TW201829661A - 聚烯烴系塗料組成物 - Google Patents
聚烯烴系塗料組成物 Download PDFInfo
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- TW201829661A TW201829661A TW107101015A TW107101015A TW201829661A TW 201829661 A TW201829661 A TW 201829661A TW 107101015 A TW107101015 A TW 107101015A TW 107101015 A TW107101015 A TW 107101015A TW 201829661 A TW201829661 A TW 201829661A
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 58
- 239000008199 coating composition Substances 0.000 title claims abstract description 48
- 229920005989 resin Polymers 0.000 claims abstract description 65
- 239000011347 resin Substances 0.000 claims abstract description 65
- 239000002904 solvent Substances 0.000 claims abstract description 26
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
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- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 14
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 239000003759 ester based solvent Substances 0.000 claims description 12
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- ZGRBAARUJQJDID-UHFFFAOYSA-N 9H-fluorene 1H-indene Chemical compound C1C=CC2=CC=CC=C12.C1=CC=CC=2C3=CC=CC=C3CC12 ZGRBAARUJQJDID-UHFFFAOYSA-N 0.000 claims description 2
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- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 20
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- 239000003973 paint Substances 0.000 description 10
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
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- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 2
- 150000001907 coumarones Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 1
- VIIIJFZJKFXOGG-UHFFFAOYSA-N 3-methylchromen-2-one Chemical compound C1=CC=C2OC(=O)C(C)=CC2=C1 VIIIJFZJKFXOGG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
