JP5013497B2 - 繊維強化ポリアセタール樹脂組成物およびそれを含む樹脂成形品 - Google Patents
繊維強化ポリアセタール樹脂組成物およびそれを含む樹脂成形品 Download PDFInfo
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- JP5013497B2 JP5013497B2 JP2005136771A JP2005136771A JP5013497B2 JP 5013497 B2 JP5013497 B2 JP 5013497B2 JP 2005136771 A JP2005136771 A JP 2005136771A JP 2005136771 A JP2005136771 A JP 2005136771A JP 5013497 B2 JP5013497 B2 JP 5013497B2
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- 229930182556 Polyacetal Natural products 0.000 title claims description 53
- 229920006324 polyoxymethylene Polymers 0.000 title claims description 53
- 229920005989 resin Polymers 0.000 title claims description 51
- 239000011347 resin Substances 0.000 title claims description 51
- 239000011342 resin composition Substances 0.000 title claims description 24
- 239000000835 fiber Substances 0.000 title claims description 21
- 239000003365 glass fiber Substances 0.000 claims description 33
- -1 amino-substituted triazine Chemical class 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims description 8
- 239000004643 cyanate ester Substances 0.000 claims description 6
- 230000001788 irregular Effects 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001913 cyanates Chemical class 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000003918 triazines Chemical class 0.000 claims 1
- 239000011521 glass Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 10
- 239000012779 reinforcing material Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 6
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- 125000005702 oxyalkylene group Chemical group 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
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- 239000011324 bead Substances 0.000 description 4
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- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 3
- HZQMAGZJUOWDHN-UHFFFAOYSA-N 2-[2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HZQMAGZJUOWDHN-UHFFFAOYSA-N 0.000 description 3
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- UYVWNPAMKCDKRB-UHFFFAOYSA-N 1,2,4,5-tetraoxane Chemical compound C1OOCOO1 UYVWNPAMKCDKRB-UHFFFAOYSA-N 0.000 description 2
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 2
- KSJNLHWGUSIAIF-UHFFFAOYSA-N 2-[2-[2-[3-(4-hydroxy-3,5-dimethylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(4-hydroxy-3,5-dimethylphenyl)propanoate Chemical compound CC1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C)C(O)=C(C)C=2)=C1 KSJNLHWGUSIAIF-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- MILSYCKGLDDVLM-UHFFFAOYSA-N 2-phenylpropan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 MILSYCKGLDDVLM-UHFFFAOYSA-N 0.000 description 2
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
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- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
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- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- JDIPZHAYUYYGSN-UHFFFAOYSA-N (4-propylphenyl) cyanate Chemical compound CCCC1=CC=C(OC#N)C=C1 JDIPZHAYUYYGSN-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- AUAGGMPIKOZAJZ-UHFFFAOYSA-N 1,3,6-trioxocane Chemical compound C1COCOCCO1 AUAGGMPIKOZAJZ-UHFFFAOYSA-N 0.000 description 1
