JP2021181563A - Alloy resin and molding - Google Patents
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- 229920005989 resin Polymers 0.000 title claims abstract description 135
- 239000011347 resin Substances 0.000 title claims abstract description 135
- 239000000956 alloy Substances 0.000 title claims abstract description 71
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 71
- 238000000465 moulding Methods 0.000 title claims abstract description 13
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000009477 glass transition Effects 0.000 claims abstract description 22
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 6
- 238000002485 combustion reaction Methods 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 41
- 238000006116 polymerization reaction Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000000646 scanning calorimetry Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920005497 Acrypet® Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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Abstract
Description
本発明は、アロイ樹脂及び成形品に関する。 The present invention relates to alloy resins and molded articles.
硬質塩化ビニル系樹脂は、一般に難燃性及び耐薬品性に優れるため、パイプ、一般建材等の用途に広く用いられている。また、硬質塩化ビニル系樹脂の特性を改善する目的で、塩化ビニル系樹脂にアクリル樹脂やＡＢＳ樹脂等をアロイとして添加することも知られている（例えば、特許文献１）。 Rigid vinyl chloride resins are generally excellent in flame retardancy and chemical resistance, and are therefore widely used in pipes, general building materials, and the like. It is also known to add an acrylic resin, an ABS resin, or the like as an alloy to the vinyl chloride resin for the purpose of improving the characteristics of the rigid vinyl chloride resin (for example, Patent Document 1).
しかし、特許文献１のような従来のアロイ樹脂では、難燃性と硬度が両立された成形品を得ることは難しい。 However, with the conventional alloy resin as in Patent Document 1, it is difficult to obtain a molded product having both flame retardancy and hardness.
本発明は、難燃性に優れ、硬度が高い成形品が得られるアロイ樹脂、及び前記アロイ樹脂を用いた成形品を提供することを目的とする。 An object of the present invention is to provide an alloy resin from which a molded product having excellent flame retardancy and high hardness can be obtained, and a molded product using the alloy resin.
本発明は、以下の態様を有する。
［１］塩化ビニル系樹脂とメチルメタクリレート系樹脂とが配合されたアロイ樹脂であって、ＪＩＳ Ｋ ７１２１に従って測定されるガラス転移温度Ｔｇ（単位：℃）とＪＩＳ Ｋ ７１６１に従って測定される引張応力Ｓ（単位：ＭＰａ）とを、前記ガラス転移温度Ｔｇを横軸、前記引張応力Ｓを縦軸としたグラフにプロットしたときに下記式（１）で表される直線と下記式（２）で表される直線で挟まれた領域内にあり、かつ前記ガラス転移温度Ｔｇが７０℃以上である、アロイ樹脂。
Ｓ＝３４＋Ｔｇ×０．４８ ・・・（１）
Ｓ＝２４＋Ｔｇ×０．４８ ・・・（２）
［２］ＪＩＳ Ｋ５６００−５−４に従って測定される鉛筆硬度がＦ以上である、［１］に記載のアロイ樹脂。
［３］ＡＳＴＭ Ｄ３８０１に準拠したＵＬ９４Ｖ ２０ｍｍ垂直燃焼試験により測定される燃焼性分類がＶ−１以上である、［１］又は［２］に記載のアロイ樹脂。
［４］前記塩化ビニル系樹脂と前記メチルメタクリレート系樹脂とが質量比５０：５０〜８０：２０で配合されている、［１］〜［３］のいずれかに記載のアロイ樹脂。
［５］［１］〜［４］のいずれかに記載のアロイ樹脂が成形された成形品。
The present invention has the following aspects.
[1] An alloy resin in which a vinyl chloride resin and a methyl methacrylate resin are blended, and the glass transition temperature Tg (unit: ° C.) measured according to JIS K 7121 and the tensile stress S measured according to JIS K 7161. (Unit: MPa) is represented by the following formula (1) and the following formula (2) when plotted on a graph with the glass transition temperature Tg on the horizontal axis and the tensile stress S on the vertical axis. An alloy resin that is in the region sandwiched by the straight lines and has a glass transition temperature Tg of 70 ° C. or higher.
S = 34 + Tg × 0.48 ・ ・ ・ (1)
S = 24 + Tg × 0.48 ・ ・ ・ (2)
[2] The alloy resin according to [1], wherein the pencil hardness measured according to JIS K5600-5-4 is F or more.
[3] The alloy resin according to [1] or [2], wherein the flammability classification measured by the UL94V 20 mm vertical combustion test according to ASTM D3801 is V-1 or higher.
