CN1120564A - 制备基于丙烯酸类聚合物的抗擦刮和耐磨的成型制品的方法 - Google Patents
制备基于丙烯酸类聚合物的抗擦刮和耐磨的成型制品的方法 Download PDFInfo
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- CN1120564A CN1120564A CN95107127A CN95107127A CN1120564A CN 1120564 A CN1120564 A CN 1120564A CN 95107127 A CN95107127 A CN 95107127A CN 95107127 A CN95107127 A CN 95107127A CN 1120564 A CN1120564 A CN 1120564A
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 19
- 230000008569 process Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008119 colloidal silica Substances 0.000 claims abstract description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 26
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 14
- -1 diacrylate 1,6-hexylene glycol ester Chemical class 0.000 claims description 11
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 10
- 238000007790 scraping Methods 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 7
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- DHQIYHHEPUYAAX-UHFFFAOYSA-N n-(4,6-diamino-1,3,5-triazin-2-yl)prop-2-enamide Chemical class NC1=NC(N)=NC(NC(=O)C=C)=N1 DHQIYHHEPUYAAX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 229920000800 acrylic rubber Polymers 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000007046 ethoxylation reaction Methods 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 125000005908 glyceryl ester group Chemical group 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 24
- 238000000576 coating method Methods 0.000 abstract description 24
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
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- 230000000379 polymerizing effect Effects 0.000 abstract 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 3
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- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 229940051250 hexylene glycol Drugs 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08F214/06—Vinyl chloride
