolymer resin having a Shore D hardness, as measured immediately after insertion of an indenter point into a test piece by the method in accordance with JIS K 6253-3:2012, of 40 or greater, the amount of the copolymer resin being 30-190 parts by weight per 100 parts by weight of the thermoplastic polyurethane resin.

Description

透明熱可塑性ポリウレタン樹脂組成物Transparent thermoplastic polyurethane resin composition
　本発明は、透明熱可塑性ポリウレタン樹脂組成物に関する。 The present invention relates to a transparent thermoplastic polyurethane resin composition.
　特許文献１には、透明性を有するショアＡ硬度が９０以上の熱可塑性ポリウレタンの単体樹脂又は混合樹脂１００重量部に対して、少なくとも、メタクリル酸メチル・ブタジエン・スチレンの３元共重合体樹脂を５～２０重量部配合した熱可塑性ポリウレタン組成物をカレンダー成形して得られ、全光線透過率８５％以上の透明性を有することを特徴とする透明ポリウレタンフィルムが記載されている。 In Patent Document 1, at least a terpolymer resin of methyl methacrylate/butadiene/styrene is added to 100 parts by weight of a transparent thermoplastic polyurethane single resin or mixed resin having a Shore A hardness of 90 or more. A transparent polyurethane film obtained by calendering a thermoplastic polyurethane composition containing 5 to 20 parts by weight of the composition and having transparency with a total light transmittance of 85% or more is disclosed.
特開２０１１－０２１１６７号公報JP 2011-021167 A
　一方、本発明の発明者らは、優れた透明性と、混錬機や加工装置の表面からの優れた剥離性とを兼ね備えた熱可塑性ポリウレタン樹脂組成物を実現するための技術的手段について検討を行ってきた。 On the other hand, the inventors of the present invention have investigated technical means for realizing a thermoplastic polyurethane resin composition having both excellent transparency and excellent releasability from the surfaces of kneaders and processing equipment. I've been to
　本発明は、上記課題に鑑みて為されたものであり、優れた透明性と剥離性とを兼ね備えた透明熱可塑性ポリウレタン樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a transparent thermoplastic polyurethane resin composition having both excellent transparency and releasability.
　上記課題を解決するための本発明の一実施形態に係る透明熱可塑性ポリウレタン樹脂組成物は、ＪＩＳ　Ｋ　６２５３－３：２０１２に準拠した方法において試験片に押針を押し込んだ直後に測定されるショアＡ硬さが９０以上である熱可塑性ポリウレタン樹脂と、前記熱可塑性ポリウレタン樹脂１００重量部に対して３０重量部以上、１９０重量部以下の、ＪＩＳ　Ｋ　６２５３－３：２０１２に準拠した方法において試験片に押針を押し込んだ直後に測定されるショアＤ硬さが４０以上であるメチルメタクリレート－ブタジエン－スチレン共重合体樹脂と、を含む。本発明によれば、優れた透明性と剥離性とを兼ね備えた透明熱可塑性ポリウレタン樹脂組成物が提供される。 A transparent thermoplastic polyurethane resin composition according to one embodiment of the present invention for solving the above problems has a Shore value measured immediately after pushing an indentation needle into a test piece in a method conforming to JIS K 6253-3:2012. A thermoplastic polyurethane resin having an A hardness of 90 or more, and 30 parts by weight or more and 190 parts by weight or less per 100 parts by weight of the thermoplastic polyurethane resin, a test piece in accordance with JIS K 6253-3:2012 and a methyl methacrylate-butadiene-styrene copolymer resin having a Shore D hardness of 40 or more measured immediately after the indenter is pushed into the hole. INDUSTRIAL APPLICABILITY According to the present invention, a transparent thermoplastic polyurethane resin composition having both excellent transparency and releasability is provided.
　また、前記透明熱可塑性ポリウレタン樹脂組成物は、ＪＩＳ　Ｋ　７１３６：２０００に準拠した方法により測定されるヘーズ値が、１９．０％以下であることとしてもよい。また、前記透明熱可塑性ポリウレタン樹脂組成物は、ＪＩＳ　Ｋ　６２５１：２０１７に準拠した方法により測定される引張強さが、２６ＭＰａ以上であることとしてもよい。また、前記透明熱可塑性ポリウレタン樹脂組成物は、ＪＩＳ　Ｋ　６７２３－１９９５に準拠した方法により測定される耐寒性が、マイナス５０℃以下であることとしてもよい。また、前記透明熱可塑性ポリウレタン樹脂組成物は、ＪＩＳ　Ｋ　７２１０－１：２０１４に準拠した方法により１９０℃、１０ｋｇ荷重の条件で測定されるメルトフローレイトが、２９．０ｇ／１０ｍｉｎ以下であることとしてもよい。また、前記透明熱可塑性ポリウレタン樹脂組成物は、バッチ式混錬機内において溶融混錬された後に、温度が１７０℃に設定された前記混錬機から自重で全量が剥離する剥離性を有することとしてもよい。 In addition, the transparent thermoplastic polyurethane resin composition may have a haze value of 19.0% or less as measured by a method conforming to JIS K 7136:2000. Further, the transparent thermoplastic polyurethane resin composition may have a tensile strength of 26 MPa or more as measured by a method conforming to JIS K 6251:2017. In addition, the transparent thermoplastic polyurethane resin composition may have cold resistance of -50°C or less as measured by a method conforming to JIS K 6723-1995. In addition, the transparent thermoplastic polyurethane resin composition has a melt flow rate of 29.0 g/10 min or less as measured under conditions of 190°C and a load of 10 kg by a method conforming to JIS K 7210-1:2014. good too. In addition, the transparent thermoplastic polyurethane resin composition, after being melt-kneaded in a batch-type kneader, has a peelability in which the entire amount is peeled off from the kneader set at a temperature of 170° C. under its own weight. good too.
　本発明によれば、優れた透明性と剥離性とを兼ね備えた透明熱可塑性ポリウレタン樹脂組成物が提供される。 According to the present invention, a transparent thermoplastic polyurethane resin composition having both excellent transparency and releasability is provided.
本発明の一実施形態に係る実施例において使用した熱可塑性ポリウレタン樹脂の特性を示す説明図である。FIG. 2 is an explanatory diagram showing properties of thermoplastic polyurethane resins used in examples according to one embodiment of the present invention. 本発明の一実施形態に係る実施例において使用したメチルメタクリレート－ブタジエン－スチレン共重合体樹脂の特性を示す説明図である。FIG. 2 is an explanatory diagram showing properties of a methyl methacrylate-butadiene-styrene copolymer resin used in examples according to one embodiment of the present invention. 本発明の一実施形態に係る実施例において製造した熱可塑性ポリウレタン樹脂組成物の特性を評価した結果の一部を示す説明図である。FIG. 2 is an explanatory diagram showing part of the results of evaluation of properties of thermoplastic polyurethane resin compositions produced in examples according to one embodiment of the present invention. 本発明の一実施形態に係る実施例において製造した熱可塑性ポリウレタン樹脂組成物の特性を評価した結果の他の一部を示す説明図である。FIG. 4 is an explanatory diagram showing another part of the results of evaluating the properties of the thermoplastic polyurethane resin composition produced in the examples according to one embodiment of the present invention.
　以下に、本発明の一実施形態に係る透明熱可塑性ポリウレタン樹脂組成物（以下、「本組成物」という。）について説明する。なお、本発明は本実施形態に限られるものではない。 A transparent thermoplastic polyurethane resin composition (hereinafter referred to as "this composition") according to one embodiment of the present invention will be described below. Note that the present invention is not limited to this embodiment.
　本組成物は、ＪＩＳ　Ｋ　６２５３－３：２０１２に準拠した方法において試験片に押針を押し込んだ直後に測定されるショアＡ硬さ（以下、「ショアＡ硬さ（直後）」という。）が９０以上である熱可塑性ポリウレタン樹脂と、当該熱可塑性ポリウレタン樹脂１００重量部に対して３０重量部以上、１９０重量部以下の、ＪＩＳ　Ｋ　６２５３－３：２０１２に準拠した方法において試験片に押針を押し込んだ直後に測定されるショアＤ硬さ（以下、「ショアＤ硬さ（直後）」という。）が４０以上であるメチルメタクリレート－ブタジエン－スチレン共重合体樹脂と、を含む、透明熱可塑性ポリウレタン樹脂組成物である。 The composition has a Shore A hardness (hereinafter referred to as "Shore A hardness (immediately after)") measured immediately after the indenter is pushed into the test piece in accordance with JIS K 6253-3:2012. 90 or more thermoplastic polyurethane resin and 30 parts by weight or more and 190 parts by weight or less with respect to 100 parts by weight of the thermoplastic polyurethane resin, in accordance with JIS K 6253-3:2012. A transparent thermoplastic polyurethane containing a methyl methacrylate-butadiene-styrene copolymer resin having a Shore D hardness measured immediately after being pushed (hereinafter referred to as "Shore D hardness (immediately)") of 40 or more. It is a resin composition.
　すなわち、本組成物は、熱可塑性ポリウレタン樹脂（Ｔｈｅｒｍｏｐｌａｓｔｉｃ　ｐｏｌｙｕｒｅｔｈａｎｅ）（以下、「ＴＰＵ」という。）として、９０以上のショアＡ硬さ（直後）を有する特定のものを採用し、且つ、メチルメタクリレート－ブタジエン－スチレン共重合体樹脂（以下、「ＭＢＳ樹脂」という。）として、４０以上のショアＤ硬さ（直後）を有する特定のものを採用し、さらに、当該ＴＰＵ１００重量部に対して、３０重量部以上、１９０重量部以下という特定範囲内の量で当該ＭＢＳ樹脂を含む、透明性を有する熱可塑性ポリウレタン樹脂組成物である。 That is, the present composition employs a specific thermoplastic polyurethane resin (hereinafter referred to as "TPU") having a Shore A hardness (immediately) of 90 or more, and methyl methacrylate- As a butadiene-styrene copolymer resin (hereinafter referred to as "MBS resin"), a specific one having a Shore D hardness (immediately) of 40 or more is adopted, and further, 30 parts by weight per 100 parts by weight of the TPU It is a transparent thermoplastic polyurethane resin composition containing the MBS resin in an amount within a specific range of 190 parts by weight or less.
　本組成物に含まれるＴＰＵは、ポリイソシアネートとポリオールとの化学反応により合成される、熱可塑性を有するポリウレタン樹脂である。また、本組成物に含まれるＭＢＳ樹脂は、メチルメタクリレートとブタジエンとスチレンとの三元共重合体である。 The TPU contained in this composition is a thermoplastic polyurethane resin synthesized by a chemical reaction between polyisocyanate and polyol. Also, the MBS resin contained in the composition is a terpolymer of methyl methacrylate, butadiene and styrene.
