JP2011508045A - 柔らかな表面質感を有する低光沢熱可塑性樹脂組成物及びその成形品 - Google Patents
柔らかな表面質感を有する低光沢熱可塑性樹脂組成物及びその成形品 Download PDFInfo
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- 239000005060 rubber Substances 0.000 claims abstract description 65
- 229920006164 aromatic vinyl copolymer Polymers 0.000 claims abstract description 63
- 125000003118 aryl group Chemical group 0.000 claims abstract description 42
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- STSRVFAXSLNLLI-UHFFFAOYSA-N penta-2,4-dienenitrile Chemical compound C=CC=CC#N STSRVFAXSLNLLI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims description 60
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 29
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- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 claims description 4
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- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 4
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 claims description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- -1 N-substituted maleimide Chemical class 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
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- XCPFSALHURPPJE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XCPFSALHURPPJE-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
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- 206010016322 Feeling abnormal Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 150000002825 nitriles Chemical group 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- 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
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
本発明の目的は、柔らかい表面質感を有する熱可塑性樹脂組成物及びその成形品を提供することである。
本発明は、柔らかい表面質感を有し、かつ低光沢性及び衝撃強度に優れた熱可塑性樹脂組成物及びその成形品を提供する。
(A)軟ゴム質芳香族ビニル系共重合樹脂
ゴム質粒子を含むABS樹脂を品物に成形すると、ゴム質粒子の一部が成形品の表面に分散されて、成形品の表面上に微細な突出部を形成する。このような突出部は、入射光を散乱させて、光沢を低くすることができる。
本発明に用いられるゴム改質芳香族ビニル系共重合樹脂(B)は、ゴム改質芳香族ビニル系共重合樹脂(B)の総重量を基準として、共役ジエン系ゴム約40〜約80重量%を含むことができる。これらの範囲の時、所望の耐衝撃性を得ることができる。
芳香族ビニル−シアン化ビニル系共重合樹脂(C)は、芳香族ビニル−シアン化ビニル系共重合樹脂(C)の総重量を基準として、芳香族ビニル系単量体約40〜約90重量%及びシアン化ビニル系単量体約10〜約60重量%を共重合させて製造する。
(a1)スチレン53.4重量部と、アクリロニトリル17.8重量部と、エチルベンゼン20重量部とを含む混合物に、5%のスチレン溶液での溶液粘度が170cpsのブタジエンゴム8.8重量部を添加した。次いで、そこへ開始剤である1,1−ビス(t−ブチルペルオキシ)シクロヘキサン0.015重量部と、分子量調節剤であるt−ドデシルメルカプタン0.07重量部とを添加して混合溶液を用意した。混合溶液を25kg/hrの速度で反応器に投入した。第一の反応器は、攪拌速度を100rpmとし、変換率を35%に調節した。第2の反応器は、攪拌速度を70rpmに調節し、変換率を75%に調節した。反応器から排出された反応物を連続的に液化装置に移して、未反応の単量体および溶媒を除去した。次いで、重合産物をペレット化し、ABS樹脂(a1)を得た。製造されたABS樹脂(a1)の膨潤指数は約16.2で、平均ゴム粒子径は8.58μmで、グラフト率は77.8%であった。ABS樹脂(a1)のゴム粒子のTEM像を図1に示した。