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- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
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Abstract
本发明涉及一种赋予基于热塑性丙烯酸类聚合物的成型制品以抗擦刮性和耐磨性的方法,该方法在于用包含:a)40~98.5%(重量)的至少一种(甲基)丙烯酸类单体和/或具有至少二个可聚合双键的低聚物;b)1~20%(重量)的至少一种(甲基)丙烯酸类单体和/或含有极性基团的低聚物;c)0.5~10%(重量)的UV光引发剂。还可任意地包含胶态二氧化硅、UV稳定剂和非离子表面活性剂的组合物涂覆制品并通过用UV光在20~65℃下就地聚合和交联该组合物。
Description
本发明涉及一种通过用一种特定的可聚合的丙烯酸类单体和UV光引发剂的混合物涂覆并随后通过UV辐照此涂层聚合并交联而赋予基于热塑性丙烯酸类聚合物的成形制品、板材和薄膜的表面以抗擦刮性和耐磨性的方法。
此外,本发明还涉及由上述方法所得到的抗擦刮和耐磨的成形制品。
众所周知,在使用基于热塑性丙烯酸类聚合物例如聚甲基丙烯酸甲酯(PMMA)的板材和薄膜、特别是透明制品时,所遇到的问题之一是由于制品易被擦刮与磨损而使它们的透明度降低并损及其表面外观。
本技术领域现已提出许多热塑性聚合物(其中包括丙烯酸类聚合物)的板材和成形制品的表面处理方法,正是为了避免上述的麻烦。
这样的处理方法通常包括在制品或热塑性板材(基底)上敷施一层可聚合的不饱和单体,所说的单体在自由基聚合引发剂存在下通过从80℃至基底的Tg的高温加热而被就地聚合和交联。
用这种方法可获得具有足够硬度的聚合和交联的涂层,提高了热塑性制品的耐磨性。
然而,由于这类处理方法必须在无氧场合中,特别是在惰性气氛(氮气)中进行以避免氧对在高温下进行的聚合反应与交联反应的抑制作用以及不希望出现的黄色老化和形成的聚合物基底的老化,因此这类处理存在不可避免的麻烦。此外,这样得到的涂层不能总是良好地粘附在基底上,也不会总是显示出良好的透明度。
因此,其结果是在无氧条件下,特别是对在工厂中连续地生产热塑性聚合物的板材和薄膜来说,进行所述的处理是困难和复杂的。
还有一些被建议的处理方法,其中被涂敷在聚合物基底上的单体层是通过在光引发剂存在下使用UV射线而被聚合和交联的,该方法可在室内条件下,即,在空气中和不超过40℃的相当低的温度下进行,从而不影响聚合物基底的尺寸稳定性及其机械性能、外观和透明性,或者,无论如何能避免其老化。
然而,如此获得的聚合和交联涂层显示出对聚合物基底的不充分或较差的粘附。
为了避免聚合和交联涂层对基底的不充分粘附,DE2928512号专利中建议,在从70℃至150℃,总之在接近形成基底的聚合物的Tg的高温下,使用具有至少两个双键的、沸点高于聚合和交联温度的单体,通过UV辐照单体层进行聚合和交联。
在基于聚甲基丙烯酸甲酯(PMMA)的热塑性基底的情况下,获得良好粘附的有利温度是从90℃至110℃。
在上述德国专利中提到的方法,其中为了获得良好的粘着,必须在接近丙烯酸类聚合物的Tg的高温下操作,然而这样的高温操作会导致聚丙烯酸类基底机械性能的变劣,会导致形成表面缺陷,会使其易脆,并会由于形成不希望有的微黄色或桔黄色而导致表面降级及导致其透明度降低。
我们现已发现一种赋予基于热塑性丙烯酸类聚合物、特别是PMMA的成形制品以抗擦刮性和耐磨性的简单方法,该方法没有已知方法所显示的缺陷,它包括用一种包含具有至少两个可聚合的双键的丙烯酸类单体和具有极性基团的丙烯酸类单体和UV光引发剂的混合物涂覆制品的表面,然后在20℃至65℃的低温下在UV光下聚合和交联所说的涂层。
用所述方法获得的制品显示出良好的表面硬度、高的抗擦刮性和耐磨性,以及聚合和交联的单体涂层对基底的最佳的粘附性,此外,它们还保持未被改变的透明度和机械性能及表面外观,没有显示出不希望有的微黄色变。
因此,本发明的一个目的是提供一种制备基于丙烯酸类的热塑性聚合物的、具有抗擦刮性和耐磨性的成形制品、板材和薄膜的方法,它包括在基于热塑性丙烯酸类聚合物的成形制品表面上涂覆一层均匀的单体组合物,该组合物包含
a)40~98.5%(重量)的至少一种(甲基)丙烯酸类单体和/或具有至少两个可聚合双键且沸点高于形成制品的丙烯酸类聚合物的Tg的低聚物;