　本組成物におけるＭＢＳ樹脂の含有量は、ＴＰＵ１００重量部に対して、例えば、３５重量部以上であることが好ましく、４０重量部以上であることがより好ましく、４５重量部以上であることがさらに好ましく、４８重量部以上であることがさらに好ましく、５０重量部以上であることが特に好ましい。 The content of the MBS resin in the present composition is, for example, preferably 35 parts by weight or more, more preferably 40 parts by weight or more, and further preferably 45 parts by weight or more with respect to 100 parts by weight of TPU. It is preferably 48 parts by weight or more, and particularly preferably 50 parts by weight or more.
　また、本組成物におけるＭＢＳ樹脂の含有量は、ＴＰＵ１００重量部に対して、例えば、１８０重量部以下であることが好ましく、１７０重量部以下であることがより好ましく、１６０重量部以下であることがさらに好ましく、１５０重量部以下であることがさらに好ましく、１４０重量部以下であることがさらに好ましく、１３０重量部以下であることがさらに好ましく、１２０重量部以下であることがさらに好ましく、１１０重量部以下であることがさらに好ましく、１００重量部以下であることがさらに好ましく、９０重量部以下であることがさらに好ましく、８０重量部以下であることがさらに好ましく、７０重量部以下であることがさらに好ましく、６０重量部以下であることが特に好ましい。本組成物におけるＭＢＳ樹脂の含有量は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。 In addition, the content of the MBS resin in the present composition is, for example, preferably 180 parts by weight or less, more preferably 170 parts by weight or less, and 160 parts by weight or less with respect to 100 parts by weight of TPU. is more preferably 150 parts by weight or less, more preferably 140 parts by weight or less, more preferably 130 parts by weight or less, further preferably 120 parts by weight or less, 110 parts by weight It is more preferably 100 parts by weight or less, further preferably 90 parts by weight or less, further preferably 80 parts by weight or less, and 70 parts by weight or less. More preferably, it is particularly preferably 60 parts by weight or less. The content of the MBS resin in the present composition may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
　ＴＰＵのショアＡ硬さ（直後）は、９０以上であって本発明の効果が得られれば特に限られないが、例えば、９１以上であることが特に好ましい。また、ＴＰＵのショアＡ硬さ（直後）は、例えば、１００以下であってもよく、９７以下であってもよく、９５以下であってもよく、９３以下であってもよく、９２以下であってもよい。ＴＰＵのショアＡ硬さ（直後）は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。ＴＰＵのショアＡ硬さ（直後）が大きいほど、本組成物の弾性が高くなるため、例えば、本組成物の加工品は、外部からの負荷を受けた場合の変形性に優れ、耐久性が向上する。ただし、ＴＰＵのショアＡ硬さ（直後）が大きすぎると、本組成物は、加工時に溶融しにくくなるため、加工性に劣ることとなる。 The Shore A hardness (immediately) of TPU is not particularly limited as long as it is 90 or more and the effect of the present invention can be obtained, but for example, 91 or more is particularly preferable. Further, the Shore A hardness (immediately) of the TPU may be, for example, 100 or less, 97 or less, 95 or less, 93 or less, or 92 or less. There may be. The Shore A hardness (immediate) of the TPU may be specified by any combination of any of the above lower limits and any of the above upper limits. The higher the Shore A hardness (immediately) of the TPU, the higher the elasticity of the composition. improves. However, if the Shore A hardness (immediately after) of the TPU is too high, the composition becomes difficult to melt during processing, resulting in poor workability.
　ＴＰＵのＪＩＳ　Ｋ　７１４２：２０１４に準拠した方法により測定される屈折率（例えば、アッベ式屈折率計で測定される）（以下、「屈折率」という。）は、本発明の効果が得られれば特に限られないが、例えば、１．５２０以上であってもよく、１．５２５以上であることが好ましく、１．５３０以上であることがより好ましく、１．５３５以上であることがさらに好ましく、１．５３７以上であることが特に好ましい。 The refractive index measured by a method conforming to JIS K 7142:2014 for TPU (for example, measured with an Abbe refractometer) (hereinafter referred to as "refractive index") is Although not particularly limited, for example, it may be 1.520 or more, preferably 1.525 or more, more preferably 1.530 or more, further preferably 1.535 or more, 1.537 or more is particularly preferable.
　また、ＴＰＵの屈折率は、例えば、１．５６０以下であってもよく、１．５５５以下であることが好ましく、１．５５０以下であることがより好ましく、１．５４５以下であることがさらに好ましく、１．５４２以下であることが特に好ましい。ＴＰＵの屈折率は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。 Further, the refractive index of the TPU may be, for example, 1.560 or less, preferably 1.555 or less, more preferably 1.550 or less, and further preferably 1.545 or less. It is preferably 1.542 or less, and particularly preferably 1.542 or less. The refractive index of the TPU may be specified by any combination of any of the above lower limits and any of the above upper limits.
　ＴＰＵの溶解度パラメータ（Ｓｏｌｕｂｉｌｉｔｙ　Ｐａｒａｍｅｔｅｒ）（以下、「ＳＰ値」という。）は、本発明の効果が得られれば特に限られないが、例えば、１０．０（ｃａｌ／ｃｍ３）０．５以上であってもよく、１０．２（ｃａｌ／ｃｍ３）０．５以上であることが好ましく、１０．４（ｃａｌ／ｃｍ３）０．５以上であることがより好ましく、１０．５（ｃａｌ／ｃｍ３）０．５以上であことが特に好ましい。 The solubility parameter (hereinafter referred to as "SP value") of TPU is not particularly limited as long as the effect of the present invention can be obtained, but for example, 10.0 (cal/cm 3 ) 0.5 or more. 10.2 (cal/cm 3 ) 0.5 or more is preferable, 10.4 (cal/cm 3 ) 0.5 or more is more preferable, and 10.5 (cal/cm 3 ) is more preferable. cm 3 ) is particularly preferably 0.5 or more.
　また、ＴＰＵのＳＰ値は、例えば、１１．０（ｃａｌ／ｃｍ３）０．５以下であってもよく、１０．８（ｃａｌ／ｃｍ３）０．５以下であってもよく、１０．７（ｃａｌ／ｃｍ３）０．５以下であってもよい。ＴＰＵのＳＰ値は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。 Further, the SP value of TPU may be, for example, 11.0 (cal/cm 3 ) 0.5 or less, 10.8 (cal/cm 3 ) 0.5 or less, or 10.8 (cal/cm 3 ) 0.5 or less. 7 (cal/cm 3 ) It may be 0.5 or less. The SP value of the TPU may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
　ＴＰＵのＪＩＳ　Ｋ　７１３６：２０００に準拠した方法により測定される全光線透過率（以下、「全光線透過率」という。）（％）は、本発明の効果が得られれば特に限られないが、例えば、８０．０％以上であってもよく、８５．０％以上であることが好ましく、８８．０％以上であることがより好ましく、８９．０％以上であることがさらに好ましく、９０．０％以上であることが特に好ましい。また、ＴＰＵの全光線透過率は、例えば、９９．０％以下であってもよく、９５．０％以下であってもよい。ＴＰＵの全光線透過率は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。ＴＰＵの全光線透過率が大きいほど、本組成物は透光性に優れる。 The total light transmittance (hereinafter referred to as "total light transmittance") (%) measured by a method conforming to JIS K 7136:2000 for TPU is not particularly limited as long as the effects of the present invention can be obtained. For example, it may be 80.0% or more, preferably 85.0% or more, more preferably 88.0% or more, further preferably 89.0% or more, and 90.0% or more. 0% or more is particularly preferable. Further, the total light transmittance of TPU may be, for example, 99.0% or less, or 95.0% or less. The total light transmittance of the TPU may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the total light transmittance of the TPU, the better the translucency of the present composition.
　ＴＰＵのＪＩＳ　Ｋ　７１３６：２０００に準拠した方法により測定される平行光線透過率（以下、「平行光線透過率」という。）（％）は、本発明の効果が得られれば特に限られないが、例えば、７５．０％以上であってもよく、８０．０％以上であることが好ましく、８４．０％以上であることがより好ましく、８５．０％以上であることがさらに好ましく、８６．０％以上であることが特に好ましい。また、ＴＰＵの平行光線透過率は、例えば、９９．０％以下であってもよく、９５．０％以下であってもよい。ＴＰＵの平行光線透過率は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。ＴＰＵの平行光線透過率が大きいほど、本組成物は透光性に優れる。 The parallel light transmittance (hereinafter referred to as "parallel light transmittance") (%) measured by a method conforming to JIS K 7136:2000 for TPU is not particularly limited as long as the effect of the present invention is obtained. For example, it may be 75.0% or more, preferably 80.0% or more, more preferably 84.0% or more, further preferably 85.0% or more, and 86.0% or more. 0% or more is particularly preferred. Further, the parallel light transmittance of TPU may be, for example, 99.0% or less, or may be 95.0% or less. The parallel light transmittance of the TPU may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The greater the parallel light transmittance of the TPU, the more excellent the translucency of the present composition.
　ＴＰＵのＪＩＳ　Ｋ　７１３６：２０００に準拠した方法により測定される拡散光線透過率（以下、「拡散光線透過率」という。）（％）は、本発明の効果が得られれば特に限られないが、例えば、１．５％以上であってもよく、２．０％以上であることが好ましく、２．５％以上であることがより好ましく、３．０％以上であることがさらに好ましく、３．５％以上であることが特に好ましい。また、ＴＰＵの拡散光線透過率は、例えば、１５．０％以下であってもよく、１０．０％以下であってもよく、５．０％以下であってもよい。ＴＰＵの拡散光線透過率は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。ＴＰＵの拡散光線透過率が大きいほど、本組成物は透光性に優れる。 The diffuse light transmittance (hereinafter referred to as "diffuse light transmittance") (%) measured by a method conforming to JIS K 7136:2000 for TPU is not particularly limited as long as the effects of the present invention can be obtained. For example, it may be 1.5% or more, preferably 2.0% or more, more preferably 2.5% or more, further preferably 3.0% or more. 5% or more is particularly preferable. Further, the diffuse light transmittance of the TPU may be, for example, 15.0% or less, 10.0% or less, or 5.0% or less. The diffuse light transmittance of the TPU may be specified by any combination of any of the above lower limits and any of the above upper limits. The higher the diffuse light transmittance of the TPU, the better the translucency of the composition.