[4] The alloy resin according to any one of [1] to [3], wherein the vinyl chloride resin and the methyl methacrylate resin are blended in a mass ratio of 50:50 to 80:20.
[5] A molded product obtained by molding the alloy resin according to any one of [1] to [4].
本発明によれば、難燃性に優れ、硬度が高い成形品が得られるアロイ樹脂、及び前記アロイ樹脂を用いた成形品を提供できる。 According to the present invention, it is possible to provide an alloy resin capable of obtaining a molded product having excellent flame retardancy and high hardness, and a molded product using the alloy resin.
［アロイ樹脂］
本発明のアロイ樹脂は、塩化ビニル系樹脂（以下、「ＰＶＣ系樹脂」と記す。）とメチルメタクリレート系樹脂（以下、「ＭＭＡ系樹脂」と記す。）とが配合されたアロイ樹脂である。
[Alloy resin]
The alloy resin of the present invention is an alloy resin in which a vinyl chloride resin (hereinafter referred to as "PVC resin") and a methyl methacrylate resin (hereinafter referred to as "MMA resin") are blended.
本発明のアロイ樹脂は、ＪＩＳ Ｋ ７１２１に従って測定されるガラス転移温度Ｔｇ（単位：℃）とＪＩＳ Ｋ７１６１に従って測定される引張応力Ｓ（単位：ＭＰａ）とを、ガラス転移温度Ｔｇを横軸、引張応力Ｓを縦軸としたグラフにプロットしたときに、下記式（１）で表される直線（以下、「直線（１）」とも記す。）と下記式（２）で表される直線（以下、「直線（２）」とも記す。）で挟まれた領域（以下、「領域Ａ」とも記す。）内にあり、かつガラス転移温度Ｔｇ（以下、単に「Ｔｇ」とも記す。）が７０℃以上である。ただし、「プロットが領域Ａ内にある」とは、プロットが直線（１）上にある場合、及びプロットが直線（２）上にある場合も含むものとする。
Ｓ＝３４＋Ｔｇ×０．４８ ・・・（１）
Ｓ＝２４＋Ｔｇ×０．４８ ・・・（２）
アロイ樹脂のＴｇと引張応力Ｓのプロットが領域Ａ内にあり、かつＴｇが７０℃以上であることで、難燃性に優れ、硬度が高い成形品を得ることができる。
The alloy resin of the present invention has a glass transition temperature Tg (unit: ° C.) measured according to JIS K 7121 and a tensile stress S (unit: MPa) measured according to JIS K 7161, with the glass transition temperature Tg on the horizontal axis and tension. When plotted on a graph with the stress S as the vertical axis, a straight line represented by the following formula (1) (hereinafter, also referred to as “straight line (1)”) and a straight line represented by the following formula (2) (hereinafter referred to as “straight line”). , Also referred to as "straight line (2)"), and the glass transition temperature Tg (hereinafter, also simply referred to as "Tg") is 70 ° C. in the region (hereinafter, also referred to as "region A"). That is all. However, "the plot is in the area A" includes the case where the plot is on the straight line (1) and the case where the plot is on the straight line (2).
S = 34 + Tg × 0.48 ・ ・ ・ (1)
S = 24 + Tg × 0.48 ・ ・ ・ (2)
When the plot of Tg and tensile stress S of the alloy resin is in the region A and the Tg is 70 ° C. or higher, a molded product having excellent flame retardancy and high hardness can be obtained.
アロイ樹脂のＴｇは、７０℃以上であり、７５℃以上が好ましく、７６℃以上１０５℃以下がより好ましく、８０℃以上９０℃以下がさらに好ましい。アロイ樹脂のＴｇが前記範囲の下限値以上であれば、成形品の肉厚を薄くでき、軽量化となる。アロイ樹脂のＴｇが前記範囲の上限値以下であれば、成形加工性が良く、応力や弾性率が向上する。
なお、アロイ樹脂のＴｇは、ＪＩＳ Ｋ ７１２１に準じ、示差熱走査熱量測定（ＤＳＣ）によって中間点ガラス転移温度として測定される。アロイ樹脂のＴｇは、ＰＶＣ系樹脂の平均重合度や配合剤、ＭＭＡ系樹脂の重量平均分子量及び数平均分子量を調節することによって調節することができる。
The Tg of the alloy resin is 70 ° C. or higher, preferably 75 ° C. or higher, more preferably 76 ° C. or higher and 105 ° C. or lower, and even more preferably 80 ° C. or higher and 90 ° C. or lower. When the Tg of the alloy resin is at least the lower limit of the above range, the wall thickness of the molded product can be reduced and the weight can be reduced. When the Tg of the alloy resin is not more than the upper limit of the above range, the molding processability is good and the stress and elastic modulus are improved.