b)1~20%(重量)的至少一种具有下式的极性(甲基)丙烯酸类单体,式中:R′是H、CH3;R″是C2~C6的亚烷基;Z是-OH、-COOH、-SO3H、-NH2、-CONH2和/或其由2~7个单体单元形成的低聚物;
c)0.5~10%(重量)的UV光聚合引发剂;
d)0~3%(重量)的胶态二氧化硅和/或胶态金属氧化物;
e)0~8%(重量)的UV稳定剂;
f)0~3%(重量)的非离子表面活性剂,a+b+c+d+e+f的量之和为100%,然后将如此涂覆的制品在20℃~65℃的温度下受到UV辐照。
作为形成成形制品的热塑性聚合物的例子可被引证的是通常为透明的(共)聚合物,如(甲基)丙烯酸酯、特别是PMMA,所说的(共)聚合物与聚氯乙烯(PVC)或聚偏氟乙烯(PVDF)的透明合金,含有丙烯酸类弹性体分散相的聚甲基丙烯酸甲酯(耐冲击性PMMA)。
多官能(甲基)丙烯酸酯,例如甘醇、多元醇、乙氧基化多元醇、脂族的氨基甲酸乙酯、蜜胺的(甲基)丙烯酸酯及其混合物可被用作组分(a)。
这类化合物的例子是二丙烯酸三聚丙烯甘油酯(TPDGA)、三丙烯酸1,6-己二醇酯(HDDA)、三羟甲基丙烷三丙烯酸酯(TMPTA)、三丙烯酸季戊四醇酯(PETIA)、乙氧基化三羟甲基丙烷的三丙烯酸酯、由多元醇与异氰酸酯和(甲基)丙烯酸羟乙酯反应得到的聚(甲基)丙烯酸氨基甲酸乙酯、以及不饱和的二丙烯酰基蜜胺。
脂族的己基丙烯酸氨基甲酸乙酯和不饱和的二丙烯酰基蜜胺,以及它们与TPGDA、HDDA、TMPTA、PETIA的混合物已被证明是尤其适用的。
(甲基)丙烯酸羟烷基酯、(甲基)丙烯酸羧烷基酯、(甲基)丙烯酸磺烷基酯、(甲基)丙烯酸氨烷基酯、(甲基)丙烯酸氨羰烷基酯可被用作组分(b)的例子。
(甲基)丙烯酸羟烷基酯,特别是甲基丙烯酸羟乙酯(HEMA)和(甲基)丙烯酸羧烷基酯、特别是丙烯酸羧乙酯(βCEA)已被证明是尤为适宜的。
作为组分(C)可被使用的是本技术领域中已知的UV光自由基聚合引发剂,例如2-羟基-2-甲基-1-苯基-1-丙酮(Ciba-Geigy的DAROCURE-1173)、1-羟基-环己基-苯基-酮(Ciba-Geigy的IRGACURE-184)和那些基于苯酮的化合物例如FratelliLamberti的ESACURE KIP 100E、或它们的混合物。
作为涂料单体混合物的粘度调节剂,组分(d)的用量通常很少,优选为0.1~1%(重量);就此用途而言,具有原粒径小于20纳米和pH为3~4的胶态二氧化硅尤为适用。
作为组分(e),为了在通过UV交联涂层时保护聚合物制品,可以使用本技术领域已知的UV稳定剂。
UV稳定剂通常是由苯并***和位阻胺组成,例如Ciba-Geigy的TINUVIN 1130和TINUVIN 2292。
特别是,如果a+b+c的混合物具有很小流动性的话,为了消除这样混合物的分布不良从而提高涂层的外观美学程度,通常使用少量的组分(f)作为流动性改进剂。
氟代脂族聚合物的酯,例如3-M的FC-430是特别适用于此目的的。
其粘度可通过改变单体的百分含量和使用胶态二氧化硅和/或促进流动的非离子表面活性剂而任意调节的涂料单体组合物,可使用现有技术的任何方法例如喷涂、展涂而被涂到基底上,以便形成能够在聚合和UV交联后成为厚度为0.5~40μm、优选为5~15μm的薄膜的均匀涂层。
厚度大的薄膜一般具有更大的刚性和较低的柔性。
涂料单体层a+b+c进行聚合反应和交联反应的温度为20℃~65℃、优选为20℃~60℃、更优选为30℃~55℃。
通常不需要无氧操作,但是,如果使用相对长时间的UV辐照的话,最好在氮气流下操作,以避免由于氧而引起的一定程度的限制。
本发明的方法可以连续地进行,与支持物成形制品的制备例如成膜和挤出联成一体。
更具体地说,本发明的方法可连续地在挤出丙烯酸类板材的生产线上,板材温度不低于65℃处进行。
为了避免由于通常用于聚合和交联涂层的UV灯发出的UV辐照中红外线成分而引起的板材过热,可以使用具有减少了的红外线释放的UV灯,或在UV灯与板材之间放置滤波器以消除大部份红外辐射,例如放置2~3mm厚的PYREX和/或利用冷气体流(空气和/或氮气),以保持***在上述的温度范围内。
本发明的另一个目的是提供通过本发明方法获得的、具有抗擦刮和耐磨涂层的、基于热塑性丙烯酸类聚合物的成形制品、板材和薄膜。
根据本发明方法涂覆的成形制品显示出高的抗擦刮性和耐磨性,最佳的涂膜对基底粘着性,保持其不变的起始透明度、尺寸稳定性和机械性能,并且未显示不希望有的微黄色变。