　ＴＰＵのＪＩＳ　Ｋ　７１３６：２０００に準拠した方法により測定されるヘーズ値（以下、「ヘーズ値」という。）（％）は、本発明の効果が得られれば特に限られないが、例えば、２０．０％以下であってもよく、７．０％以下であることが好ましく、５．０％以下であることが特に好ましい。また、ＴＰＵのヘーズ値は、例えば、１．０％以上であってもよい。なお、ヘーズ値は、次の式により算出される：ヘーズ値Ｈ（％）＝Ｔｄ／Ｔｔ×１００（当該式において、Ｔｔは全光線透過率（％）であり、Ｔｄは拡散光線透過率（％）である。）。ＴＰＵのヘーズ値が小さいほど、曇りが低減され、本組成物は透明性に優れる。 The haze value (hereinafter referred to as "haze value") (%) measured by a method conforming to JIS K 7136:2000 for TPU is not particularly limited as long as the effects of the present invention can be obtained. It may be 0% or less, preferably 7.0% or less, and particularly preferably 5.0% or less. Further, the haze value of TPU may be, for example, 1.0% or more. The haze value is calculated by the following formula: Haze value H (%) = Td/Tt x 100 (wherein Tt is the total light transmittance (%) and Td is the diffuse light transmittance ( %).). The smaller the haze value of the TPU, the less the haze and the better the transparency of the composition.
　本組成物に含まれるＴＰＵの種類は、本発明の効果が得られれば特に限られず、例えば、エーテル系ＴＰＵ、エステル系ＴＰＵ、及びポリカーボネート系ＴＰＵからなる群より選択される１以上が好ましく用いられるが、エーテル系ＴＰＵが特に好ましく用いられる。すなわち、エステル系ＴＰＵは、例えば、熱や光によって加水分解が起きやすいため、引張特性が低下することがある。また、ポリカーボネート系ＴＰＵは、例えば、比較的高価であるため汎用性に劣る側面がある。これらに対し、エーテル系ＴＰＵは、熱や光に対する耐久性が比較的高く、且つ比較的安価であるため、汎用性にも優れる。 The type of TPU contained in the present composition is not particularly limited as long as the effect of the present invention can be obtained, and for example, one or more selected from the group consisting of ether-based TPU, ester-based TPU, and polycarbonate-based TPU is preferably used. However, ether type TPU is particularly preferably used. That is, ester-based TPUs are susceptible to hydrolysis due to, for example, heat and light, which may reduce tensile properties. In addition, polycarbonate-based TPU, for example, is relatively expensive, and thus has an aspect of inferior versatility. On the other hand, the ether-based TPU has relatively high durability against heat and light, and is relatively inexpensive, so it is also excellent in versatility.
　本組成物に含まれるＴＰＵの総重量に対する、本組成物に含まれるエーテル系ＴＰＵの重量の割合（％）は、例えば、５０重量％以上であることが好ましく、６０重量％以上であることがより好ましく、７０重量％以上であることがさらに好ましく、８０重量％以上であることがさらに好ましく、９０重量％以上であることがさらに好ましく、９５重量％以上であることがさらに好ましく、１００重量％であることが特に好ましい。 The ratio (%) of the weight of the ether-based TPU contained in the composition with respect to the total weight of the TPU contained in the composition is, for example, preferably 50% by weight or more, and preferably 60% by weight or more. More preferably, 70% by weight or more, still more preferably 80% by weight or more, still more preferably 90% by weight or more, further preferably 95% by weight or more, 100% by weight is particularly preferred.
　本組成物に含まれるＭＢＳ樹脂は、上述のとおり、４０以上のショアＤ硬さ（直後）を有する。ＭＢＳ樹脂のショアＤ硬さ（直後）は、４２以上であることが好ましく、４５以上であることがより好ましく、４８以上であることがさらに好ましく、５０以上であることがさらに好ましく、５１以上であることがさらに好ましく、５２以上であることが特に好ましい。 As described above, the MBS resin contained in this composition has a Shore D hardness (immediately) of 40 or more. The Shore D hardness (immediately) of the MBS resin is preferably 42 or more, more preferably 45 or more, still more preferably 48 or more, further preferably 50 or more, and 51 or more. It is more preferable to be 1, and 52 or more is particularly preferable.
　また、ＭＢＳ樹脂のショアＤ硬さ（直後）は、例えば、７０以下であってもよく、６７以下であることが好ましく、６４以下であることがより好ましく、６２以下であることがさらに好ましく、６０以下であることがさらに好ましく、５８以下であることがさらに好ましく、５６以下であることがさらに好ましく、５４以下であることが特に好ましい。ＭＢＳ樹脂のショアＤ硬さ（直後）は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。ＭＢＳ樹脂のショアＤ硬さ（直後）が大きいほど、本組成物は引張強さに優れる。ただし、ショアＤ硬さ（直後）が大きすぎると、本組成物の比重が大きくなるため、軽量性に劣ることとなる。 In addition, the Shore D hardness (immediately after) of the MBS resin may be, for example, 70 or less, preferably 67 or less, more preferably 64 or less, and even more preferably 62 or less. It is more preferably 60 or less, more preferably 58 or less, even more preferably 56 or less, and particularly preferably 54 or less. The Shore D hardness (immediately) of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the Shore D hardness (immediate) of the MBS resin, the better the tensile strength of the composition. However, if the Shore D hardness (immediately) is too high, the specific gravity of the present composition increases, resulting in poor lightweight properties.
　ＭＢＳ樹脂のＪＩＳ　Ｋ　６２５３－３：２０１２に準拠した方法において試験片に押針を押し込んでから１０秒後に測定されるショアＤ硬さ（以下、「ショアＤ硬さ（１０秒後）」という。）は、本発明の効果が得られれば特に限られないが、例えば、３０以上であってもよく、３５以上であることが好ましく、４０以上であることがより好ましく、４３以上であることがさらに好ましく、４５以上であることがさらに好ましく、４７以上であることが特に好ましい。 Shore D hardness (hereinafter referred to as "Shore D hardness (after 10 seconds)") measured 10 seconds after the indenter is pushed into the test piece in accordance with MBS resin JIS K 6253-3:2012. ) is not particularly limited as long as the effect of the present invention can be obtained, but for example, it may be 30 or more, preferably 35 or more, more preferably 40 or more, and 43 or more It is more preferably 45 or more, and particularly preferably 47 or more.
　また、ＭＢＳ樹脂のショアＤ硬さ（１０秒後）は、例えば、６５以下であってもよく、５９以下であることが好ましく、５５以下であることがより好ましく、５３以下であることがさらに好ましく、５０以下であることが特に好ましい。ＭＢＳ樹脂のショアＤ硬さ（１０秒後）は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。ＭＢＳ樹脂のショアＤ硬さ（１０秒後）が大きいほど、本組成物は引張強さに優れる。ただし、ショアＤ硬さ（１０秒後）が大きすぎると、本組成物の比重が大きくなるため、軽量性に劣ることとなる。 In addition, the Shore D hardness (after 10 seconds) of the MBS resin may be, for example, 65 or less, preferably 59 or less, more preferably 55 or less, and further preferably 53 or less. It is preferably 50 or less, and particularly preferably 50 or less. The Shore D hardness (after 10 seconds) of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the Shore D hardness (after 10 seconds) of the MBS resin, the better the tensile strength of the composition. However, if the Shore D hardness (after 10 seconds) is too high, the specific gravity of the present composition increases, resulting in poor lightweight properties.
　ＭＢＳ樹脂のＪＩＳ　Ｋ　６２５３－３：２０１２に準拠した方法において試験片に押針を押し込んだ直後に測定されるショアＡ硬さ（以下、「ショアＡ硬さ（直後）」という。）は、本発明の効果が得られれば特に限られないが、例えば、８５以上であってもよく、９０以上であることが好ましく、９３以上であることがより好ましく、９５以上であることが特に好ましい。 The Shore A hardness (hereinafter referred to as "Shore A hardness (immediately)") measured immediately after the indenter is pushed into the test piece in a method conforming to JIS K 6253-3:2012 of MBS resin is Although not particularly limited as long as the effect of the invention can be obtained, for example, it may be 85 or more, preferably 90 or more, more preferably 93 or more, and particularly preferably 95 or more.
　また、ＭＢＳ樹脂のショアＡ硬さ（直後）は、例えば、９９以下であってもよく、９８以下であることが好ましく、９７以下であることが特に好ましい。ＭＢＳ樹脂のショアＡ硬さ（直後）は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。ＭＢＳ樹脂のショアＡ硬さ（直後）が大きいほど、本組成物は引張強さに優れる。ただし、ショアＡ硬さ（直後）が大きすぎると、本組成物の比重が大きくなるため、軽量性に劣ることとなる。 In addition, the Shore A hardness (immediately after) of the MBS resin may be, for example, 99 or less, preferably 98 or less, and particularly preferably 97 or less. The Shore A hardness (immediately after) of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the Shore A hardness (immediately) of the MBS resin, the better the tensile strength of the composition. However, if the Shore A hardness (immediately after) is too high, the specific gravity of the composition increases, resulting in poor lightweight properties.
　ＭＢＳ樹脂のＪＩＳ　Ｋ　６２５３－３：２０１２に準拠した方法において試験片に押針を押し込んでから１０秒後に測定されるショアＡ硬さ（以下、「ショアＡ硬さ（１０秒後）」という。）は、本発明の効果が得られれば特に限られないが、例えば、８５以上であってもよく、９１以上であることが好ましく、９３以上であることがより好ましく、９５以上であることがさらに好ましく、９６以上であることが特に好ましい。 Shore A hardness (hereinafter referred to as "Shore A hardness (after 10 seconds)" measured 10 seconds after the indenter is pushed into the test piece in accordance with MBS resin JIS K 6253-3:2012. ) is not particularly limited as long as the effect of the present invention can be obtained, but for example, it may be 85 or more, preferably 91 or more, more preferably 93 or more, and 95 or more More preferably, it is particularly preferably 96 or more.
　また、ＭＢＳ樹脂のショアＡ硬さ（１０秒後）は、例えば、９９以下であってもよく、９８以下であることが好ましく、９７以下であることが特に好ましい。ＭＢＳ樹脂のショアＡ硬さ（１０秒後）は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。ＭＢＳ樹脂のショアＡ硬さ（１０秒後）が大きいほど、本組成物は引張強さに優れる。ただし、ショアＡ硬さ（１０秒後）が大きすぎると、本組成物の比重が大きくなるため、軽量性に劣ることとなる。 In addition, the Shore A hardness (after 10 seconds) of the MBS resin may be, for example, 99 or less, preferably 98 or less, and particularly preferably 97 or less. The Shore A hardness (after 10 seconds) of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the Shore A hardness (after 10 seconds) of the MBS resin, the better the tensile strength of the composition. However, if the Shore A hardness (after 10 seconds) is too high, the specific gravity of the present composition increases, resulting in poor lightweight properties.