The Tg of the alloy resin is measured as the intermediate point glass transition temperature by differential thermal scanning calorimetry (DSC) according to JIS K 7121. The Tg of the alloy resin can be adjusted by adjusting the average degree of polymerization and the compounding agent of the PVC-based resin, and the weight average molecular weight and the number average molecular weight of the MMA-based resin.
アロイ樹脂の引張応力Ｓは、６０ＭＰａ以上９０ＭＰａ以下が好ましく、６２ＭＰａ以上８０ＭＰａ以下がより好ましい。アロイ樹脂の引張応力Ｓが前記範囲の下限値以上であれば、成形品の鉛筆硬度が向上する。アロイ樹脂の引張応力Ｓが前記範囲の上限値以下であれば、成形品の加工性が良好となる。アロイ樹脂の引張応力Ｓは、ＰＶＣ系樹脂の平均重合度や配合剤、ＭＭＡ系樹脂の重量平均分子量及び数平均分子量、射出成形加工条件等によって調節できる。 The tensile stress S of the alloy resin is preferably 60 MPa or more and 90 MPa or less, and more preferably 62 MPa or more and 80 MPa or less. When the tensile stress S of the alloy resin is at least the lower limit of the above range, the pencil hardness of the molded product is improved. When the tensile stress S of the alloy resin is not more than the upper limit of the above range, the workability of the molded product is good. The tensile stress S of the alloy resin can be adjusted by the average degree of polymerization of the PVC resin, the compounding agent, the weight average molecular weight and the number average molecular weight of the MMA resin, the injection molding processing conditions, and the like.
アロイ樹脂の鉛筆硬度は、Ｆ以上が好ましく、Ｈ以上がより好ましい。鉛筆硬度が前記下限値以上であれば、耐傷付き性に優れた成形品が得られる。アロイ樹脂の鉛筆硬度は、ＰＶＣ系樹脂とＭＭＡ系樹脂との質量比等によって調節できる。なお、アロイ樹脂の鉛筆硬度は、ＪＩＳ Ｋ５６００−５−４に準拠して測定される。 The pencil hardness of the alloy resin is preferably F or higher, more preferably H or higher. When the pencil hardness is at least the above lower limit value, a molded product having excellent scratch resistance can be obtained. The pencil hardness of the alloy resin can be adjusted by the mass ratio of the PVC resin and the MMA resin and the like. The pencil hardness of the alloy resin is measured according to JIS K5600-5-4.
アロイ樹脂のＡＳＴＭ Ｄ３８０１に準拠したＵＬ９４Ｖ ２０ｍｍ垂直燃焼試験により測定される燃焼性分類は、Ｖ−１以上が好ましく、Ｖ−０がより好ましい。アロイ樹脂の前記燃焼性分類がＶ−１以上であれば、難燃性に優れた成形品が得られる。アロイ樹脂の燃焼性は、ＰＶＣ系樹脂とＭＭＡ系樹脂との質量比等によって調節できる。 The combustibility classification measured by the UL94V 20 mm vertical combustion test according to ASTM D3801 of the alloy resin is preferably V-1 or higher, and more preferably V-0. When the flammability classification of the alloy resin is V-1 or higher, a molded product having excellent flame retardancy can be obtained. The flammability of the alloy resin can be adjusted by the mass ratio of the PVC resin and the MMA resin and the like.
アロイ樹脂の引張弾性率は、２，０００ＭＰａ以上３，５００ＭＰａ以下が好ましく、２，５００ＭＰａ以上３，０００ＭＰａ以下がより好ましい。アロイ樹脂の引張弾性率が前記範囲の下限値以上であれば、成型品の鉛筆硬度が向上する。アロイ樹脂の引張弾性率が前記範囲の上限値以下であれば、成型品の経済性が良好となる。アロイ樹脂の引張弾性率は、ＰＶＣ系樹脂の平均重合度や配合剤、ＭＭＡ系樹脂の重量平均分子量及び数平均分子量、ＰＶＣ系樹脂とＭＭＡ系樹脂との質量比等によって調節できる。なお、アロイ樹脂の引張弾性率は、ＪＩＳ Ｋ７１６１に準拠して測定される。 The tensile elastic modulus of the alloy resin is preferably 2,000 MPa or more and 3,500 MPa or less, and more preferably 2,500 MPa or more and 3,000 MPa or less. When the tensile elastic modulus of the alloy resin is at least the lower limit of the above range, the pencil hardness of the molded product is improved. When the tensile elastic modulus of the alloy resin is not more than the upper limit of the above range, the economic efficiency of the molded product is good. The tensile elastic modulus of the alloy resin can be adjusted by the average degree of polymerization and compounding agent of the PVC resin, the weight average molecular weight and the number average molecular weight of the MMA resin, the mass ratio of the PVC resin and the MMA resin, and the like. The tensile elastic modulus of the alloy resin is measured according to JIS K7161.