- CZLMRJZAHXYRIX-UHFFFAOYSA-N 1,3-dioxepane Chemical compound C1CCOCOC1 CZLMRJZAHXYRIX-UHFFFAOYSA-N 0.000 description 1
- KTTREBBQQKBBPI-UHFFFAOYSA-N 1-(3,5-ditert-butyl-4-hydroxyphenyl)nonadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCC(P(O)(O)=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 KTTREBBQQKBBPI-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- XVRAZNHPBNTPCG-UHFFFAOYSA-N 2,6-ditert-butyl-4-(5-chlorobenzotriazol-2-yl)phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1 XVRAZNHPBNTPCG-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- VMZVBRIIHDRYGK-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VMZVBRIIHDRYGK-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
(A)繊維断面の最短径に対する最長径の比が2.4以上12以下である異形断面ガラス繊維を1重量部以上100重量部以下
(B)アミノ置換トリアジン類を0.01重量部以上10重量部以下
(C)多官能性シアン酸エステル類を0.01重量部以上10重量部以下
アミノ置換トリアジン化合物の具体例としては、例えばグアナミン、メラミン、メチロールメラミン、N−ブチルメラミン、N−フェニルメラミン、N,N−ジフェニルメラミン、N,N−ジアリルメラミン、N,N’,N”−トリフェニルメラミン、N,N’,N”−トリメチロールメラミン、ベンゾグアナミン、2,4−ジアミノ−6−メチル−sym−トリアジン、2,4−ジアミノ−6−ブチル−sym−トリアジン、2,4−ジアミノ−6−ベンジルオキシ−sym−トリアジン、2,4−ジアミノ−6−ブトキシ−sym−トリアジン、2,4−ジアミノ−6−シクロヘキシル−sym−トリアジン、2,4−ジアミノ−6−クロロ−sym−トリアジン、2,4−ジアミノ−6−メルカプト−sym−トリアジン、アメリン(N,N,N’,N’−テトラシアノエチルベンゾグアナミン)等が挙げられる。またこれらアミノ置換トリアジン類は、ホルムアルデヒドとの初期重縮合物(プレポリマー)として用いてもよく、具体的にはメラミン、メチロールメラミン、ベンゾグアナミンとホルムアルデヒドとの初期重縮合物であることが好ましく、これらの中でも水溶性のメラミン−ホルムアルデヒド樹脂が特に好ましい。
R4−(−O−C≡N)m (2)
(但し式(2)において、R4は芳香族性の多価有機基を示し、mは2以上の整数を示す)。
(b)複数個の芳香族基同士が単結合にて直接結合した有機基;
(c)複数個の芳香族基が連結基によって結合した芳香環含有基;
(a)の具体例としては、ベンゼン、ナフタレン、アントラセン等が挙げられる。(b)の具体例としてはビフェニル基等が挙げられる。(c)の具体例としては、例えば芳香族基がベンゼン環である場合に、下記一般式(3)で表される構造を有する芳香環含有有機基、
一般式(4)における立体障害性フェノールの好ましい具体例としては、前記の中でも一般式(5)を含むものとして、N,N’−ヘキサメチレンビス(3,5−ジ−t−ブチル−4−ヒドロキシ−ヒドロシンナマミド)、オクタデシル−3−(3,5−ジ−ブチル−4−ヒドロキシフェニル)プロピオネート、1,6−ヘキサンジオール−ビス〔3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート〕、ペンタエリスリチル−テトラキス〔3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート〕、トリエチレングリコール−ビス〔3−(3,5−ジメチル−4−ヒドロキシフェニル)プロピオネート〕、トリエチレングリコール−ビス〔3−(3−t−ブチル−5−メチル−4−ヒドロキシフェニル)プロピオネート〕、トリエチレングリコール−ビス〔3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート〕、2,2’−チオジエチル−ビス〔3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート〕が挙げられる。
<材料>
(1)ポリアセタール樹脂:
コモノマーとして1,3−ジオキソランを樹脂全体に対して4.2重量%含有するアセタールコポリマー。メルトインデックス(10.5g/10分)。
(2)異形断面ガラス繊維:
ガラス繊維断面における最長径の最短径に対する比が4(ガラス繊維20本の繊維断面測定の平均値)の異形断面ガラス繊維、商品名:CSG 3PA−820、日東紡社製。
(3)ガラス繊維:
ガラス繊維断面における最長径の最短径に対する比が1のガラス繊維。商品名:CS03MA486A 旭ファイバーグラス社製
(4)ガラスフレーク:
ガラスビーズ。商品名:ガラスビーズEGB731D−PN、ボッターズ・バロティーニ社製
(5)アミノ置換トリアジン化合物:
メラミン。
(6)多官能性シアン酸エステル類:
2,2’−ビス(4−シアナートフェニル)プロパン。
<物性評価方法>
(a)引張強度:ASTM D638に準拠して測定した。
(b)曲げ強度:ASTM D790に準拠して測定した。
(c)反り量:40×100×1mm外観片を成形し、ゲート側を基準にした際の反ゲート側の浮いている高さを確認した。
[実施例1,比較例1〜6]
ポリアセタール樹脂100重量部に対し、表1に示す配合処方で原料を秤量し、タンブラー型ブレンダーによって混合し、得られた混合物を40mmΦ単軸押出機(田辺プラスチックス社製、型式:VS−40)にてシリンダー温度200℃、吐出速度20kg/hrで溶融混練してペレット化し、所望のポリアセタール樹脂組成物のペレットを得た。
Claims (4)
- ポリアセタール樹脂100重量部に対して、以下の(A)〜(C)を含有することを特徴とする繊維強化ポリアセタール樹脂組成物。
(A)繊維断面の最短径に対する最長径の比が2.4以上12以下である異形断面ガラス繊維を1重量部以上100重量部以下
(B)アミノ置換トリアジン類を0.01重量部以上10重量部以下
(C)多官能性シアン酸エステル類を0.01重量部以上10重量部以下 - (C)多官能性シアン酸エステル類が、下記一般式(2)で表されるポリシアン酸エステル化合物および/またはそのプレポリマーであることを特徴とする請求項1または2に記載の繊維強化ポリアセタール樹脂組成物。
R4−(−O−C≡N)m (2)
(式中、R4は芳香族性の多価有機基を示し、mは2以上の整数を示す)。 - 請求項1乃至3の何れかに記載の繊維強化ポリアセタール樹脂組成物を含む繊維強化ポリアセタール樹脂成形品。
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