　ＭＢＳ樹脂のＪＩＳ　Ｋ　６２５１：２０１７に準拠した方法により測定される引張強さ（試験片を切断するまで引っ張ったときに記録される最大の引張力を当該試験片の初期断面積で除した値）（以下、「引張強さ」という。）（ＭＰａ）は、本発明の効果が得られれば特に限られないが、例えば、１０ＭＰａ以上であってもよく、１２ＭＰａ以上であることが好ましく、１４ＭＰａ以上であることがより好ましく、１５ＭＰａ以上であることが特に好ましい。 Tensile strength of MBS resin measured by a method conforming to JIS K 6251:2017 (value obtained by dividing the maximum tensile force recorded when the test piece is pulled until it breaks by the initial cross-sectional area of the test piece) (Hereinafter referred to as "tensile strength") (MPa) is not particularly limited as long as the effect of the present invention can be obtained, but for example, it may be 10 MPa or more, preferably 12 MPa or more, and 14 MPa or more. is more preferable, and 15 MPa or more is particularly preferable.
　また、ＭＢＳ樹脂の引張強さは、例えば、３０ＭＰａ以下であってもよく、２５ＭＰａ以下であってもよく、２１ＭＰａ以下であってもよく、２０ＭＰａ以下であってもよい。ＭＢＳ樹脂の引張強さは、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。引張強さが大きいほど、機械的強度に優れる。ただし、引張強さが大きすぎると、柔軟性に劣ることとなる。 Also, the tensile strength of the MBS resin may be, for example, 30 MPa or less, 25 MPa or less, 21 MPa or less, or 20 MPa or less. The tensile strength of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the tensile strength, the better the mechanical strength. However, if the tensile strength is too high, the flexibility will be poor.
　ＭＢＳ樹脂のＪＩＳ　Ｋ　６２５１：２０１７に準拠した方法により測定される切断時伸び（試験片が切断した時点の伸びを初期長さに対する比率（％）で表した値）（以下、「切断時伸び」という。）（％）は、本発明の効果が得られれば特に限られないが、例えば、１４０％以上であってもよく、１５０％以上であることが好ましく、１６０％以上であることがより好ましく、１７０％以上であることがさらに好ましく、１８０％以上であることがさらに好ましく、１９０％以上であることがさらに好ましく、２００％以上であることがさらに好ましく、２１０％以上であることがさらに好ましく、２２０％以上であることがさらに好ましく、２３０％以上であることがさらに好ましく、２４０％以上であることが特に好ましい。 Elongation at break measured by a method conforming to JIS K 6251:2017 of MBS resin (value expressed as a ratio (%) of the elongation at the time the test piece is cut to the initial length) (hereinafter referred to as "elongation at break" (%) is not particularly limited as long as the effect of the present invention can be obtained, but for example, it may be 140% or more, preferably 150% or more, and more preferably 160% or more. It is preferably 170% or more, more preferably 180% or more, further preferably 190% or more, further preferably 200% or more, further preferably 210% or more. It is preferably 220% or more, more preferably 230% or more, and particularly preferably 240% or more.
　また、ＭＢＳ樹脂の切断時伸びは、例えば、４００％以下であってもよく、３５０％以下であってもよく、３００％以下であってもよく、２８０％以下であってもよく、２６０％以下であってもよい。ＭＢＳ樹脂の切断時伸びは、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。切断時伸びが大きいほど、伸張性に優れる。ただし、切断時伸びが大きすぎると、機械的強度に劣ることとなる。 Further, the elongation at break of the MBS resin may be, for example, 400% or less, 350% or less, 300% or less, 280% or less, or 260%. It may be below. The elongation at break of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The greater the elongation at break, the more excellent the extensibility. However, if the elongation at break is too large, the mechanical strength will be poor.
　ＭＢＳ樹脂のＪＩＳ　Ｋ　６２５１：２０１７に準拠した方法により測定される１００％モジュラス（試験片に１００％の伸びを与えたときの引張応力を試験片の初期断面積で除した値）（以下、「１００％モジュラス」という。）（ＭＰａ）は、本発明の効果が得られれば特に限られないが、例えば、２５．０ＭＰａ以下であってもよく、２０．０ＭＰａ以下であることが好ましく、１７．０ＭＰａ以下であることがより好ましく、１５．０ＭＰａ以下であることがさらに好ましく、１３．０ＭＰａ以下であることがさらに好ましく、１２．０ＭＰａ以下であることが特に好ましい。 100% modulus of MBS resin measured by a method conforming to JIS K 6251:2017 (the value obtained by dividing the tensile stress when 100% elongation is applied to the test piece by the initial cross-sectional area of the test piece) (hereinafter referred to as " (referred to as "100% modulus") (MPa) is not particularly limited as long as the effects of the present invention can be obtained, but may be, for example, 25.0 MPa or less, preferably 20.0 MPa or less. It is more preferably 0 MPa or less, further preferably 15.0 MPa or less, even more preferably 13.0 MPa or less, and particularly preferably 12.0 MPa or less.
　また、ＭＢＳ樹脂の１００％モジュラスは、例えば、３．０ＭＰａ以下であってもよく、５．０ＭＰａ以下であることが好ましく、６．０ＭＰａ以下であることがより好ましく、７．０ＭＰａ以下であることがさらに好ましく、８．０ＭＰａ以下であることがより好ましく、９．０ＭＰａ以下であることが特に好ましい。ＭＢＳ樹脂の１００％モジュラスは、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。１００％モジュラスが小さいほど、柔軟性に優れる。ただし、１００％モジュラスが大きすぎると、機械的強度に劣ることとなる。 In addition, the 100% modulus of the MBS resin may be, for example, 3.0 MPa or less, preferably 5.0 MPa or less, more preferably 6.0 MPa or less, and 7.0 MPa or less. is more preferable, 8.0 MPa or less is more preferable, and 9.0 MPa or less is particularly preferable. The 100% modulus of the MBS resin may be specified by any combination of any of the above lower limits and any of the above upper limits. The smaller the 100% modulus, the better the flexibility. However, if the 100% modulus is too large, the mechanical strength will be poor.
　ＭＢＳ樹脂のＪＩＳ　Ｋ　６７２３－１９９５に準拠した方法により測定される耐寒性（以下、「耐寒性」という。）（℃）は、本発明の効果が得られれば特に限られないが、例えば、０℃以下であってもよく、マイナス１０℃以下であることが好ましく、マイナス２０℃以下であることがより好ましく、マイナス２５℃以下であることがさらに好ましく、マイナス３０℃以下であることが特に好ましい。耐寒性が低いほど、耐寒性に優れる。 Cold resistance (hereinafter referred to as "cold resistance") (°C) measured by a method conforming to JIS K 6723-1995 of MBS resin is not particularly limited as long as the effect of the present invention can be obtained. ° C. or lower, preferably -10 ° C. or lower, more preferably -20 ° C. or lower, even more preferably -25 ° C. or lower, and particularly preferably -30 ° C. or lower. . The lower the cold resistance, the better the cold resistance.
　ＭＢＳ樹脂の屈折率は、本発明の効果が得られれば特に限られないが、例えば、１．５２０以上であってもよく、１．５２５以上であることが好ましく、１．５３０以上であることがより好ましく、１．５３２以上であることが特に好ましい。 The refractive index of the MBS resin is not particularly limited as long as the effects of the present invention can be obtained. is more preferable, and 1.532 or more is particularly preferable.
　また、ＭＢＳ樹脂の屈折率は、例えば、１．５６０以下であってもよく、１．５５５以下であることが好ましく、１．５５０以下であることがより好ましく、１．５４５以下であることがさらに好ましく、１．５４０以下であることがさらに好ましく、１．５３８以下であることが特に好ましい。ＭＢＳ樹脂の屈折率は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。 In addition, the refractive index of the MBS resin may be, for example, 1.560 or less, preferably 1.555 or less, more preferably 1.550 or less, and preferably 1.545 or less. It is more preferably 1.540 or less, and particularly preferably 1.538 or less. The refractive index of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
　本組成物に含まれるＭＢＳ樹脂の屈折率と、本組成物に含まれるＴＰＵの屈折率との差の絶対値は、本発明の効果が得られれば特に限られないが、例えば、０．０２０以下であってもよく、０．０１５以下であることが好ましく、０．０１０以下であることがより好ましく、０．００７以下であることがさらに好ましく、０．００６以下であることがさらに好ましく、０．００５以下であることが特に好ましい。ＭＢＳ樹脂の屈折率と、ＴＰＵの屈折率との差が小さいほど、本組成物の透明性が向上する。 The absolute value of the difference between the refractive index of the MBS resin contained in the present composition and the refractive index of the TPU contained in the present composition is not particularly limited as long as the effects of the present invention can be obtained, but for example 0.020. or less, preferably 0.015 or less, more preferably 0.010 or less, further preferably 0.007 or less, further preferably 0.006 or less, 0.005 or less is particularly preferable. The smaller the difference between the refractive index of the MBS resin and the TPU, the better the transparency of the composition.
　ＭＢＳ樹脂のＳＰ値は、本発明の効果が得られれば特に限られないが、例えば、９．０（ｃａｌ／ｃｍ３）０．５以上であってもよく、９．２（ｃａｌ／ｃｍ３）０．５以上であることが好ましく、９．４（ｃａｌ／ｃｍ３）０．５以上であることがより好ましく、９．５（ｃａｌ／ｃｍ３）０．５以上であることがさらに好ましく、９．６（ｃａｌ／ｃｍ３）０．５以上であことが特に好ましい。 The SP value of the MBS resin is not particularly limited as long as the effects of the present invention can be obtained . ) is preferably 0.5 or more, more preferably 9.4 (cal/cm 3 ) 0.5 or more, and even more preferably 9.5 (cal/cm 3 ) 0.5 or more , 9.6 (cal/cm 3 ) 0.5 or more is particularly preferable.
　また、ＭＢＳ樹脂のＳＰ値は、例えば、１１．０（ｃａｌ／ｃｍ３）０．５以下であってもよく、１０．５（ｃａｌ／ｃｍ３）０．５以下であってもよく、１０．２（ｃａｌ／ｃｍ３）０．５以下であってもよく、１０．０（ｃａｌ／ｃｍ３）０．５以下であってもよく、９．８（ｃａｌ／ｃｍ３）０．５以下であってもよい。ＭＢＳ樹脂のＳＰ値は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。 In addition, the SP value of the MBS resin may be, for example, 11.0 (cal/cm 3 ) 0.5 or less, 10.5 (cal/cm 3 ) 0.5 or less, or 10 .2 (cal/cm 3 ) 0.5 or less, 10.0 (cal/cm 3 ) 0.5 or less, or 9.8 (cal/cm 3 ) 0.5 or less may be The SP value of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits.