ＰＶＣ系樹脂とＭＭＡ系樹脂とが質量比は、５０：５０〜８０：２０が好ましく、６０：４０〜７５：２５がより好ましい。ＰＶＣ系樹脂の割合が高いほど、難燃性に優れる。ＭＭＡ系樹脂の割合が高いほど、表面硬度が向上する。 The mass ratio of the PVC-based resin and the MMA-based resin is preferably 50:50 to 80:20, more preferably 60:40 to 75:25. The higher the proportion of PVC resin, the better the flame retardancy. The higher the proportion of MMA-based resin, the higher the surface hardness.
アロイ樹脂中のＰＶＣ系樹脂とＭＭＡ系樹脂の合計の割合は、アロイ樹脂の総質量に対して、８０質量％以上が好ましく、８５質量％以上がより好ましく、９０質量％以上がさらに好ましい。 The total ratio of the PVC-based resin and the MMA-based resin in the alloy resin is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, based on the total mass of the alloy resin.
ＰＶＣ系樹脂は、塩化ビニル由来の繰り返し単位（以下、「塩化ビニル単位」とも記す。）の割合が全繰り返し単位に対して５０質量％超の重合体である。ＰＶＣ系樹脂は、塩化ビニルの単独重合体であってもよく、塩化ビニルと、塩化ビニルと共重合可能なビニル系単量体との共重合体であってもよい。ＰＶＣ系樹脂が共重合体である場合、ランダム共重合体であってもよく、ブロック共重合体であってもよく、グラフト共重合体であってもよい。アロイ樹脂に含まれるＰＶＣ系樹脂は、１種であってもよく、２種以上であってもよい。 The PVC-based resin is a polymer in which the ratio of the repeating unit derived from vinyl chloride (hereinafter, also referred to as “vinyl chloride unit”) is more than 50% by mass with respect to all the repeating units. The PVC-based resin may be a homopolymer of vinyl chloride, or may be a copolymer of vinyl chloride and a vinyl-based monomer copolymerizable with vinyl chloride. When the PVC-based resin is a copolymer, it may be a random copolymer, a block copolymer, or a graft copolymer. The PVC-based resin contained in the alloy resin may be one kind or two or more kinds.
ＰＶＣ系樹脂中の塩化ビニル単位の割合は、全繰り返し単位に対して、７５質量％以上が好ましく、８０質量％以上がより好ましく、８５質量％以上がさらに好ましく、９８質量％以上が特に好ましい。 The ratio of the vinyl chloride unit in the PVC resin is preferably 75% by mass or more, more preferably 80% by mass or more, further preferably 85% by mass or more, and particularly preferably 98% by mass or more with respect to all the repeating units.
塩化ビニルと共重合可能なビニル系単量体としては、特に限定されず、例えば、脂肪酸ビニルエステル、アクリレート、メタクリレート、シアン化ビニル、ビニルエーテル、α−オレフィン、不飽和カルボン酸又はその酸無水物、塩化ビニリデン、臭化ビニル、各種ウレタン等が挙げられる。 The vinyl-based monomer copolymerizable with vinyl chloride is not particularly limited, and for example, fatty acid vinyl ester, acrylate, methacrylate, vinyl cyanide, vinyl ether, α-olefin, unsaturated carboxylic acid or its acid anhydride, Examples thereof include vinylidene chloride, vinyl bromide, and various types of urethane.