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- 238000011088 calibration curve Methods 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
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- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 239000010421 standard material Substances 0.000 description 1
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- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 239000003643 water by type Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
- C09D123/30—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by oxidation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
-
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Abstract
本發明之課題係提供可形成耐水性、酒精汽油(gasohol)耐性、耐燃料性等耐藥品性及密接性優異的塗膜且儲藏安定性良好的塗料組成物。一種塗料組成物,其特徵為:包含酸改性聚烯烴(A)、香豆酮(coumarone)・茚樹脂(B)及烴系溶劑(C),相對於酸改性聚烯烴(A)100質量份,香豆酮・茚樹脂(B)為25~400質量份,且更包含酯系溶劑、或酮系溶劑(D)中之至少一者。
Description
本發明關於包含酸改性聚烯烴與香豆酮(coumarone)・茚樹脂,且塗料儲藏安定性、對於聚烯烴基材的密接性、耐藥品性良好的塗料組成物。
對於為了在汽車保險桿等形成塗膜而使用的底漆塗料之耐藥品性之要求變高。為了滿足該要求,過去已有各種方案被提出。
例如,專利文獻1揭示使用有酸改性氯化聚烯烴與分散樹脂的底漆塗料組成物。
專利文獻2揭示使用有酸改性聚烯烴與香豆酮樹脂、或茚樹脂的水性之塗料組成物。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開2013-10248號公報 [專利文獻2]日本特開2006-225551號公報
[發明所欲解決之課題] 但,專利文獻1記載之底漆塗料組成物係使用酸改性氯化聚烯烴作為底漆用樹脂成分,在環境上存有問題,而且不能說具有充分的耐藥品性。又,專利文獻2記載的是水性分散體,不能說具有充分的耐水性及耐藥品性。
本發明之目的在於提供一種塗料組成物,可作為使用於汽車保險桿等的聚丙烯基材之底漆使用,具有比起以往的保險桿底漆更優異的密接性、及耐水性、酒精汽油(gasohol)耐性、耐燃料性等耐藥品性,且塗料之儲藏安定性良好。 [解決課題之手段]
本案發明人等針對上述課題努力進行了研究,結果發現藉由將酸改性聚烯烴與特定的香豆酮・茚樹脂及特定的溶劑一起摻合,可獲得密接性及耐藥品性優異,塗料之儲藏安定性良好的塗膜,乃至完成本發明。
亦即,本發明包括以下之構成。
一種塗料組成物,其特徵為: 包含酸改性聚烯烴(A)、香豆酮・茚樹脂(B)及烴系溶劑(C), 相對於酸改性聚烯烴(A)100質量份,香豆酮・茚樹脂(B)為25~400質量份, 更包含酯系溶劑、或酮系溶劑(D)中之至少一者。
酸改性聚烯烴(A)之酸價為5~40mgKOH/g-樹脂,重量平均分子量為20,000~180,000為較佳。
相對於酸改性聚烯烴(A)100質量份含有烴系溶劑(C)200~3000質量份為較佳,更包含醇系溶劑(E)為較佳。
一種聚烯烴基材用底漆塗料,含有前述塗料組成物。 [發明之效果]
依據本發明,可獲得能形成耐水性、酒精汽油耐性、耐燃料性等耐藥品性及密接性優異的塗膜,且儲藏安定性良好的塗料組成物。