　本組成物に含まれるＭＢＳ樹脂のＳＰ値と、本組成物に含まれるＴＰＵのＳＰ値との差の絶対値は、本発明の効果が得られれば特に限られないが、例えば、１．５以下であってもよく、１．４以下であることが好ましく、１．３以下であることがより好ましく、１．２以下であることがさらに好ましく、１．１以下であることがさらに好ましく、１．０以下であることが特に好ましい。ＭＢＳ樹脂のＳＰ値とＴＰＵのＳＰ値との差が小さいほど、本組成物における当該ＭＢＳ樹脂と当該ＴＰＵとの相溶性が向上し、その結果、例えば、本組成物の透明性が向上し、及び／又は、機械的強度が向上する。 The absolute value of the difference between the SP value of the MBS resin contained in the present composition and the SP value of the TPU contained in the present composition is not particularly limited as long as the effects of the present invention can be obtained, but is, for example, 1.5. or less, preferably 1.4 or less, more preferably 1.3 or less, further preferably 1.2 or less, further preferably 1.1 or less, 1.0 or less is particularly preferable. The smaller the difference between the SP value of the MBS resin and the SP value of the TPU, the better the compatibility between the MBS resin and the TPU in the present composition. As a result, for example, the transparency of the present composition is improved, and/or improved mechanical strength.
　ＭＢＳ樹脂のＪＩＳ　Ｋ　７１１２：１９９９に準拠した方法により測定される比重（以下、「比重」という。）は、本発明の効果が得られれば特に限られないが、例えば、１．０５以下であってもよく、１．０４以下であることが好ましく、１．０３以下であることがより好ましく、１．０２以下であることがさらに好ましく、１．０１以下であることが特に好ましい。 The specific gravity of MBS resin measured by a method conforming to JIS K 7112:1999 (hereinafter referred to as "specific gravity") is not particularly limited as long as the effects of the present invention can be obtained, but is, for example, 1.05 or less. It is preferably 1.04 or less, more preferably 1.03 or less, even more preferably 1.02 or less, and particularly preferably 1.01 or less.
　また、ＭＢＳ樹脂の比重は、例えば、０．９５以上であってもよく、０．９６以上であってもよく、０．９７以上であってもよく、０．９８以上であってもよく、０．９９以上であってもよい。ＭＢＳ樹脂の比重は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。比重が小さいほど、軽量性が向上する。 Further, the specific gravity of the MBS resin may be, for example, 0.95 or more, 0.96 or more, 0.97 or more, or 0.98 or more. It may be 0.99 or more. The specific gravity of the MBS resin may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. As the specific gravity is smaller, the lightness is improved.
　本組成物のショアＡ硬さ（直後）は、本発明の効果が得られれば特に限られないが、例えば、８５以上であってもよく、９０以上であることが好ましく、９１以上であることがより好ましく、９２以上であることがさらに好ましく、９３以上であることがさらに好ましく、９４以上であることが特に好ましい。 The Shore A hardness (immediately after) of the present composition is not particularly limited as long as the effects of the present invention can be obtained, but for example, it may be 85 or more, preferably 90 or more, and 91 or more. is more preferably 92 or more, more preferably 93 or more, and particularly preferably 94 or more.
　また、本組成物のショアＡ硬さ（直後）は、例えば、９９以下であってもよく、９８以下であることが好ましく、９７以下であることがより好ましく、９６以下であることが特に好ましい。本組成物のショアＡ硬さ（直後）は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。本組成物は、ショアＡ硬さ（直後）が大きいほど、引張強さに優れる。ただし、ショアＡ硬さ（直後）が大きすぎると、比重が大きくなるため、本組成物は軽量性に劣ることとなる。 In addition, the Shore A hardness (immediately after) of the present composition may be, for example, 99 or less, preferably 98 or less, more preferably 97 or less, and particularly preferably 96 or less. . The Shore A hardness (immediately) of the present composition may be specified by any combination of any of the above lower limits and any of the above upper limits. The higher the Shore A hardness (immediately), the better the tensile strength of the composition. However, if the Shore A hardness (immediately after) is too high, the specific gravity of the composition increases, resulting in poor lightweight properties of the composition.
　本組成物のショアＡ硬さ（１０秒後）は、本発明の効果が得られれば特に限られないが、例えば、８５以上であってもよく、９０以上であることが好ましく、９１以上であることがより好ましく、９２以上であることがさらに好ましく、９３以上であることが特に好ましい。 The Shore A hardness (after 10 seconds) of the present composition is not particularly limited as long as the effects of the present invention can be obtained. It is more preferably 1, more preferably 92 or more, and particularly preferably 93 or more.
　また、本組成物のショアＡ硬さ（１０秒後）は、例えば、９９以下であってもよく、９８以下であることが好ましく、９７以下であることがより好ましく、９６以下であることがさらに好ましく、９５以下であることが特に好ましい。本組成物のショアＡ硬さ（１０秒後）は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。本組成物は、ショアＡ硬さ（１０秒後）が大きいほど、引張強さに優れる。ただし、ショアＡ硬さ（１０秒後）が大きすぎると、比重が大きくなるため、本組成物は軽量性に劣ることとなる。 In addition, the Shore A hardness (after 10 seconds) of the present composition may be, for example, 99 or less, preferably 98 or less, more preferably 97 or less, and 96 or less. More preferably, it is particularly preferably 95 or less. The Shore A hardness (after 10 seconds) of the present composition may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the Shore A hardness (after 10 seconds) of the composition, the better the tensile strength. However, if the Shore A hardness (after 10 seconds) is too high, the composition will have a high specific gravity and will be inferior in lightness.
　本組成物の引張強さは、本発明の効果が得られれば特に限られないが、例えば、２０ＭＰａ以上であってもよく、２１ＭＰａ以上であることが好ましく、２２ＭＰａ以上であることがより好ましく、２３ＭＰａ以上であることがさらに好ましく、２４ＭＰａ以上であることがさらに好ましく、２５ＭＰａ以上であることがさらに好ましく、２６ＭＰａ以上であることがさらに好ましく、２７ＭＰａ以上であることがさらに好ましく、２８ＭＰａ以上であることがさらに好ましく、２９ＭＰａ以上であることがさらに好ましく、３０ＭＰａ以上であることがさらに好ましく、３１ＭＰａ以上であることがさらに好ましく、３２ＭＰａ以上であることがさらに好ましく、３３ＭＰａ以上であることがさらに好ましく、３４ＭＰａ以上であることがさらに好ましく、３５ＭＰａ以上であることが特に好ましい。 The tensile strength of the present composition is not particularly limited as long as the effects of the present invention can be obtained. It is more preferably 23 MPa or more, more preferably 24 MPa or more, further preferably 25 MPa or more, further preferably 26 MPa or more, further preferably 27 MPa or more, and 28 MPa or more. is more preferably 29 MPa or more, more preferably 30 MPa or more, further preferably 31 MPa or more, still more preferably 32 MPa or more, further preferably 33 MPa or more, and 34 MPa It is more preferably 35 MPa or more, and particularly preferably 35 MPa or more.
　また、本組成物の引張強さは、例えば、５０ＭＰａ以下であってもよく、４５ＭＰａ以下であってもよく、４０ＭＰａ以下であってもよく、３９ＭＰａ以下であってもよく、３８ＭＰａ以下であってもよく、３７ＭＰａ以下であってもよい。本組成物の引張強さは、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。引張強さが大きいほど、機械的強度に優れる。ただし、引張強さが大きすぎると、柔軟性に劣ることとなる。 Further, the tensile strength of the present composition may be, for example, 50 MPa or less, 45 MPa or less, 40 MPa or less, 39 MPa or less, or 38 MPa or less. may be 37 MPa or less. The tensile strength of the present composition may be specified by any combination of any of the above lower limits and any of the above upper limits. The higher the tensile strength, the better the mechanical strength. However, if the tensile strength is too high, the flexibility will be poor.
　本組成物の切断時伸びは、本発明の効果が得られれば特に限られないが、例えば、３００％以上であってもよく、３５０％以上であることが好ましく、３８０％以上であることが好ましく、４００％以上であることがより好ましく、４１０％以上であることがさらに好ましく、４２０％以上であることがさらに好ましく、４２５％以上であることがさらに好ましく、４３０％以上であることがさらに好ましく、４３５％以上であることがさらに好ましく、４４０％以上であることがさらに好ましく、４４５％以上であることがさらに好ましく、４５０％以上であることがさらに好ましく、４５５％以上であることがさらに好ましく、４６０％以上であることが特に好ましい。 The elongation at break of the present composition is not particularly limited as long as the effects of the present invention can be obtained, but for example, it may be 300% or more, preferably 350% or more, and 380% or more. It is preferably 400% or more, more preferably 410% or more, still more preferably 420% or more, still more preferably 425% or more, and further preferably 430% or more. It is preferably 435% or more, more preferably 440% or more, further preferably 445% or more, further preferably 450% or more, further preferably 455% or more. It is preferably 460% or more, and particularly preferably 460% or more.
　また、本組成物の切断時伸びは、例えば、６００％以下であってもよく、５５０％以下であってもよく、５００％以下であってもよく、４９０％以下であってもよく、４８０％以下であってもよく、４７０％以下であってもよい。本組成物の切断時伸びは、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。切断時伸びが大きいほど、伸張性に優れる。ただし、切断時伸びが大きすぎると、機械的強度に劣ることとなる。 Further, the elongation at break of the present composition may be, for example, 600% or less, 550% or less, 500% or less, 490% or less, or 480% or less. % or less, or 470% or less. The elongation at break of the present composition may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The greater the elongation at break, the more excellent the extensibility. However, if the elongation at break is too large, the mechanical strength will be poor.
　本組成物のＪＩＳ　Ｋ　６２５１：２０１７に準拠した方法により測定される１００％モジュラスは、本発明の効果が得られれば特に限られないが、例えば、２５．０ＭＰａ以下であってもよく、２０．０ＭＰａ以下であることが好ましく、１７．０ＭＰａ以下であることがより好ましく、１５．０ＭＰａ以下であることがさらに好ましく、１３．０ＭＰａ以下であることがさらに好ましく、１２．０ＭＰａ以下であることがさらに好ましく、１１．０ＭＰａ以下であることがさらに好ましく、１０．０ＭＰａ以下であることが特に好ましい。 The 100% modulus of the present composition measured by a method conforming to JIS K 6251:2017 is not particularly limited as long as the effects of the present invention can be obtained. It is preferably 0 MPa or less, more preferably 17.0 MPa or less, even more preferably 15.0 MPa or less, further preferably 13.0 MPa or less, and further preferably 12.0 MPa or less. It is preferably 11.0 MPa or less, more preferably 10.0 MPa or less.