脂肪酸ビニルエステルとしては、酢酸ビニル、プロピオン酸ビニル、ラウリン酸ビニル等が挙げられる。アクリレートとしては、メチルアクリレート、エチルアクリレート、ブチルアクリレート等が挙げられる。メタクリレートとしては、メチルメタクリレート、エチルメタクリレート等が挙げられる。シアン化ビニルとしては、アクリロニトリル、メタクリロニトリル等が挙げられる。ビニルエーテルとしては、ビニルメチルエーテル、ビニルブチルエーテル、ビニルオクチルエーテル等が挙げられる。α−オレフィンとしては、エチレン、プロピレン、ブチレン等が挙げられる。不飽和カルボン酸又はその酸無水物類としては、アクリル酸、メタクリル酸、無水マレイン酸等が挙げられる。塩化ビニルと共重合可能なビニル系単量体は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the fatty acid vinyl ester include vinyl acetate, vinyl propionate, vinyl laurate and the like. Examples of the acrylate include methyl acrylate, ethyl acrylate, butyl acrylate and the like. Examples of the methacrylate include methyl methacrylate and ethyl methacrylate. Examples of vinyl cyanide include acrylonitrile and methacrylonitrile. Examples of the vinyl ether include vinyl methyl ether, vinyl butyl ether, vinyl octyl ether and the like. Examples of the α-olefin include ethylene, propylene and butylene. Examples of unsaturated carboxylic acid or acid anhydride thereof include acrylic acid, methacrylic acid, maleic anhydride and the like. As the vinyl-based monomer copolymerizable with vinyl chloride, one type may be used alone, or two or more types may be used in combination.
ＰＶＣ系樹脂の平均重合度は、４００以上１２００以下が好ましく、５００以上８００以下がより好ましく、５５０以上７００以下がさらに好ましい。ＰＶＣ系樹脂の平均重合度が前記範囲の下限値以上であれば、鉛筆硬度が向上する。ＰＶＣ系樹脂の平均重合度が前記範囲の上限値以下であれば、成形加工性が向上する。なお、平均重合度は、ＪＩＳ Ｋ ６７２０−２によって測定される。 The average degree of polymerization of the PVC resin is preferably 400 or more and 1200 or less, more preferably 500 or more and 800 or less, and further preferably 550 or more and 700 or less. When the average degree of polymerization of the PVC resin is at least the lower limit of the above range, the pencil hardness is improved. When the average degree of polymerization of the PVC resin is not more than the upper limit of the above range, the molding processability is improved. The average degree of polymerization is measured by JIS K 6720-2.
塩化ビニル系樹脂としては、硬質塩化ビニル樹脂であってもよく、軟質塩化ビニル樹脂であってもよいが、成形品の表面硬度が高く、耐傷付き性に優れる点から、硬質塩化ビニル系樹脂が好ましい。 The vinyl chloride resin may be a hard vinyl chloride resin or a soft vinyl chloride resin, but the hard vinyl chloride resin is used because the surface hardness of the molded product is high and the scratch resistance is excellent. preferable.
ＭＭＡ系樹脂は、メチルメタクリレート（ＭＭＡ）由来の繰り返し単位（以下、「ＭＭＡ単位」とも記す。）の割合が全繰り返し単位に対して８０質量％以上の重合体である。ＭＭＡ系樹脂は、ＭＭＡの単独重合体であってもよく、ＭＭＡと、ＭＭＡ以外の（メタ）アクリレートとの共重合体であってもよい。なお、（メタ）アクリレートは、メタクリレートとアクリレートの総称である。ＭＭＡ系樹脂が共重合体である場合、ランダム共重合体であってもよく、ブロック共重合体であってもよい。アロイ樹脂に含まれるＭＭＡ系樹脂は、１種であってもよく、２種以上であってもよい。 The MMA-based resin is a polymer in which the ratio of repeating units derived from methyl methacrylate (MMA) (hereinafter, also referred to as “MMA units”) is 80% by mass or more with respect to all repeating units. The MMA-based resin may be a homopolymer of MMA, or may be a copolymer of MMA and a (meth) acrylate other than MMA. In addition, (meth) acrylate is a general term for methacrylate and acrylate. When the MMA-based resin is a copolymer, it may be a random copolymer or a block copolymer. The MMA-based resin contained in the alloy resin may be one kind or two or more kinds.
ＭＭＡ系樹脂中のＭＭＡ単位の割合は、全繰り返し単位に対して、８０質量％以上が好ましく、９０質量％以上がより好ましい。ＭＭＡ単位の割合が前記範囲の下限値以上であれば、成形性が向上する。 The ratio of MMA units in the MMA-based resin is preferably 80% by mass or more, more preferably 90% by mass or more, based on all the repeating units. When the ratio of MMA units is equal to or higher than the lower limit of the above range, the moldability is improved.
ＭＭＡ以外の（メタ）アクリレートとしては、例えば、メチルアクリレート、エチルアクリレート、ｎ−ブチルアクリレート、イソブチルアクリレート、２−エチルヘキシルアクリレート、エチルメタクリレート、ｎ−ブチルメタクリレート、イソブチルメタクリレート、２−エチルヘキシルメタクリレートを例示できる。ＭＭＡ系樹脂に用いるＭＭＡ以外の（メタ）アクリレートは、１種であってもよく、２種以上であってもよい。 Examples of (meth) acrylates other than MMA include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate. The (meth) acrylate other than MMA used for the MMA-based resin may be one kind or two or more kinds.