本發明之塗料組成物,為包含酸改性聚烯烴(A)、香豆酮・茚樹脂(B)、烴系溶劑(C),並更組合酯系、或酮系溶劑(D)而成的多成分系之組成物。再者,本發明組成物作為聚烯烴基材用底漆亦為有用。就聚烯烴基材而言,為聚丙烯基材特佳。
本發明之塗料組成物含有酸改性聚烯烴(A)及香豆酮・茚樹脂(B),相對於酸改性聚烯烴(A)100質量份含有香豆酮・茚樹脂(B)25~400質量份。藉由含有酸改性聚烯烴(A)與香豆酮・茚樹脂(B),由塗料組成物製作而得的塗膜的密接性、耐藥品性良好,且塗料組成物的儲藏安定性優異。相對於酸改性聚烯烴(A)100質量份,香豆酮・茚樹脂(B)宜為30質量份以上,更佳為60質量份以上,又更佳為100質量份以上。若過少,有時會有塗料儲藏安定性降低之情形。又,宜為350質量份以下,更佳為300質量份以下,又更佳為200質量份以下。若過多,有時會有密接性、耐藥品性降低之情形。
<酸改性聚烯烴(A)> 本發明中,酸改性聚烯烴(A)宜為藉由對於聚乙烯、聚丙烯及丙烯-α-烯烴共聚物中之至少1種接枝α,β-不飽和羧酸及其酸酐中之至少1種而得者。
丙烯-α-烯烴共聚物為以丙烯作為主體並對其共聚合α-烯烴而得者。就α-烯烴而言,例如可使用乙烯、1-丁烯、1-庚烯、1-辛烯、4-甲基-1-戊烯、乙酸乙烯酯等中之1種或數種。該等α-烯烴之中,乙烯、1-丁烯為較佳。丙烯-α-烯烴共聚物的丙烯成分與α-烯烴成分之比率不予以限定,但丙烯成分宜為50莫耳%以上,更佳為70莫耳%以上。即便丙烯-α-烯烴共聚物之乙烯成分含量為50莫耳%以下,本發明之塗料組成物之密接性、耐藥品性及塗料之儲藏安定性仍為良好。再者,即便乙烯成分含量為30莫耳%以下,本發明之塗料組成物仍充分展現密接性、耐藥品性及塗料之儲藏安定性,乙烯成分含量亦可為9莫耳%以下。
作為α,β-不飽和羧酸及其酸酐中之至少1種,例如可列舉馬來酸、伊康酸、檸康酸及它們的酸酐。該等之中為酸酐較佳,為馬來酸酐更佳。具體而言,可列舉酸改性聚丙烯、酸改性丙烯-乙烯共聚物、酸改性丙烯-丁烯共聚物、酸改性丙烯-乙烯-丁烯共聚物等,該等酸改性聚烯烴可使用1種或組合2種以上來使用。
酸改性聚烯烴(A)之重量平均分子量(Mw)宜為20,000~180,000之範圍。更佳為40,000~180,000之範圍。若未達前述值,有時會有耐藥品性變差之情況。另一方面,若超過前述值,有時會有塗料儲藏安定性出現問題之情況。
考慮與聚烯烴樹脂基材之黏接性之觀點,酸改性聚烯烴(A)之酸價宜為5~40mgKOH/g-樹脂之範圍。更佳為10~30mgKOH/g-樹脂之範圍。若未達前述值,有時會有塗料之儲藏安定性出現問題之情況。另一方面,若超過前述值,有時會有耐藥品性變差之情況。
酸改性聚烯烴(A)熔點(Tm)宜為40℃以上,更佳為50℃以上。若過低,有時會有密接性、耐藥品性降低之情形。又,宜為120℃以下,更佳為100℃以下。若過高,有時會有塗料儲藏安定性降低之情形。
酸改性聚烯烴(A)之熔解熱(△H)宜為5J/g以上,更佳為10J/g以上。若過小,有時會有密接性、耐藥品性降低之情形。又,宜為60J/g以下,更佳為50J/g以下。若過高,有時會有塗料儲藏安定性降低之情形。
酸改性聚烯烴(A)宜為實質上未經氯化者。為實質上經氯化者時,不僅在環境上存有問題,而且有時會有耐藥品性降低之情形。實質上未經氯化,係指就氯含量而言宜為10wt%以下,更佳為5wt%以下,又更佳為1wt%以下,特佳為0wt%。
酸改性聚烯烴(A)宜為結晶性。藉由為結晶性,與非晶性相比,密接性、耐藥品性更優異。為結晶性,係指使用差示掃描型熱量計(DSC),以20℃/分鐘從-100℃升溫至250℃,並於該升溫過程中顯示明確的熔解峰部者。
酸改性聚烯烴(A)之製造方法不特別限定,例如可列舉自由基接枝反應(亦即對於成為主鏈之聚合物生成自由基物種,以此自由基物種作為聚合起始點,而使不飽和羧酸及酸酐進行接枝聚合之反應)等。
自由基產生劑不特別限定,宜使用有機過氧化物。有機過氧化物不特別限定,可列舉:過氧化鄰苯二甲酸二第三丁酯、第三丁基過氧化氫、過氧化二異丙苯、過氧化苯甲醯、過氧化苯甲酸第三丁酯、過氧化-2-乙基己酸第三丁酯、過氧化三甲基乙酸第三丁酯、過氧化甲乙酮、二第三丁基過氧化物、過氧化月桂醯等過氧化物;偶氮雙異丁腈、偶氮雙異丙腈等偶氮腈類等。