　また、本組成物の１００％モジュラスは、例えば、３．０ＭＰａ以下であってもよく、５．０ＭＰａ以下であることが好ましく、６．０ＭＰａ以下であることがより好ましく、７．０ＭＰａ以下であることがさらに好ましく、８．０ＭＰａ以下であることがより好ましく、９．０ＭＰａ以下であることが特に好ましい。本組成物の１００％モジュラスは、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。１００％モジュラスが小さいほど、柔軟性に優れる。ただし、１００％モジュラスが大きすぎると、機械的強度に劣ることとなる。 Further, the 100% modulus of the present composition may be, for example, 3.0 MPa or less, preferably 5.0 MPa or less, more preferably 6.0 MPa or less, and 7.0 MPa or less. is more preferably 8.0 MPa or less, and particularly preferably 9.0 MPa or less. The 100% modulus of the composition may be specified by any combination of any of the above lower limits and any of the above upper limits. The smaller the 100% modulus, the better the flexibility. However, if the 100% modulus is too large, the mechanical strength will be poor.
　本組成物のＪＩＳ　Ｋ　７２１０－１：２０１４に準拠した方法により１９０℃、１０ｋｇ荷重の条件で測定されるメルトフローレイト（Ｍｅｌｔ　Ｆｌｏｗ　Ｒａｔｅ）（以下、「ＭＦＲ」という。）（ｇ／１０ｍｉｎ）は、本発明の効果が得られれば特に限られないが、例えば、１．０ｇ／１０ｍｉｎ以上であってもよく、２．０ｇ／１０ｍｉｎ以上であることが好ましく、３．０ｇ／１０ｍｉｎ以上であることがより好ましく、４．０ｇ／１０ｍｉｎ以上であることがさらに好ましく、５．０ｇ／１０ｍｉｎ以上であることがさらに好ましく、６．０ｇ／１０ｍｉｎ以上であることがさらに好ましく、７．０ｇ／１０ｍｉｎ以上であることがさらに好ましく、８．０ｇ／１０ｍｉｎ以上であることがさらに好ましく、８．５ｇ／１０ｍｉｎ以上であることがさらに好ましく、９．０ｇ／１０ｍｉｎ以上であることがさらに好ましく、９．５ｇ／１０ｍｉｎ以上であることがさらに好ましく、１０．０ｇ／１０ｍｉｎ以上であることがさらに好ましく、１０．５ｇ／１０ｍｉｎ以上であることがさらに好ましく、１１．０ｇ／１０ｍｉｎ以上であることがさらに好ましく、１１．５ｇ／１０ｍｉｎ以上であることがさらに好ましく、１２．０ｇ／１０ｍｉｎ以上であることがさらに好ましく、１２．５ｇ／１０ｍｉｎ以上であることがさらに好ましく、１３．０ｇ／１０ｍｉｎ以上であることがさらに好ましく、１３．５ｇ／１０ｍｉｎ以上であることがさらに好ましく、１４．０ｇ／１０ｍｉｎ以上であることがさらに好ましく、１４．５ｇ／１０ｍｉｎ以上であることがさらに好ましく、１５．０ｇ／１０ｍｉｎ以上であることが特に好ましい。 Melt Flow Rate (hereinafter referred to as "MFR") (g/10 min) measured at 190°C and 10 kg load by a method in accordance with JIS K 7210-1:2014 of this composition is , Although not particularly limited as long as the effect of the present invention can be obtained, for example, it may be 1.0 g/10 min or more, preferably 2.0 g/10 min or more, and 3.0 g/10 min or more is more preferably 4.0 g/10 min or more, more preferably 5.0 g/10 min or more, even more preferably 6.0 g/10 min or more, and 7.0 g/10 min or more. more preferably 8.0 g/10 min or more, more preferably 8.5 g/10 min or more, even more preferably 9.0 g/10 min or more, 9.5 g/10 min more preferably 10.0 g/10 min or more, more preferably 10.5 g/10 min or more, even more preferably 11.0 g/10 min or more, and 11.5 g /10 min or more, more preferably 12.0 g/10 min or more, more preferably 12.5 g/10 min or more, further preferably 13.0 g/10 min or more, 13 It is more preferably 0.5 g/10 min or more, further preferably 14.0 g/10 min or more, still more preferably 14.5 g/10 min or more, and particularly preferably 15.0 g/10 min or more. .
　また、本組成物のＭＦＲは、例えば、３５．０ｇ／１０ｍｉｎ以下であってもよく、３０．０ｇ／１０ｍｉｎ以下であることが好ましく、２５．０ｇ／１０ｍｉｎ以下であることがより好ましく、２０．０ｇ／１０ｍｉｎ以下であることがさらに好ましく、１８．０ｇ／１０ｍｉｎ以下であることがさらに好ましく、１７．０ｇ／１０ｍｉｎ以下であることがさらに好ましく、１６．０ｇ／１０ｍｉｎ以下であることが特に好ましい。本組成物のＭＦＲは、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。ＭＦＲが小さすぎると、流動性に乏しく、加工性に劣ることとなる。ＭＦＲが大きすぎると、加工後の形状維持に劣ることとなる。 In addition, the MFR of the present composition may be, for example, 35.0 g/10 min or less, preferably 30.0 g/10 min or less, more preferably 25.0 g/10 min or less. It is more preferably 0 g/10 min or less, further preferably 18.0 g/10 min or less, still more preferably 17.0 g/10 min or less, and particularly preferably 16.0 g/10 min or less. The MFR of the present composition may be specified by any combination of any of the above lower limits and any of the above upper limits. If the MFR is too small, the fluidity will be poor and the workability will be poor. If the MFR is too large, the shape maintenance after processing will be poor.
　本組成物の耐寒性は、本発明の効果が得られれば特に限られないが、例えば、０℃以下であってもよく、マイナス１０℃以下であることが好ましく、マイナス２０℃以下であることがより好ましく、マイナス３０℃以下であることがさらに好ましく、マイナス４０℃以下であることがさらに好ましく、マイナス５０℃以下であることがさらに好ましく、マイナス５５℃以下であることがさらに好ましく、マイナス６０℃以下であることがさらに好ましく、マイナス６５℃以下であることが特に好ましい。耐寒性が低いほど、耐寒性に優れる。 The cold resistance of the present composition is not particularly limited as long as the effects of the present invention can be obtained, but for example, it may be 0 ° C. or lower, preferably -10 ° C. or lower, and -20 ° C. or lower. is more preferably -30°C or lower, more preferably -40°C or lower, even more preferably -50°C or lower, further preferably -55°C or lower, and -60°C. ° C. or less is more preferable, and -65° C. or less is particularly preferable. The lower the cold resistance, the better the cold resistance.
　本組成物の全光線透過率（％）は、本発明の効果が得られれば特に限られないが、例えば、８０．０％以上であってもよく、８１．０％以上であることが好ましく、８２．０％以上であることがより好ましく、８２．５％以上であることがさらに好ましく、８３．０％以上であることが特に好ましい。また、本組成物の全光線透過率は、例えば、９９．０％以下であってもよく、９５．０％以下であってもよい。本組成物の全光線透過率は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。全光線透過率が大きいほど、透光性に優れる。 The total light transmittance (%) of the present composition is not particularly limited as long as the effect of the present invention is obtained, but may be, for example, 80.0% or more, preferably 81.0% or more. , is more preferably 82.0% or more, still more preferably 82.5% or more, and particularly preferably 83.0% or more. Moreover, the total light transmittance of the present composition may be, for example, 99.0% or less, or 95.0% or less. The total light transmittance of the present composition may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The higher the total light transmittance, the better the translucency.
　本組成物のヘーズ値（％）は、本発明の効果が得られれば特に限られないが、例えば、２５．０％以下であってもよく、２０．０％以下であることが好ましく、１９．０％以下であることがより好ましく、１８．５％以下であることがさらに好ましく、１８．０％以下であることがさらに好ましく、１７．５％以下であることがさらに好ましく、１７．０％以下であることが特に好ましい。また、本組成物のヘーズ値は、例えば、１．０％以上であってもよい。ヘーズ値が小さいほど、曇りが低減され、透明性に優れる。 The haze value (%) of the present composition is not particularly limited as long as the effects of the present invention can be obtained. 0% or less, more preferably 18.5% or less, even more preferably 18.0% or less, even more preferably 17.5% or less, and 17.0% % or less is particularly preferred. Moreover, the haze value of the present composition may be, for example, 1.0% or more. The smaller the haze value, the less fogging and the better the transparency.
　本組成物の比重は、本発明の効果が得られれば特に限られないが、例えば、１．１５以下であってもよく、１．１２以下であることが好ましく、１．１０以下であることがより好ましく、１．０９以下であることがさらに好ましく、１．０８以下であることが特に好ましい。 The specific gravity of the present composition is not particularly limited as long as the effects of the present invention can be obtained, but for example, it may be 1.15 or less, preferably 1.12 or less, and 1.10 or less. is more preferably 1.09 or less, and particularly preferably 1.08 or less.
　また、本組成物の比重は、例えば、０．９５以上であってもよく、１．００以上であってもよく、１．０２以上であってもよく、１．０４以上であってもよく、１．０５以上であってもよく、１．０６以上であってもよい。本組成物の比重は、上述した下限値のいずれかと、上述した上限値のいずれかとを任意に組みわせて特定されてもよい。比重が小さいほど、軽量性に優れる。 Further, the specific gravity of the present composition may be, for example, 0.95 or more, 1.00 or more, 1.02 or more, or 1.04 or more. , may be 1.05 or more, or may be 1.06 or more. The specific gravity of the present composition may be specified by arbitrarily combining any of the above lower limits and any of the above upper limits. The smaller the specific gravity, the more excellent the lightness.
　本組成物は、ＴＰＵ及びＭＢＳ樹脂に加えて、さらに他の成分を含んでもよい。本組成物が含んでもよい他の成分は、本発明の効果が得られれば特に限られないが、例えば、滑剤、安定剤、酸化防止剤、塩素吸収剤、光安定剤、紫外線吸収剤、帯電防止剤、防曇剤、難燃剤、発煙抑制剤、分散剤、銅害防止剤、可塑剤、防カビ剤、抗菌剤、抗ウイルス剤、気泡防止剤、架橋剤、過酸化物、有機顔料、無機顔料及び充填剤からなる群より選択される１以上であることが好ましい。 The composition may further contain other components in addition to TPU and MBS resin. Other components that the present composition may contain are not particularly limited as long as the effect of the present invention can be obtained. Inhibitors, antifog agents, flame retardants, smoke suppressants, dispersants, copper damage inhibitors, plasticizers, antifungal agents, antibacterial agents, antiviral agents, antifoam agents, crosslinkers, peroxides, organic pigments, It is preferably one or more selected from the group consisting of inorganic pigments and fillers.