ＭＭＡ系樹脂の重量平均分子量は、１０，０００以上６００，０００以下が好ましく、２０，０００以上４００，０００以下がより好ましい。ＭＭＡ系樹脂の重量平均分子量が前記範囲の下限値以上であれば、鉛筆硬度が向上する。ＭＭＡ系樹脂の重量平均分子量が前記範囲の上限値以下であれば、強度が向上する。 The weight average molecular weight of the MMA resin is preferably 10,000 or more and 600,000 or less, and more preferably 20,000 or more and 400,000 or less. When the weight average molecular weight of the MMA resin is at least the lower limit of the above range, the pencil hardness is improved. When the weight average molecular weight of the MMA resin is not more than the upper limit of the above range, the strength is improved.
ＭＭＡ系樹脂の数平均分子量は、５，０００以上３００，０００以下が好ましく、１０，０００以上２００，０００以下がより好ましい。ＭＭＡ系樹脂の数平均分子量が前記範囲の下限値以上であれば、鉛筆硬度が向上する。ＭＭＡ系樹脂の数平均分子量が前記範囲の上限値以下であれば、強度が向上する。重量平均分子量及び数平均分子量は、ゲル浸透クロマトグラフィを用いて測定されるポリスチレン換算の平均分子量である。 The number average molecular weight of the MMA resin is preferably 5,000 or more and 300,000 or less, and more preferably 10,000 or more and 200,000 or less. When the number average molecular weight of the MMA resin is at least the lower limit of the above range, the pencil hardness is improved. When the number average molecular weight of the MMA resin is not more than the upper limit of the above range, the strength is improved. The weight average molecular weight and the number average molecular weight are polystyrene-equivalent average molecular weights measured using gel permeation chromatography.
ＭＭＡ系樹脂のメルトフローレート（ＭＦＲ）は、１．０ｇ／１０分以上２０ｇ／１０分以下が好ましく、２．０ｇ／１０分以上１５ｇ／１０分以下がより好ましい。ＭＭＡ系樹脂のＭＦＲが前記範囲の下限値以上であれば、加工性が良好となる。ＭＭＡ系樹脂のＭＦＲが前記範囲の上限値以下であれば、鉛筆硬度が向上する。なお、ＭＦＲは、ＪＩＳ Ｋ ７２１０に準拠し、荷重３７．３Ｎ、温度２３０℃の条件で測定される。 The melt flow rate (MFR) of the MMA resin is preferably 1.0 g / 10 minutes or more and 20 g / 10 minutes or less, and more preferably 2.0 g / 10 minutes or more and 15 g / 10 minutes or less. When the MFR of the MMA-based resin is at least the lower limit of the above range, the workability is good. When the MFR of the MMA resin is not more than the upper limit of the above range, the pencil hardness is improved. The MFR is measured in accordance with JIS K 7210 under the conditions of a load of 37.3 N and a temperature of 230 ° C.
本発明のアロイ樹脂は、本発明の効果を損なわない範囲であれば、必要に応じて熱安定剤、光安定剤、滑剤、酸化防止剤、可塑剤、防汚剤、衝撃改質剤、着色剤、充填剤等の添加剤を添加することができる。本発明のアロイ樹脂の形態は、特に限定されず、例えば、ペレット状を例示できる。 The alloy resin of the present invention can be used as a heat stabilizer, a light stabilizer, a lubricant, an antioxidant, a plasticizer, an antifouling agent, an impact modifier, and a coloring agent as long as the effects of the present invention are not impaired. Additives such as agents and fillers can be added. The form of the alloy resin of the present invention is not particularly limited, and examples thereof include pellets.
（製造方法）
本発明のアロイ樹脂の製造方法は、特に限定されない。アロイ樹脂の製造における配合及び混練では、通常用いられる、リボンブレンダー、ヘンシェルミキサー、バンバリーミキサー、単軸スクリュー押出機、二軸スクリュー押出機、コニーダー押出機、射出成形機などを単独で用いてもよく、複数組み合わせてもよい。
(Production method)
The method for producing the alloy resin of the present invention is not particularly limited. For compounding and kneading in the production of alloy resins, commonly used ribbon blenders, henschel mixers, Banbury mixers, single-screw screw extruders, twin-screw screw extruders, conider extruders, injection molding machines and the like may be used alone. , Multiple combinations may be used.