<香豆酮・茚樹脂(B)> 本發明中香豆酮・茚樹脂(B)宜為就單體成分而言以香豆酮類、及茚類作為主成分者。較佳為在香豆酮・茚樹脂中以合計量計含有50質量%以上之香豆酮類及茚類者,若含有60質量%以上則更佳。香豆酮類之具體例可列舉香豆酮、甲基香豆酮等,茚類之具體例可列舉茚、甲基茚等。就香豆酮類、茚類以外的單體成分而言,可列舉苯乙烯、乙烯基甲苯、二環戊二烯等。單體組成可視樹脂之用途等適當地選擇,通常香豆酮類為約1~80質量%,茚類為約20~95質量%。又,宜含有1~20質量%之苯乙烯。也可在香豆酮・茚樹脂中含有羥基或羧酸基。
又,關於香豆酮・茚樹脂(B)之軟化點不特別限定,但考慮對於所希望之應用用途之適用性、良好的摻合特性、塗佈性、密接性之觀點,宜為60℃以上,更佳為70~170℃。
香豆酮・茚樹脂(B)之重量平均分子量(Mw)宜為100~2000之範圍,更佳為500~1500之範圍。若未達前述值,有時會有塗料之密接性變差之情況。另一方面,若超過前述值,有時會有塗料之儲藏安定性出現問題之情況。
香豆酮・茚樹脂(B)之酸價不特別限定,宜為2.0mgKOH/g-樹脂以下,更佳為1.0mgKOH/g-樹脂以下。若超過前述值,有時會有塗料之儲藏安定性出現問題之情況。
香豆酮・茚樹脂(B)之羥基價不特別限定,宜為5mgKOH/g-樹脂以上,更佳為10mgKOH/g-樹脂以上。若未達前述值,有時會有塗料之密接性降低之情形。又,宜為200mgKOH/g-樹脂以下,更佳為150mgKOH/g-樹脂以下。若超過前述值,有時會有塗料之儲藏安定性降低之情形。
本發明之塗料組成物中可含有顏料。就顏料而言,可列舉氧化鈦、碳酸鈣、硫酸鋇、滑石、碳黑等。該等可使用1種或併用2種以上。顏料之合計量,相對於酸改性聚烯烴100質量份宜含有50~500質量份,更佳為含有75~350質量份。
本發明中,塗料組成物包含烴系溶劑(C),更包含酯系溶劑、或酮系溶劑(D)中之至少一者。宜相對於酸改性聚烯烴(A)100質量份包含200質量份以上之烴系溶劑(C),更佳為包含300質量份以上。又,宜為3000質量份以下,更佳為2500質量份以下。又再更佳為1800質量份以下。藉由設定在上述範圍內,可顯現優異的塗料儲藏安定性。
酯系溶劑、或酮系溶劑(D)之合計量,相對於酸改性聚烯烴(A)100質量份宜為20質量份以上,更佳為50質量份以上。又,宜為500質量份以下,更佳為400質量份以下,又再更佳為200質量份以下。藉由設定在上述範圍內,可顯現優異的塗料儲藏安定性。
就烴系溶劑(C)而言,可列舉甲苯、二甲苯、Solvesso(註冊商標)100等芳香族烴系溶劑、環己烷、甲基環己烷、乙基環己烷等脂環族烴系溶劑,其中為二甲苯、或環己烷較佳。尤其,為二甲苯、Solvesso(註冊商標)100及環己烷之組合較佳。
就酯系溶劑、或酮系溶劑(D)之酯系溶劑而言,可列舉乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸異丙酯、乙酸丁酯、乙酸異丁酯、乙酸戊酯等。其中為乙酸乙酯較佳。就酮系溶劑而言,可列舉丙酮、甲乙酮、甲基異丁酮、甲基戊酮,其中為甲乙酮較佳。也可從酯溶劑及酮溶劑之中組合2種以上。
也可在塗料組成物中進一步添加醇系溶劑(E)。藉由添加醇系溶劑(E),可更提升塗料儲藏安定性。摻合醇系溶劑(E)時,相對於酸改性聚烯烴100質量份宜為5質量份以上,更佳為10質量份以上。又,宜為200質量份以下,更佳為150質量份以下。藉由設定在上述範圍內,可顯現極優異的塗料儲藏安定性。就醇系溶劑(E)而言,可列舉甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、2-丁醇等。
<溶劑系塗料組成物> 本發明之塗料組成物,包含酸改性聚烯烴(A)、香豆酮・茚樹脂(B)、烴系溶劑(C),更包含酯系、或酮系溶劑(D)中之至少一者,可視需要進行稀釋以提供本發明之塗料組成物。
本發明之塗料組成物實質上為溶劑系之塗料組成物為較佳。亦即,令塗料組成物中含有的全部溶劑為100質量%時,前述烴系溶劑(C)、酯系溶劑、酮系溶劑(D)及醇系溶劑(E)之合計宜為90質量%以上,更佳為95質量%以上,又更佳為99質量%以上,也可為100質量%。藉由實質上為溶劑系塗料組成物,可顯現優異的耐水性、耐藥品性。
上述塗料組成物之塗裝時之黏度不特別限制,但藉由在10~300mPa・sec之範圍以內,更佳為在15~200mPa・sec之範圍以內,塗裝作業性為良好,就成品外觀之觀點為合適。