为了证实抗擦刮和耐磨处理的效果,我们使用两种不同的方法,因为这两种性能是可区别的。
就测定抗擦刮性来说,按照ASTM D3363用木铅笔进行硬度测试。
就测定耐磨性来说,所采用的方法是按照ASTM D673通过将碳化硅粉末下落到处理过的板材上,然后测定由此引起的透明度损失。
薄膜对支持物的粘附性是按照ASTM3359标准通过将610型胶带(3M)贴附在薄膜上测定的。
为了验证耐磨涂料的效果,已进行光学测试。
按照ASTM D1003已进行对光的透光度和浊度测试。
按照ASTM D1925已测定黄度指数。
为了说明本发明特提供以下实施例。实施例1
在3mm厚的PMMA板上展涂一层10μm厚的混合物,该混合物含有50%(重量)的脂族己基丙烯酸氨基甲酸乙酯(EB1290,UCB)、40%(重量)的二丙烯酸1,6-己二醇酯(HDDA)、8%(重量)的甲基丙烯酸羟乙基酯(HEMA)和2%(重量)的UV光引发剂(DAROCURE1173,Ciba-Geigy)。
用两个具有分色石英的80W/cm UV灯使混合物组分发生聚合反应,进给速度为1m/min。
基底温度不超过60℃。交联薄膜显示出在PMMA板上的最佳粘着、耐6H铅笔硬度(未经此处理的PMMA板,其铅笔硬度为B~H)、撒落2000克碳化硅粉末后的浊度约为6%(未经此处理的PMMA板的浊度约为11.5%)和不变的黄度指数(板+薄膜)。实施例2
在3mm厚的HIPMMA板(抗冲击聚甲基丙烯酸甲酯,基料=PMMA,分散相=丙烯酸弹性体和PMMA)上展涂一层10μm厚的类似于实施例1的混合物,但有下述的不同处:使用6%(重量)的甲基丙烯酸羟乙基酯(HEMA)和4%(重量)的UV光引发剂(DAROCURE1173)。将1%(重量)的TINUVIN2292和1%(重量)的TINUVIN1130(UV稳定剂,Ciba-Geigy)添加到100%的该混合物中。
交联条件与实施例1中的相同,交联薄膜显示出在HIPMMA板上的最佳粘着、5H铅笔硬度(未处理的HIPMMA的硬度为2B)、撒落2000克碳化硅粉末后的浊度约为7%(未处理的HIPMMA板为18.5%)和不变的黄度指数。此外,该薄膜还显示出良好的弹性。实施例3
在3mm厚的PMMA板上展涂一层5μm厚的混合物,该混合物含有45%(重量)的Monsanto的Santolink AM1290(含62~68%(重量)的不饱和的二丙烯酰基蜜胺作为低聚合物相和32~28%(重量)的二丙烯酸三聚丙烯甘油酯作为单体相)、45%(重量)的三羟甲基丙烷三丙烯酸酯(TMPTA)、8%(重量)的βCEA(丙烯酸羧乙酯,UCB)和2%(重量)的UV光引发剂(IRGACURE 184,Ciba-Geigy)。
用HPK Philips灯(约25W/cm),灯至板的距离保持在10cm,在氮气流和室温条件下照射5分钟。处理过的板显示出良好的粘着性、耐7H铅笔硬度(未处理的PMMA的硬度为从B至H)、撒落2000克碳化硅粉末后的浊度为8%(未处理的PMMA板的浊度为11.5%)。黄度指数保持不变。实施例4
在3mm厚的PMMA板上展涂一层5μm厚的类似于实施例3的混合物层。
使用实施例1中所用的交联条件(高功率灯,短交联时间,在空气中交联)。
交联薄膜显示出与实施例3相同的性能。实施例5
在3mm厚的PMMA板上展涂一层5μm厚的混合物。该混合物包含50%(重量)的TMPTA、40%(重量)的乙氧基化的三羟甲基丙烷三丙烯酸酯(SR454,Cray Valley)、 5%(重量)的季戊四醇三丙烯酸酯(PETIA)、2%(重量)的βCEA和3%(重量)的UV光引发剂(Esacure KIP100,Fratelli Lamberti)。将1%的胶态二氧化硅HDKT30(Wacker)添加到100%(重量)的该混合物中。
交联条件与实施例1的相同。
此交联薄膜显示出在PMMA板上的最佳粘合、5~6H铅笔硬度和在撒落2000克碳化硅粉末后其浊度约为5.5%(未处理的PMMA板为11.5%)。板的黄度指数保持不变。比较实施例1
在3mm厚的PMMA板上展涂一层10μm厚的、DOS 2928512的实施例1中所用的单体混合物,该混合物含有75%(重量)的三羟甲基丙烷三丙烯酸酯(TMPTA)、20%(重量)的季戊四醇四甲基丙烯酸酯(PETIA)和5%(重量)的作为UV光引发剂的苯偶姻异丁基醚。
采用120W/cm的中压水银蒸汽灯以1m/min的进给速度使该混合物各组分聚合。
基底温度达到95℃。