以上説明した本発明のアロイ樹脂は、ＰＶＣ系樹脂とＭＭＡ系樹脂とが配合され、かつガラス転移温度Ｔｇと引張応力Ｓをグラフにプロットしたときに特定の領域Ａ内にあるように制御されているため、硬度が高く耐傷付き性に優れ、かつ難燃性に優れている。 The alloy resin of the present invention described above is a mixture of a PVC resin and an MMA resin, and is controlled to be within a specific region A when the glass transition temperature Tg and the tensile stress S are plotted on a graph. Therefore, it has high hardness, excellent scratch resistance, and excellent flame retardancy.
［成形品］
本発明の成形品は、本発明のアロイ樹脂が成形された成形品である。本発明の成形品は、本発明のアロイ樹脂を用いる以外は、公知の態様を採用できる。本発明の成形品の用途は、特に限定されず、例えば、車両や建材や家電等が挙げられる。
本発明の成形品の製造方法は、特に限定されず、例えば、射出成形、射出圧縮成形、押出成形、ブロー成形、プレス成形、真空成形、発泡成形、カレンダー成形等が挙げられる。
[Molding]
The molded product of the present invention is a molded product obtained by molding the alloy resin of the present invention. As the molded product of the present invention, known embodiments can be adopted except that the alloy resin of the present invention is used. The use of the molded product of the present invention is not particularly limited, and examples thereof include vehicles, building materials, and home appliances.
The method for producing a molded product of the present invention is not particularly limited, and examples thereof include injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, and calendar molding.
以下、実施例によって本発明を具体的に説明するが、本発明は以下の記載によっては限定されない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following description.
［ガラス転移温度（Ｔｇ）］
アロイ樹脂のＴｇは、ＪＩＳ Ｋ ７１２１に準じ、示差熱走査熱量測定（ＤＳＣ）によって中間点ガラス転移温度として測定した。
[Glass transition temperature (Tg)]
The Tg of the alloy resin was measured as the intermediate point glass transition temperature by differential thermal scanning calorimetry (DSC) according to JIS K 7121.
［引張応力及び引張弾性率］
アロイ樹脂の引張応力Ｓ及び引張弾性率は、ＪＩＳ Ｋ７１６１に準拠し、引張速度５０ｍｍ／分で測定した。
[Tensile stress and modulus of elasticity]
The tensile stress S and the tensile elastic modulus of the alloy resin were measured at a tensile speed of 50 mm / min according to JIS K7161.
［鉛筆硬度］
鉛筆硬度は、ＪＩＳ Ｋ５６００−５−４に準拠して測定した。
[Pencil hardness]
Pencil hardness was measured according to JIS K5600-5-4.
［燃焼試験］
ＡＳＴＭ Ｄ３８０１に準拠したＵＬ９４Ｖ ２０ｍｍ垂直燃焼試験によってアロイ樹脂の燃焼性を判定した。具体的には、アロイ樹脂を用いて縦１２５ｍｍ×横１３ｍｍ×厚さ３ｍｍの試験片を形成した。前記試験片をその縦方向が鉛直方向となるようにバーナーの上方に設置し、２０ｍｍ炎による１０秒間の接炎を２回行い、その燃焼挙動によって燃焼性を判定した。
[Combustion test]
The flammability of the alloy resin was determined by the UL94V 20 mm vertical combustion test according to ASTM D3801. Specifically, a test piece having a length of 125 mm, a width of 13 mm, and a thickness of 3 mm was formed using an alloy resin. The test piece was placed above the burner so that the vertical direction thereof was the vertical direction, and the flame contact with a 20 mm flame was performed twice for 10 seconds, and the combustibility was determined by the combustion behavior.
［実施例１］
ＰＶＣ系樹脂としてＴＪＺ−１２３３ＷＨ（商品名、信越ポリマー社製、塩化ビニル単位の割合：９１質量％、平均重合度：７００）８０質量部と、ＭＭＡ系樹脂としてアクリペット ＶＨ−００１（商品名、三菱ケミカル社製、ＭＭＡ単位の割合：９０質量％、重量平均分子量：９０，０００、数平均分子量：５０，０００、ＭＦＲ：２．０ｇ／１０分）２０質量部とを、コニーダー押出機を用いて樹脂温度１８０℃、スクリュー回転数１０ｒｐｍの条件で混練してアロイ樹脂とした。
[Example 1]
80 parts by mass of TJZ-1233WH (trade name, manufactured by Shinetsu Polymer Co., Ltd., ratio of vinyl chloride unit: 91% by mass, average degree of polymerization: 700) as a PVC resin, and Acrypet VH-001 (trade name, trade name, MMA resin). Made by Mitsubishi Chemical Co., Ltd., MMA unit ratio: 90% by mass, weight average molecular weight: 90,000, number average molecular weight: 50,000, MFR: 2.0 g / 10 minutes) 20 parts by mass using a conider extruder. The resin was kneaded under the conditions of a resin temperature of 180 ° C. and a screw rotation speed of 10 rpm to obtain an alloy resin.