在不損及本發明之效果之範圍內,也可於本發明提案的塗料組成物中含有丙烯酸樹脂、醇酸樹脂、胺甲酸酯樹脂等。 [實施例]
以下,舉實施例更具體地說明本發明,但本發明不限於該等實施。
<酸改性聚烯烴(A)之製造例> [製造例1] 於1L高壓釜中,加入利用茂金屬觸媒聚合而成之丙烯-丁烯共聚物(丙烯成分76莫耳%、及1-丁烯成分24莫耳%)100質量份、甲苯150質量份及馬來酸酐9質量份、二第三丁基過氧化物4質量份,升溫至140℃後,再攪拌3小時。然後,將得到的反應液冷卻後,將其注入到裝有大量的甲乙酮的容器中,使樹脂析出。然後,將含有該樹脂之液體進行離心分離,藉此將馬來酸酐接枝聚合而得之酸改性丙烯-丁烯共聚物與(聚)馬來酸酐及低分子量物分離,並予以純化。然後,於減壓下在70℃予以乾燥5小時,藉此得到酸改性丙烯-丁烯共聚物(酸價14mgKOH/g-樹脂,重量平均分子量90,000,Tm70℃)。令由此製造例製作而得的酸改性聚烯烴為A-1。
[製造例2] 將馬來酸酐之進料量變更為30質量份,並將二第三丁基過氧化物變更為3質量份,除此以外,以與製造例1同樣方式進行,從而得到酸改性丙烯-丁烯共聚物(酸價40mgKOH/g-樹脂,重量平均分子量90,000,Tm70℃)。令由此製造例製作而得的酸改性聚烯烴為A-2。
[製造例3] 將馬來酸酐之進料量變更為3質量份,並將二第三丁基過氧化物變更為7質量份,除此以外,以與製造例1同樣方式進行,從而得到酸改性丙烯-丁烯共聚物(酸價5mgKOH/g-樹脂,重量平均分子量90,000,Tm70℃)。令由此製造例製作而得的酸改性聚烯烴為A-3。
[製造例4] 將馬來酸酐之進料量變更為12質量份,並將二第三丁基過氧化物變更為3質量份,除此以外,以與製造例1同樣方式進行,從而得到酸改性丙烯-丁烯共聚物(酸價14mgKOH/g-樹脂,重量平均分子量180,000,Tm70℃)。令由此製造例製作而得的酸改性聚烯烴為A-4。
[製造例5] 將馬來酸酐之進料量變更為5質量份,並將二第三丁基過氧化物變更為10質量份,除此以外,以與製造例1同樣方式進行,從而得到酸改性丙烯-丁烯共聚物(酸價14mgKOH/g-樹脂,重量平均分子量20,000,Tm70℃)。令由此製造例製作而得的酸改性聚烯烴為A-5。
<酸改性聚烯烴(A)溶液之製備例> 將100質量份的A-1、環己烷280質量份、二甲苯120質量份進料於配備有水冷回流冷凝器與攪拌機之500ml四口燒瓶中,邊攪拌邊升溫至70℃,再攪拌1小時,藉此得到A-1溶液。
以和A-1溶液同樣方式溶解A-2~A~7,藉此得到A-2~A-5溶液。
<氯化聚烯烴> 將分子量70,000、氯含有率21wt%之氯化聚烯烴(A-6)100質量份、環己烷280質量份及乙酸丁酯120質量份進料於配備有水冷回流冷凝器與攪拌機的500ml四口燒瓶中,邊攪拌邊升溫至70℃,再持續攪拌1小時,藉此得到A-6溶液。
<香豆酮・茚樹脂(B)溶液之製備例> 將重量平均分子量950、軟化點120℃、羥基價30mgKOH/g-樹脂、酸價1.0mgKOH/g-樹脂以下之香豆酮・茚樹脂(B-1)100質量份、50質量份的Solvesso 100、環己烷50質量份進料於配備有水冷回流冷凝器與攪拌機的500ml四口燒瓶中,於室溫攪拌2小時,藉此得到B-1溶液。另外,香豆酮・茚樹脂(B-1)使用了日塗化學公司製之Nitto Resin(註冊商標)Coumarone V-120S。
將重量平均分子量160、羥基價50mgKOH/g-樹脂、酸價1.0mgKOH/g-樹脂以下之香豆酮・茚樹脂(B-2)100質量份、50質量份的Solvesso 100、環己烷50質量份進料於配備有水冷回流冷凝器與攪拌機的500ml四口燒瓶中,於室溫攪拌2小時,藉此得到B-2溶液。另外,香豆酮・茚樹脂(B-2)使用了日塗化學公司製之Nitto Resin(註冊商標)Coumarone L-5。
<醇酸樹脂溶液之製備例> 將係來自大豆油且油長(oil length)41wt%、鄰苯二甲酸酐42wt%、酸價8.0mgKOH/g-樹脂以下之醇酸樹脂(B-3)100質量份、50質量份的Solvesso 100、環己烷50質量份進料於配備有水冷回流冷凝器與攪拌機的500ml四口燒瓶中,於室溫攪拌2小時,藉此得到B-3溶液。另外,醇酸樹脂(B-3)使用了DIC公司製之ALUKIDIR(註冊商標)1307-60-EL。