在这些条件下,板显示出100%的粘着性、最佳的抗擦刮性(铅笔硬度测定为7H)、相当好的耐磨性和撒落2000克碳化硅后的浊度=7.5(未处理的PMMA的浊度=11.5),但出现明显的黄变。
进一步还发现板材出现某种程度的变形和机械性能诸如抗冲和抗弯性能变差。比较实施例2
在3mm厚的PMMA板上展涂一层5μm厚的具有实施例3的配方的混合物涂层。
在空气中用额定120W/cm的中压水银蒸汽灯聚合所说的混合物各组份,基底与灯之间的距离保持在15cm。
在薄膜和PMMA基底上的温度达到接近90℃(聚合时间少于5秒钟)。薄膜成为不透明且无粘合性。
Claims (10)
1、一种制备基于丙烯酸类热塑性聚合物的、具有抗擦刮性和耐磨性的成形制品、板材和薄膜的方法,该方法包括在基于热塑性丙烯酸类聚合物的成形制品的表面上敷施一层均匀的单体组合物,该组合物包含:
a)40~98.5%(重量)的至少一种(甲基)丙烯酸类单体和/或具有至少二个可聚合双键和沸点高于形成所说制品的丙烯酸类聚合物的Tg的低聚物,
b)1~20%(重量)的至少一种具有下式的极性(甲基)丙烯酸类单体,式中:R′是H、CH3;R″是C2~C6的亚烷基;Z是-OH、-COOH、-SO3H、-NH2、-CONH2和/或其由2~7个单体单元形成的低聚物,
c)0.5~10%(重量)的一种UV光聚合引发剂,
d)0~3%(重量)的胶态二氧化硅和/或胶态金属氧化物,
e)0~8%(重量)的UV稳定剂,
f)0~3%(重量)的非离子表面活性剂,a+b+c+d+e+f的量之和为100%,然后将如此涂覆的制品在20℃至65℃的温度下受到UV辐照。
2、按照权利要求1的方法,其中热塑性丙烯酸类聚合物是(甲基)丙烯酸的酯或其混合物与聚氯乙烯或聚偏氟乙烯或丙烯酸类弹性体的(共)聚合物。
3、按照权利要求1的方法,其中热塑性丙烯酸类聚合物是聚甲基丙烯酸甲酯。
4、按照权利要求1的方法,其中组分a)是至少一种甘醇、多元醇、乙氧基化多元醇、脂族的氨基甲酸乙酯和蜜胺的多官能(甲基)丙烯酸酯。
5、按照权利要求4的方法,其中组分a)选自二丙烯酸三聚丙烯甘油酯、三羟甲基丙烷三丙烯酸酯、二丙烯酸1,6-己二醇酯、季戊四醇三丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、脂族己基丙烯酸氨基甲酸乙酯、不饱和的二丙烯酰基蜜胺或它们的混合物。
6、按照权利要求1的方法,其中组分b)选自(甲基)丙烯酸羟烷基酯、(甲基)丙烯酸羧烷基酯、(甲基)丙烯酸磺烷基酯、(甲基)丙烯酸氨烷基酯、(甲基)丙烯酸氨羰烷基酯。
7、按照权利要求6的方法,其中组分b)是甲基丙烯酸羟乙酯或丙烯酸羧乙酯。
8、按照权利要求1的方法,其中UV辐照是在温度为30℃~55℃时进行的。
9、按照权利要求8的方法,其中温度为30℃~55℃。
10、通过权利要求1至9之一的方法所制得的、基于热塑性丙烯酸类聚合物的抗擦刮和耐磨的制品。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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ITMI94A001014 | 1994-05-19 | ||
ITMI941014A IT1269796B (it) | 1994-05-19 | 1994-05-19 | Processo per la preparazione di articoli formati antigraffio e antiabrasione,a base di polimeri acrilici |
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CN1120564A true CN1120564A (zh) | 1996-04-17 |
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CN95107127A Pending CN1120564A (zh) | 1994-05-19 | 1995-05-19 | 制备基于丙烯酸类聚合物的抗擦刮和耐磨的成型制品的方法 |
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US (1) | US5698270A (zh) |
EP (1) | EP0685511A3 (zh) |
JP (1) | JPH0847667A (zh) |
KR (1) | KR950032388A (zh) |