(b1)スチレン31重量部と、アクリロニトリル11重量部と、ブタジエンゴム58質量部と、を混合し、乳化重合した。平均粒径が0.32μmのゴム粒子と、共役ジエン系ゴム58重量%とを含むコア/シェル型中のグラフト−ABS(以下、「g−ABS」)を用いた。
重量平均分子量が120,000、アクリロニトリル含量が32重量%のSAN樹脂を用いた。
ヒンダードフェノール系酸化防止剤として、オクタデシル−3(4−ヒドロキシ−3,5−ジ−ターシャリー−ブチルフェニル)プロピオネートを用いた。
シリコン系衝撃改質剤として、ジメチルポリシロキサンを用いた。
表1に示す構成成分を混合し、混合物を溶融混練し、220℃の温度で従来の二軸押出器(L/Dが29、Φ=45mm)を用いて押出して、熱可塑性樹脂ペレットを製造した。樹脂ペレットは、80℃で3時間乾燥し、バレル温度40〜80℃の条件で、6Oz射出器を用いて180〜280℃で試験片に成形した。実施例1で製造された試験片のTEM像を図4に示した。
表1に示す構成成分を混合し、混合物を溶融混練し、220℃の温度で従来の二軸押出器(L/Dが29、Φ=45mm)を用いて押出して、熱可塑性樹脂ペレットを製造した。樹脂ペレットは、80℃で3時間乾燥し、バレル温度40〜80℃の条件で、6Oz射出器を用いて180〜280℃で試験片に成形した。比較例1で製造された試験片のTEM像を図5に示した。
Claims (16)
- (A)グラフト率が約40〜約90%及び平均粒径が約6〜約20μmのゴム粒子を分散相して含む軟ゴム質芳香族ビニル系共重合樹脂約10〜約80重量%と、(B)ゴム改質芳香族ビニル系共重合樹脂約4〜約60重量%と、(C)芳香族ビニル−シアン化ビニル系共重合樹脂約5〜約80重量%とを含む、柔らかな表面質感を有する低光沢熱可塑性樹脂組成物。
- 前記軟ゴム質芳香族ビニル系共重合樹脂(A)の膨潤指数が約13〜約30である、請求項1に記載の熱可塑性樹脂組成物。
- 前記軟ゴム質芳香族ビニル系共重合樹脂(A)は、芳香族ビニル−シアン化ビニル系共重合体を含むマトリックス;ならびに前記マトリックスに分散され、グラフト率が約40〜約90%及び平均粒径が約6〜20μmのゴム粒子を含む、請求項1に記載の熱可塑性樹脂組成物。
- 前記ゴム粒子は、内部に閉塞された、芳香族ビニル系単量体、シアン化ビニル系単量体、芳香族ビニル−シアン化ビニル系共重合体及びこれらの混合物を含む、請求項1に記載の熱可塑性樹脂組成物。
- 前記軟ゴム質芳香族ビニル系共重合樹脂(A)は、芳香族ビニル系単量体約45〜約90重量%、シアン化ビニル系単量体約5〜約35重量%、及び共役ジエン系ゴム約5〜約20重量%を含む、請求項1に記載の熱可塑性樹脂組成物。
- 前記軟ゴム質芳香族ビニル系共重合樹脂(A)は、連続バルク重合又は連続溶液重合によって製造される、請求項1に記載の熱可塑性樹脂組成物。
- 前記軟ゴム質芳香族ビニル系共重合樹脂(A)は、
芳香族ビニル系単量体約40〜約60重量部、シアン化ビニル系単量体約10〜約25重量部、共役ジエン系ゴム約7〜約20重量部及び溶媒約5〜約30重量部を含む混合溶液約100重量部を、重合開始剤約0.005〜約0.03重量部及び分子量調節剤約0.005〜約0.5重量部と混合する段階と、
前記混合物を変換率約30〜約40%まで重合する段階と、
前記重合物を変換率約55〜約80%まで追加重合する段階と、
によって製造される、請求項1に記載の熱可塑性樹脂組成物。 - 前記ゴム改質芳香族ビニル系共重合樹脂(B)は、共役ジエン系ゴム約40〜約80重量%と、芳香族ビニル系単量体約8〜約45重量%と、シアン化ビニル系単量体約2〜約30重量%とのグラフト共重合体であり、かつ平均粒径が約0.1〜約0.8μmのゴム粒子を含む、請求項1に記載の熱可塑性樹脂組成物。
- 前記芳香族ビニル−シアン化ビニル系共重合樹脂(C)は、芳香族ビニル系単量体約40〜約90重量%及びシアン化ビニル系単量体約10〜60重量%を含む、請求項1に記載の熱可塑性樹脂組成物。
- 前記樹脂組成物は、難燃剤、熱安定剤、衝撃改質剤、酸化防止剤、光安定剤、顔料、染料、無機充填剤及びこれらの混合物からなる群から選択された添加物をさらに含む、請求項1に記載の熱可塑性樹脂組成物。
- 前記芳香族ビニル系単量体は、スチレン、α−メチルスチレン、2−メチルスチレン、3−メチルスチレン、4−メチルスチレン、2−エチルスチレン、3−エチルスチレン、4−エチルスチレン、4−n−プロピルスチレン、4−t−ブチルスチレン、1−ビニルナフタレン、2−ビニルナフタレン及びビニルトルエンからなる群から選択された少なくとも一つである、請求項5、8及び9のいずれか一項に記載の熱可塑性樹脂組成物。
- 前記シアン化ビニル系単量体は、アクリロニトリル、メタクリロニトリル及びエタクリロニトリルからなる群から選択された少なくとも一つである、請求項5、8及び9のいずれか一項に記載の熱可塑性樹脂組成物。
- 前記共役ジエン系ゴムは、ポリブタジエン、ポリ(スチレン−ブタジエン)、ポリ(アクリロニトリル−ブタジエン)、イソプレンゴム、クロロプレンゴム、ポリアクリル酸ブチル及びエチレン−プロピレン−ジエン三元共重合体(EPDM)からなる群から選択された少なくとも一つである、請求項5または8に記載の熱可塑性樹脂組成物。
- 請求項1〜10のいずれか一項に記載の樹脂組成物から成形した成形品。
- 前記成形品は、約400〜約800nmの平均表面粗さ(Ra)及び約2,000〜約7,000nmの10点平均粗さ(Rz)の値を有する、請求項14に記載の成形品。
- 前記成形品は、60度光沢計を利用して測定した光沢度が約40以下の値を有する、請求項14に記載の熱可塑性樹脂組成物。
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US9228046B2 (en) | 2016-01-05 |
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