對於以上述方式得到的各酸改性聚烯烴根據下列方法進行分析測定及評價。
[酸改性聚烯烴(A)之酸價之測定] 本發明中的酸改性聚烯烴(A)之酸價(mgKOH/g-樹脂),係使用FT-IR(島津製作所公司製,FT-IR8200PC),使用從以馬來酸酐(東京化成製)之氯仿溶液製作而成的檢量線得到的係數(f)、酸改性聚烯烴溶液中的琥珀酸酐之羰基(C=O)鍵之伸縮峰部(1780cm-1)之吸光度(I),並利用下列算式計算而得之值。 酸價(mgKOH/g-樹脂)=[吸光度(I)×(f)×2×氫氧化鉀之分子量×1000(mg)/琥珀酸酐之分子量] 琥珀酸酐之分子量:100.07氫氧化鉀之分子量:56.11
[香豆酮・茚樹脂(B)之酸價之測定] 香豆酮・茚樹脂(B)之酸價係根據JIS K 5601-2-1(1999)進行測定。
[重量平均分子量(Mw)之測定] 本發明中之酸改性聚烯烴(A)及香豆酮・茚樹脂(B)之重量平均分子量,係利用日本WATERS公司製凝膠滲透層析儀Alliance e2695(以下稱GPC,標準物質:聚苯乙烯樹脂,移動相:四氫呋喃,管柱:Shodex KF-806+KF-803,管柱溫度:40℃,流速:1.0ml/分鐘,檢測器:光電二極體陣列檢測器(波長254nm=紫外線))測定而得之值。
[熔點之測定] 本發明中之酸改性聚烯烴(A)之熔點,係使用差示掃描熱量計(以下稱DSC,TA Instruments Japan製,Q-2000),由以20℃/分鐘之速度升溫熔解,進行冷卻樹脂化後,再度升溫熔解時之熔解峰部之峰頂溫度測定而得之值。
[軟化點之測定] 本發明中之香豆酮・茚樹脂(B)之軟化點係根據JIS K 2207(1996)進行測定。
<塗料組成物> [實施例1] 按照以下方式製作實施例1所示之塗料組成物。相對於A-1溶液500質量份(A-1,100質量份),添加二甲苯40質量份,並再添加表1所示之質量比之顏料,利用珠磨機予以分散直到利用粒度測定器(grindometer)所為之評價成為10μm以下,藉此得到顏料分散液。於顏料分散液(A-1,100質量份)中,以使B-1成為100質量份的方式加入B-1溶液,然後混合環己烷110質量份、甲乙酮105質量份,藉此得到實施例1所示之塗料組成物。
[實施例2~9] 將酸改性聚烯烴(A)、香豆酮・茚樹脂(B)、烴系溶劑(C)、酯系溶劑、或酮系溶劑(D)、以及醇系溶劑(E)以表1所示之比例混合,除此以外,以與實施例1同樣之順序進行混合,藉此製作成實施例2~8所示之塗料組成物。於顏料分散液中添加了酯系溶劑、酮系溶劑、醇系溶劑。
[比較例1~6]將
酸改性聚烯烴(A)、香豆酮・茚樹脂(B)、烴系溶劑(C)、酯系溶劑、或酮系溶劑(D)、以及醇系溶劑(E)以表2所示之比例混合,除此以外,以與實施例1同樣之順序進行混合,藉此製作成比較例1~5所示之塗料組成物。於顏料分散液中添加了酯系溶劑、酮系溶劑、醇系溶劑。另外,比較例6未含有烴系溶劑(C),故無法製作塗料組成物,因此未進行評價。
[塗料安定性] 關於實施例或比較例中製作而得之塗料組成物之塗料安定性,針對以下項目進行評價。將結果示於表1與表2。
將塗料組成物於-5℃、50℃靜置10天,評價塗料組成物之外觀、黏度。黏度係利用福特杯(FORD CUP)(No.4,25℃)進行測定。 評價基準 ◎:外觀沒有變化,在5秒以內發生增黏。 ○:外觀沒有變化,在超過5秒且10秒以內發生增黏。 △:外觀沒有變化,但需耗時超過10秒以增黏。 ×:外觀發生變化,且需耗時超過10秒以增黏。
[試驗塗板之製作] 相對於實施例或比較例中得到的塗料組成物100質量份,摻合30質量份之Solvesso 100與30質量份之甲苯,藉此調整成塗裝時之溶劑組成。以下,將調整後之塗料組成物記載為稀釋塗料組成物。
以異丙醇將聚丙烯基材脱脂,製作成試驗板。將上述製作而得之稀釋塗料組成物以乾燥膜厚成為10μm的方式噴塗於試驗板。將作為著色基底塗料的RETAN(註冊商標)PG White(商品名,關西Paint公司製)以乾燥膜厚成為50μm的方式噴塗於前述試驗板之稀釋塗料組成物面。然後於80℃之烘箱加熱30分鐘而獲得形成有疊層塗膜的試驗塗板。以此試驗塗板進行以下所示之各種塗膜性能試驗。
[塗膜性能試驗] 關於按上述方式製作而得的試驗塗板,針對以下的各項目進行評價試驗。將結果示於表1與表2。