CN (1) | CN1120564A (zh) |
CA (1) | CA2149601A1 (zh) |
IT (1) | IT1269796B (zh) |
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CN106633573A (zh) * | 2016-12-21 | 2017-05-10 | 浙江龙游展宇有机玻璃有限公司 | 一种防刮亚克力板及其制备方法 |
CN107512060A (zh) * | 2017-09-08 | 2017-12-26 | 中国乐凯集团有限公司 | 一种太阳能无人机机翼蒙皮材料及其制备方法 |
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KR100383090B1 (ko) * | 2000-07-20 | 2003-05-12 | 주식회사 엘지화학 | 내마모성이 우수한 방현성 필름용 코팅액 조성물, 그의제조방법, 그를 사용하여 제조된 필름 및 그의 제조 방법 |
KR100387535B1 (ko) * | 2000-09-19 | 2003-06-18 | 주식회사 루밴틱스 | 콜로이달 실리카 충전재를 포함하는 광학 접착제 수지조성물 및 이의 제조방법 |
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-
1994
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-
1995
- 1995-05-17 CA CA002149601A patent/CA2149601A1/en not_active Abandoned
- 1995-05-18 EP EP95107588A patent/EP0685511A3/en not_active Withdrawn
- 1995-05-19 KR KR1019950012636A patent/KR950032388A/ko not_active Application Discontinuation
- 1995-05-19 CN CN95107127A patent/CN1120564A/zh active Pending
- 1995-05-19 JP JP7121911A patent/JPH0847667A/ja active Pending
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1997
- 1997-03-06 US US08/812,768 patent/US5698270A/en not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101559687A (zh) * | 2008-04-17 | 2009-10-21 | 辉柏嘉股份公司 | 在笔的表面产生凸起结构的方法 |
CN104418988A (zh) * | 2013-09-04 | 2015-03-18 | Dic株式会社 | 自由基聚合性树脂组合物及土木建筑材料 |
CN106633573A (zh) * | 2016-12-21 | 2017-05-10 | 浙江龙游展宇有机玻璃有限公司 | 一种防刮亚克力板及其制备方法 |
CN107512060A (zh) * | 2017-09-08 | 2017-12-26 | 中国乐凯集团有限公司 | 一种太阳能无人机机翼蒙皮材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
IT1269796B (it) | 1997-04-15 |
ITMI941014A1 (it) | 1995-11-19 |
US5698270A (en) | 1997-12-16 |
EP0685511A3 (en) | 1996-03-06 |
ITMI941014A0 (it) | 1994-05-19 |
CA2149601A1 (en) | 1995-11-20 |
EP0685511A2 (en) | 1995-12-06 |
JPH0847667A (ja) | 1996-02-20 |
KR950032388A (ko) | 1995-12-20 |
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