［実施例２〜４、比較例１、２］
アロイ樹脂の組成を表１に示すとおりに変更した以外は、実施例１と同様にしてアロイ樹脂を得た。
[Examples 2 to 4, Comparative Examples 1 and 2]
An alloy resin was obtained in the same manner as in Example 1 except that the composition of the alloy resin was changed as shown in Table 1.
［参考例１］
参考として、ＭＭＡ系樹脂であるアクリペット ＶＨ−００１（商品名、三菱ケミカル社製、ＭＭＡ単位の割合：９０質量％、重量平均分子量：９０，０００、数平均分子量：５０，０００、ＭＦＲ：２．０ｇ／１０分）１００質量部を各試験に用いた。
[Reference Example 1]
For reference, Acripet VH-001 (trade name, manufactured by Mitsubishi Chemical Corporation, MMA unit ratio: 90% by mass, weight average molecular weight: 90,000, number average molecular weight: 50,000, MFR: 2), which is an MMA-based resin. .0 g / 10 min) 100 parts by weight was used for each test.
各例のアロイ樹脂のＴｇ、燃焼試験、鉛筆硬度、引張応力Ｓ及び引張弾性率を測定した結果を表１に示す。各例の成形品に用いた樹脂のガラス転移温度Ｔｇと引張応力Ｓとを、ガラス転移温度Ｔｇを横軸、引張応力Ｓを縦軸としてプロットしたグラフを図１に示す。 Table 1 shows the results of measuring the Tg, combustion test, pencil hardness, tensile stress S, and tensile elastic modulus of the alloy resin of each example. FIG. 1 shows a graph in which the glass transition temperature Tg and the tensile stress S of the resin used in the molded product of each example are plotted with the glass transition temperature Tg on the horizontal axis and the tensile stress S on the vertical axis.
表１に示すように、図１のグラフにおいてアロイ樹脂のガラス転移温度Ｔｇ及び引張応力Ｓのプロットが領域Ａ内にある実施例１〜４のアロイ樹脂は、硬度が高く耐傷付き性に優れ、難燃性にも優れていた。一方、ガラス転移温度Ｔｇ及び引張応力Ｓのプロットが領域Ａ内にはない比較例１、２のアロイ樹脂は、ＭＭＡ系単独の参考例１と同様に、難燃性が劣っていた。 As shown in Table 1, the alloy resins of Examples 1 to 4 in which the plots of the glass transition temperature Tg and the tensile stress S of the alloy resin are in the region A in the graph of FIG. 1 have high hardness and excellent scratch resistance. It was also excellent in flame retardancy. On the other hand, the alloy resins of Comparative Examples 1 and 2 in which the plots of the glass transition temperature Tg and the tensile stress S were not in the region A were inferior in flame retardancy as in Reference Example 1 of the MMA system alone.
Claims (5)
ＪＩＳ Ｋ ７１２１に従って測定されるガラス転移温度Ｔｇ（単位：℃）とＪＩＳ Ｋ ７１６１に従って測定される引張応力Ｓ（単位：ＭＰａ）とを、前記ガラス転移温度Ｔｇを横軸、前記引張応力Ｓを縦軸としたグラフにプロットしたときに下記式（１）で表される直線と下記式（２）で表される直線で挟まれた領域内にあり、
かつ前記ガラス転移温度Ｔｇが７０℃以上である、アロイ樹脂。
Ｓ＝３４＋Ｔｇ×０．４８ ・・・（１）
Ｓ＝２４＋Ｔｇ×０．４８ ・・・（２） An alloy resin containing a vinyl chloride resin and a methyl methacrylate resin.
The glass transition temperature Tg (unit: ° C.) measured according to JIS K 7121 and the tensile stress S (unit: MPa) measured according to JIS K 7161 are shown on the horizontal axis with the glass transition temperature Tg on the horizontal axis and the tensile stress S on the vertical axis. When plotted on a graph with the axis, it is in the area between the straight line represented by the following formula (1) and the straight line represented by the following formula (2).
An alloy resin having a glass transition temperature Tg of 70 ° C. or higher.
S = 34 + Tg × 0.48 ・ ・ ・ (1)
S = 24 + Tg × 0.48 ・ ・ ・ (2)
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