(1)初始密接性 利用刀具以到達各試驗塗板之基底的方式進行切入,並劃出100個大小1mm×1mm之棋盤格。於其表面貼附黏著賽璐芬膠帶(Cellophane Tape),檢視於20℃將該膠帶急劇地剝離後的棋盤格塗膜的殘存數。 評價基準 ◎:100個殘存 ○:99~90個殘存 △:89~41個殘存 ×:40個以下殘存
(2)耐水性 將各試驗塗板浸漬於40℃之溫水中10天後,觀察塗膜表面。 評價基準 ◎:外觀完全沒有變化,係非常良好。 ○:外觀大致上沒有變化,係良好。 ×:確認塗膜有膨潤、隆起等異常。
(3)酒精汽油耐性 將各試驗塗板在20℃浸於汽油/乙醇=90/10重量比之試驗液中,觀察經過120分鐘時之隆起、剝離之塗面狀態,並依下列的基準進行評價。 評價基準 ◎:完全沒有異常。 ○:有出現直徑未達3mm之隆起、或直徑未達3mm之剝離。 ×:有出現直徑超過3mm之隆起、或直徑超過3mm之剝離。
(4)耐燃料性 根據ISO1817中指定的試驗用添加有醇之燃料液,製備試驗液。試驗液含有2,2,4-三甲基戊烷25.35wt%、甲苯42.25wt%、二異丁烯12.68wt%、甲醇15.0wt%、乙醇4.22wt%、水0.5wt%、甲酸20ppm。將試驗塗板在25℃浸於此試驗液中120分鐘。然後,將試驗塗板於室溫風乾30分鐘,利用刀具對於各試驗塗板以到達基底的方式進行切入,並劃出100個大小1mm×1mm之棋盤格。於其表面貼附黏著賽璐芬膠帶,檢視於20℃將該膠帶急劇地剝離後的棋盤格塗膜的殘存數。 評價基準 ◎:100個殘存 〇:99~90個殘存 △:89~41個殘存 ×:40個以下殘存
【表1】
【表2】
[產業利用性] 本發明之塗料組成物,藉由含有酸改性聚烯烴與香豆酮・茚樹脂,可形成耐水性、酒精汽油耐性、耐燃料性等耐藥品性優異的塗膜。因此作為使用於汽車保險桿等的聚丙烯基材的底漆係有用。
Claims (6)
- 一種塗料組成物,其特徵為: 包含酸改性聚烯烴(A)、香豆酮(coumarone)・茚樹脂(B)及烴系溶劑(C), 相對於該酸改性聚烯烴(A)100質量份,該香豆酮・茚樹脂(B)為25~400質量份, 更包含酯系溶劑、或酮系溶劑(D)中之至少一者。
- 如申請專利範圍第1項之塗料組成物,其中,該酸改性聚烯烴(A)之酸價為5~40 mgKOH/g-樹脂。
- 如申請專利範圍第1或2項之塗料組成物,其中,該酸改性聚烯烴(A)之重量平均分子量為20,000~180,000。
- 如申請專利範圍第1或2項之塗料組成物,其中,相對於該酸改性聚烯烴(A)100質量份,含有該烴系溶劑(C)200~3000質量份。
- 如申請專利範圍第1或2項之塗料組成物,其更包含醇系溶劑(E)。
- 一種聚烯烴基材用底漆塗料,其含有如申請專利範圍第1至5項中任一項之塗料組成物。
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| CN115537145A (zh) * | 2022-09-30 | 2022-12-30 | 江苏天顺印业有限公司 | 热转印保护层、高耐醇热转印膜及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55104337A (en) * | 1979-02-02 | 1980-08-09 | Nippon Paint Co Ltd | Adhesive composition |
| JPS59136358A (ja) * | 1983-01-25 | 1984-08-04 | Dainippon Ink & Chem Inc | 塗料用樹脂組成物 |
| JPS61152755A (ja) * | 1984-12-27 | 1986-07-11 | Dainippon Ink & Chem Inc | ポリプロピレン系樹脂用プライマ−組成物 |
| JPH04108876A (ja) * | 1990-08-29 | 1992-04-09 | Nippon Steel Chem Co Ltd | 塗料組成物 |
| WO2001004209A1 (en) | 1999-07-08 | 2001-01-18 | Goyo Paper Working Co., Ltd. | Resin compositions, water-resistant/moisture-proof paper containing the same, and process for producing the same |