　本組成物は、主にＴＰＵ及びＭＢＳ樹脂を含むことが好ましい。すなわち、本組成物１００重量部に対する、ＴＰＵの重量部とＭＢＳ樹脂の重量部との合計は、例えば、５０重量部以上であることが好ましく、６０重量部以上であることがより好ましく、７０重量部以上であることがさらに好ましく、８０重量部以上であることがさらに好ましく、９０重量部以上であることがさらに好ましく、９５重量部以上であることがさらに好ましく、９６重量部以上であることがさらに好ましく、９７重量部以上であることがさらに好ましく、９８重量部以上であることがさらに好ましく、９９重量部以上であることが特に好ましい。 It is preferable that the present composition mainly contains TPU and MBS resin. That is, the total of the parts by weight of the TPU and the parts by weight of the MBS resin with respect to 100 parts by weight of the present composition is, for example, preferably 50 parts by weight or more, more preferably 60 parts by weight or more, and 70 parts by weight. parts by weight or more, more preferably 80 parts by weight or more, more preferably 90 parts by weight or more, still more preferably 95 parts by weight or more, and preferably 96 parts by weight or more. It is more preferably 97 parts by weight or more, still more preferably 98 parts by weight or more, and particularly preferably 99 parts by weight or more.
　本組成物の製造方法は、上述した特性を有する本組成物が得られれば特に限られないが、例えば、バッチ式混錬機内で、ショアＡ硬さ（直後）が９０以上であるＴＰＵと、当該ＴＰＵ１００重量部に対して３０重量部以上、１９０重量部以下の、ショアＤ硬さ（直後）が４０以上であるＭＢＳ樹脂と、を溶融混錬することを含むことが好ましい。 The method for producing the present composition is not particularly limited as long as the present composition having the properties described above can be obtained. It is preferable to melt-knead 30 parts by weight or more and 190 parts by weight or less of an MBS resin having a Shore D hardness (immediately) of 40 or more with respect to 100 parts by weight of the TPU.
　ＴＰＵとＭＢＳ樹脂とを溶融混錬する温度は、本発明の効果が得られれば特に限られないが、例えば、１００℃以上、２５０℃以下の範囲内であることが好ましく、１２５℃以上、２２５℃以下の範囲内であることがより好ましく、１５０℃以上、２００℃以下の範囲内であることがさらに好ましく、１６０℃以上、１９０℃以下の範囲内であることが特に好ましい。 The temperature at which the TPU and the MBS resin are melt-kneaded is not particularly limited as long as the effects of the present invention can be obtained. C. or less, more preferably 150.degree. C. to 200.degree. C., and particularly preferably 160.degree. C. to 190.degree.
　バッチ式混錬機は、本発明の効果が得られれば特に限られず、例えば、ブレードを有する混錬機であってもよいし、ブレードを有しない混錬機であってもよい。具体的に、バッチ式混錬機としては、例えば、加圧ニーダー又はバンバリーミキサーが好ましく用いられる。 The batch type kneader is not particularly limited as long as the effects of the present invention can be obtained. For example, it may be a kneader with blades or a kneader without blades. Specifically, as a batch type kneader, for example, a pressure kneader or a Banbury mixer is preferably used.
　本組成物は、バッチ式混錬機内において溶融混錬された後に、温度が１７０℃に設定された前記混錬機から自重で全量が剥離する剥離性を有する。すなわち、例えば、バッチ式混錬機内で、上述したＴＰＵとＭＢＳ樹脂とを溶融混錬することにより本組成物を製造する場合において、当該混錬機の取り出し口が鉛直方向における下方に向くよう、温度が１７０℃に設定された当該混錬機をセットすると、本組成物は、その自重によって当該混錬機の内面から剥離して落下し、当該取り出し口から、その全量を回収することができる。 After being melt-kneaded in a batch-type kneader, the composition has a peeling property whereby the entire amount is peeled off from the kneader set at a temperature of 170°C by its own weight. That is, for example, when the present composition is produced by melt-kneading the TPU and the MBS resin in a batch kneader, When the kneader is set at a temperature of 170°C, the composition is separated from the inner surface of the kneader by its own weight and falls, and the entire amount can be recovered from the outlet. .
　このように、本組成物は、優れた透明性に加えて、優れた剥離性を有する。このため、本組成物は、例えば、加工装置に対しても優れた剥離性を有し、優れた加工性を有する。 Thus, the present composition has excellent releasability in addition to excellent transparency. Therefore, the present composition has, for example, excellent releasability against processing equipment and excellent processability.
　次に、本実施形態に係る具体的な実施例について説明する。 Next, a specific example according to this embodiment will be described.
［組成物の製造］
　ＴＰＵとして、図１Ａに示す５種類ＴＰＵ（ＴＰＵ＃１～＃５）を用いた。また、ＭＢＳ樹脂として、図１Ｂに示す５種類のＭＢＳ樹脂（ＭＢＳ＃１～＃５）を用いた。また、滑剤として脂肪酸アミドを用い、安定剤としてリン系安定剤を用いた。なお、図１Ａ及び図１Ｂに示すＳＰ値は、濁度滴定法を用いて、文献１（K. W. Suh, D. H. Clarke : J. Polymer Sci., A-1, 5 1671 (1967)）及び文献２（K. W. Suh, J. M. Corbett : J. Appl. Polymer Sci., 12 2359 (1968)）を参考にし、良溶媒としてメチルエチルケトン、高極性貧溶媒としてエタノール、低極性貧溶媒としてｎ－ヘキサンを用いて測定した。それぞれの溶媒のＳＰ値は文献３（C. M. Hansen : J. Paint Technol., 39 511 (1967)）を参考にした。 [Production of composition]
Five types of TPU (TPU #1 to #5) shown in FIG. 1A were used as the TPU. As MBS resins, five types of MBS resins (MBS #1 to #5) shown in FIG. 1B were used. In addition, a fatty acid amide was used as a lubricant, and a phosphorus-based stabilizer was used as a stabilizer. The SP values shown in FIGS. 1A and 1B are obtained by using the turbidity titration method, document 1 (K. W. Suh, D. H. Clarke: J. Polymer Sci., A-1, 5 1671 (1967)) and document 2 ( K. W. Suh, J. M. Corbett: J. Appl. Polymer Sci., 12 2359 (1968)), methyl ethyl ketone as a good solvent, ethanol as a highly polar poor solvent, and n-hexane as a low polar poor solvent. The SP value of each solvent was referred to Reference 3 (C. M. Hansen: J. Paint Technol., 39 511 (1967)).
　ブレードを有するバッチ式のニーダー混錬機（容積３Ｌ）内に、上記５種類のＴＰＵのいずれか１種を１００重量部と、上記５種類のＭＢＳ樹脂のいずれか１種を所定重量部と、滑剤を１重量部と、安定剤を０．１重量部とを入れて、約１６０℃で１０分間、溶融混錬することにより、熱可塑性ポリウレタン樹脂組成物を製造した。 100 parts by weight of any one of the above five types of TPU and a predetermined weight part of any one of the above five types of MBS resin are placed in a batch-type kneader kneader having a blade (volume of 3 L), A thermoplastic polyurethane resin composition was produced by adding 1 part by weight of a lubricant and 0.1 part by weight of a stabilizer and melt-kneading them at about 160° C. for 10 minutes.
　また、ＭＢＳ樹脂に代えて、アクリロニトリル－スチレン（ＡＳ）樹脂、アクリロニトリル－ブタジエン－スチレン（ＡＢＳ）樹脂、ポリメチルメタクリレート（ＰＭＭＡ）樹脂、コアシェル型のアクリルゴム（ＡＲ＃１）、透明アクリルゴム（ＡＲ＃２）又はシリコーン・アクリルゴム（ＳＡＲ）を用いた組成物も同様にして製造した。また、ＭＢＳ樹脂を用いない組成物、及びＴＰＵを用いない組成物も同様にして製造した。 In place of MBS resin, acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, polymethyl methacrylate (PMMA) resin, core-shell type acrylic rubber (AR#1), transparent acrylic rubber (AR Compositions using #2) or silicone-acrylic rubber (SAR) were also prepared in the same manner. A composition without MBS resin and a composition without TPU were also prepared in the same manner.
［剥離性の評価］
　混錬後、ニーダー混錬機を、その取り出し口が鉛直方向下向きとなるようにセットし、当該ニーダー混錬機内の組成物を自重によって落下させて回収した。この回収の際に、温度が１７０℃に設定されたニーダー混錬機の金属製の内表面から組成物が自重によって剥離する様子を目視で確認し、当該組成物の剥離性を評価した。 [Evaluation of peelability]
After the kneading, the kneader kneader was set so that the outlet was vertically downward, and the composition in the kneader kneader was dropped by its own weight and collected. At the time of recovery, peeling of the composition from the metal inner surface of the kneader kneader set at 170° C. by its own weight was visually observed to evaluate the peelability of the composition.
［組成物の特性の評価］
　また、回収された組成物について、比重、ショアＡ硬さ（直後）、ショアＡ硬さ（１０秒後）、引張強さ（ＭＰａ）、切断時伸び（％）、１００％モジュラス（ＭＰａ）、ＭＦＲ（ｇ／１０ｍｉｎ）、耐寒性（℃）、全光線透過率（％）及びヘーズ値（％）を評価した。なお、耐寒性については、ＪＩＳ　Ｋ　６７２３－１９９５に準拠した方法において、ドライアイス－メタノール浴による冷却を用い、マイナス６５℃を下限値として測定した。 [Evaluation of Composition Properties]
In addition, the recovered composition, specific gravity, Shore A hardness (immediately), Shore A hardness (10 seconds later), tensile strength (MPa), elongation at break (%), 100% modulus (MPa), MFR (g/10min), cold resistance (°C), total light transmittance (%) and haze value (%) were evaluated. The cold resistance was measured in accordance with JIS K 6723-1995 using cooling in a dry ice-methanol bath with a lower limit of -65°C.
［結果］
　図２Ａ及び図２Ｂには、組成物の特性を評価した結果を示す。図２Ａ及び図２Ｂのニーダー剥離性の欄において「〇」印は、組成物の全量が自重によってニーダー混錬機の内表面から剥離して回収できた（すなわち、剥離性に優れていた）ことを示し、「×」印は、組成物の一部又は全部がニーダー混錬機の内表面に付着して剥離しなかった（すなわち、剥離性に劣るものであった）ことを示す。また、図２のＭＦＲの欄における「×」印は、組成物に荷重をかけても流動せず、ＭＦＲの測定が不可能であったことを示す。 [result]
2A and 2B show the results of evaluating the properties of the composition. In the column of kneader releasability in FIGS. 2A and 2B, the "○" mark indicates that the entire amount of the composition was detached and recovered from the inner surface of the kneader kneader by its own weight (that is, the releasability was excellent). , and the "x" mark indicates that part or all of the composition adhered to the inner surface of the kneader kneader and was not peeled off (that is, the peelability was poor). In addition, the "x" mark in the MFR column of FIG. 2 indicates that the composition did not flow even when a load was applied, and the MFR could not be measured.