| JP4741058B2 (ja) * | 2000-05-19 | 2011-08-03 | 五洋紙工株式会社 | 耐水・防湿紙用樹脂組成物及びこれを用いた耐水・防湿紙並びにその製造方法 |
| ES2229965T1 (es) * | 2001-12-28 | 2005-05-01 | Nippon Paper Industries Co., Ltd. | Composiciones ligantes de resina, procedimiento de produccion y uso de las mismas. |
| US7635520B2 (en) * | 2004-05-31 | 2009-12-22 | Nippon Paper Chemicals Co., Ltd. | Chlorinated propylene random copolymer and compositions containing the same |
| JP4717463B2 (ja) | 2005-02-18 | 2011-07-06 | ユニチカ株式会社 | 水性分散体および積層体 |
| US20090286077A1 (en) * | 2008-05-16 | 2009-11-19 | Hirokazu Okamoto | One-pack type adhesive precoating composition |
| JP2013010248A (ja) | 2011-06-29 | 2013-01-17 | Nippon Bee Chemical Co Ltd | 複層塗膜の形成方法 |
| JP5905167B2 (ja) * | 2013-12-04 | 2016-04-20 | ユニチカ株式会社 | ポリオレフィン樹脂水性分散体 |
-
2018
- 2018-01-11 TW TW107101015A patent/TW201829661A/zh unknown
- 2018-01-15 JP JP2018563303A patent/JP6569827B2/ja active Active
- 2018-01-15 US US16/479,264 patent/US10563082B2/en active Active
- 2018-01-15 WO PCT/JP2018/000758 patent/WO2018135418A1/ja not_active Ceased
- 2018-01-15 CN CN201880007691.4A patent/CN110198994A/zh active Pending
- 2018-01-15 EP EP18741466.9A patent/EP3572472A4/en not_active Withdrawn
- 2018-01-15 KR KR1020197023815A patent/KR20190103387A/ko not_active Withdrawn
- 2018-01-15 MX MX2019008625A patent/MX2019008625A/es unknown
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|---|---|
| EP3572472A1 (en) | 2019-11-27 |
| EP3572472A4 (en) | 2020-06-10 |
| JPWO2018135418A1 (ja) | 2019-06-27 |
| US20190382611A1 (en) | 2019-12-19 |
| MX2019008625A (es) | 2019-12-02 |
| US10563082B2 (en) | 2020-02-18 |
| WO2018135418A1 (ja) | 2018-07-26 |
| CN110198994A (zh) | 2019-09-03 |
| KR20190103387A (ko) | 2019-09-04 |
| JP6569827B2 (ja) | 2019-09-04 |
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