　図２Ａに示すように、ＴＰＵ＃１を１００重量部に対してＭＢＳ＃１を５０～１００重量部含む例１～３の組成物は、高い透明性（全光線透過率８３．２％以上、ヘーズ値１６．８％以下）を有し、且つ、剥離性に優れていた。 As shown in FIG. 2A, the compositions of Examples 1 to 3 containing 50 to 100 parts by weight of MBS#1 to 100 parts by weight of TPU#1 have high transparency (total light transmittance of 83.2% or more, haze value of 16.8% or less) and excellent peelability.
　これに対し、ＴＰＵ＃１を１００重量部に対してＭＢＳ＃１を５～２０重量部含む例Ｃ６～Ｃ８の組成物は、剥離性が悪く、自重のみによっては、その全量をニーダー混錬機から回収できなかった。また、これら例Ｃ６～Ｃ８の組成物は、ＭＦＲが大きく、３０ｇ／１０ｍｉｎ以上であった。また、ＭＢＳ＃１を２０重量部含む例Ｃ８の組成物は、ヘーズ値が高めで１９．６％であった。また、ＴＰＵ＃１を１００重量部に対してＭＢＳ＃１を２００重量部含む例Ｃ９の組成物は、剥離性が悪く、ＭＦＲの測定において流動性を示さなかった。 On the other hand, the compositions of Examples C6 to C8 containing 5 to 20 parts by weight of MBS#1 to 100 parts by weight of TPU#1 had poor release properties, and the entire amount could be could not be recovered from Also, the compositions of Examples C6 to C8 had a large MFR of 30 g/10 min or more. Also, the composition of Example C8, which contained 20 parts by weight of MBS #1, had a higher haze value of 19.6%. Also, the composition of Example C9, which contained 200 parts by weight of MBS#1 to 100 parts by weight of TPU#1, had poor release properties and did not flow as measured by MFR.
　一方、ＴＰＵ＃１を含みＭＢＳ樹脂を含まない例Ｃ１の組成物は、剥離性が悪く、ＭＦＲが大きく３７ｇ／１０ｍｉｎであり、ヘーズ値が高めで１９．７％であった。同様に、他の４種のＴＰＵ＃２～＃５のいずれかを含みＭＢＳ樹脂を含まない例Ｃ２～Ｃ5の組成物もまた、剥離性、ＭＦＲ又はヘーズ値の点で十分な特性を有しなかった。また、ＭＢＳ＃１を含みＴＰＵを含まない例Ｃ１０の組成物は、ＭＦＲの測定において流動性を示さず、引張強さ及び切断時伸びの点で機械的強度に劣るものであった。 On the other hand, the composition of Example C1 containing TPU#1 and not containing MBS resin had poor release properties, a large MFR of 37 g/10 min, and a high haze value of 19.7%. Similarly, the compositions of Examples C2-C5 containing any of the other four TPUs #2-#5 but no MBS resin also have satisfactory properties in terms of release, MFR or haze. I didn't. Also, the composition of Example C10, which contained MBS#1 but did not contain TPU, showed no fluidity in MFR measurements and had poor mechanical strength in terms of tensile strength and elongation at break.
　ＴＰＵ＃１を１００重量部に対してＭＢＳ＃２を２０重量部含む例Ｃ１１の組成物は、ニーダー剥離性が悪く、ＭＦＲが大きく４８ｇ／１０ｍｉｎであった。ＴＰＵ＃１を１００重量部に対してＭＢＳ＃２を５０重量部又は８０重量部含む例Ｃ１２及び１３の組成物は、引張強さ及び切断時伸びの点で機械的強度に劣り、耐寒性も劣る（－４５℃程度）ものであった。 The composition of Example C11, which contained 100 parts by weight of TPU# 1 and 20 parts by weight of MBS#2, had poor kneader releasability and a large MFR of 48 g/10 min. The compositions of Examples C12 and 13 containing 50 or 80 parts MBS#2 to 100 parts TPU#1 have poor mechanical strength in terms of tensile strength and elongation at break, and poor cold resistance. It was inferior (about -45°C).
　また、図２Ｂに示すように、ＴＰＵ＃１を１００重量部に対してＭＢＳ＃３、ＭＢＳ＃４、ＭＢＳ＃５、ＡＳ、ＡＢＳ、ＰＭＭＡ、ＡＲ＃１、ＡＲ＃２又はＳＡＲを５０重量部含む例Ｃ１４～Ｃ２２の組成物は、ヘーズ値が大きく、透明性に欠けるものであった。 Further, as shown in FIG. 2B, 50 parts by weight of MBS#3, MBS#4, MBS#5, AS, ABS, PMMA, AR#1, AR#2 or SAR to 100 parts by weight of TPU#1 The compositions of Examples C14-C22 containing high haze values and lack of transparency.
　また、ＴＰＵ＃１以外の４種のＴＰＵ＃２～＃５を１００重量部に対してＭＢＳ＃１を５０重量部又は８０重量部含む例Ｃ２３～Ｃ３０の組成物もまた、ヘーズ値が大きく、透明性に欠けるものであった。

  In addition, the compositions of Examples C23 to C30, which contain 50 or 80 parts by weight of MBS#1 for 100 parts by weight of four TPUs #2 to #5 other than TPU#1, also have high haze values, It lacked transparency.

Claims (6)

  1. 　ＪＩＳ　Ｋ　６２５３－３：２０１２に準拠した方法において試験片に押針を押し込んだ直後に測定されるショアＡ硬さが９０以上である熱可塑性ポリウレタン樹脂と、
    　前記熱可塑性ポリウレタン樹脂１００重量部に対して３０重量部以上、１９０重量部以下の、ＪＩＳ　Ｋ　６２５３－３：２０１２に準拠した方法において試験片に押針を押し込んだ直後に測定されるショアＤ硬さが４０以上であるメチルメタクリレート－ブタジエン－スチレン共重合体樹脂と、
    　を含む、
    　透明熱可塑性ポリウレタン樹脂組成物。     A thermoplastic polyurethane resin having a Shore A hardness of 90 or more measured immediately after pushing an indentation needle into a test piece in accordance with JIS K 6253-3:2012;
    30 parts by weight or more and 190 parts by weight or less with respect to 100 parts by weight of the thermoplastic polyurethane resin, JIS K 6253-3: Shore D hardness measured immediately after pushing a needle into the test piece in a method conforming to 2012 a methyl methacrylate-butadiene-styrene copolymer resin having a polystyrene of 40 or more;
    including,
    A transparent thermoplastic polyurethane resin composition.
  2. 　ＪＩＳ　Ｋ　７１３６：２０００に準拠した方法により測定されるヘーズ値が、１９．０％以下である、
    　請求項１に記載の透明熱可塑性ポリウレタン樹脂組成物。     A haze value measured by a method conforming to JIS K 7136:2000 is 19.0% or less.
    The transparent thermoplastic polyurethane resin composition according to claim 1.
  3. 　ＪＩＳ　Ｋ　６２５１：２０１７に準拠した方法により測定される引張強さが、２６ＭＰａ以上である、
    　請求項１又は２に記載の透明熱可塑性ポリウレタン樹脂組成物。     Tensile strength measured by a method conforming to JIS K 6251: 2017 is 26 MPa or more,
    The transparent thermoplastic polyurethane resin composition according to claim 1 or 2.
  4. 　ＪＩＳ　Ｋ　６７２３－１９９５に準拠した方法により測定される耐寒性が、マイナス５０℃以下である、
    　請求項１乃至３のいずれかに記載の透明熱可塑性ポリウレタン樹脂組成物。     Cold resistance measured by a method in accordance with JIS K 6723-1995 is -50 ° C. or less,
    The transparent thermoplastic polyurethane resin composition according to any one of claims 1 to 3.
  5. 　ＪＩＳ　Ｋ　７２１０－１：２０１４に準拠した方法により１９０℃、１０ｋｇ荷重の条件で測定されるメルトフローレイトが、２５．０ｇ／１０ｍｉｎ以下である、
    　請求項１乃至４のいずれかに記載の透明熱可塑性ポリウレタン樹脂組成物。     The melt flow rate measured under conditions of 190° C. and 10 kg load by a method in accordance with JIS K 7210-1:2014 is 25.0 g/10 min or less.
    The transparent thermoplastic polyurethane resin composition according to any one of claims 1 to 4.
  6. 　バッチ式混錬機内において溶融混錬された後に、温度が１７０℃に設定された前記混錬機から自重で全量が剥離する剥離性を有する、
    　請求項１乃至５のいずれか記載の透明熱可塑性ポリウレタン樹脂組成物。

          After being melted and kneaded in a batch type kneader, the kneader set at a temperature of 170 ° C. has a peeling property that the entire amount is peeled off by its own weight.
    The transparent thermoplastic polyurethane resin composition according to any one of claims 1 to 5.
PCT/JP2023/003249 2022-03-03 2023-02-01 Transparent thermoplastic polyurethane resin composition WO2023166904A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6038458A (en) * 1983-07-18 1985-02-28 ザ　ダウ　ケミカル　コンパニ− Polymer blend
KR20070051450A (en) * 2005-11-15 2007-05-18 주식회사 엘지화학 Thermoplastic polyurethane resin composition having excellent low-temperature toughness and transparency
KR20080045436A (en) * 2006-11-20 2008-05-23 에스케이케미칼주식회사 Composition for thermoplastic polyurethane elastomer blend with excellent high frequency weldability
KR20100001513A (en) * 2008-06-27 2010-01-06 주식회사 엘지화학 Low hardness, low weight and high performance transparent polyurethane resin composition
JP2011021167A (en) * 2009-07-21 2011-02-03 Okamoto Kk Transparent polyurethane film and method of manufacturing the same
CN109836708A (en) * 2017-11-29 2019-06-04 万华化学集团股份有限公司 A kind of high-damping thermoplastic urethane elastomer composition and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6038458A (en) * 1983-07-18 1985-02-28 ザ　ダウ　ケミカル　コンパニ− Polymer blend
KR20070051450A (en) * 2005-11-15 2007-05-18 주식회사 엘지화학 Thermoplastic polyurethane resin composition having excellent low-temperature toughness and transparency
KR20080045436A (en) * 2006-11-20 2008-05-23 에스케이케미칼주식회사 Composition for thermoplastic polyurethane elastomer blend with excellent high frequency weldability
KR20100001513A (en) * 2008-06-27 2010-01-06 주식회사 엘지화학 Low hardness, low weight and high performance transparent polyurethane resin composition
JP2011021167A (en) * 2009-07-21 2011-02-03 Okamoto Kk Transparent polyurethane film and method of manufacturing the same
CN109836708A (en) * 2017-11-29 2019-06-04 万华化学集团股份有限公司 A kind of high-damping thermoplastic urethane elastomer composition and preparation method thereof

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