CN102471508B - 丙烯酸薄膜的制备方法及丙烯酸薄膜 - Google Patents
丙烯酸薄膜的制备方法及丙烯酸薄膜 Download PDFInfo
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- CN102471508B CN102471508B CN201080031629.2A CN201080031629A CN102471508B CN 102471508 B CN102471508 B CN 102471508B CN 201080031629 A CN201080031629 A CN 201080031629A CN 102471508 B CN102471508 B CN 102471508B
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- acrylate
- methyl
- preparation
- film
- resin slurry
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- -1 acryl Chemical group 0.000 claims abstract description 110
- 238000000034 method Methods 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000006188 syrup Substances 0.000 claims abstract description 13
- 235000020357 syrup Nutrition 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 48
- 239000002002 slurry Substances 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 38
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
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- 239000000203 mixture Substances 0.000 claims description 10
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- 230000007704 transition Effects 0.000 claims description 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
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- 150000003003 phosphines Chemical class 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000006182 dimethyl benzyl group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
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- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 5
- 208000034189 Sclerosis Diseases 0.000 description 5
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- 229940117969 neopentyl glycol Drugs 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
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- 238000000227 grinding Methods 0.000 description 4
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
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- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229940063557 methacrylate Drugs 0.000 description 3
- 229940063559 methacrylic acid Drugs 0.000 description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 3
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- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 2
- SVFBPYWZNHLAGQ-UHFFFAOYSA-N 1-isocyanatopropan-2-yl prop-2-enoate Chemical compound O=C=NCC(C)OC(=O)C=C SVFBPYWZNHLAGQ-UHFFFAOYSA-N 0.000 description 2
- MUOYRBYBTJDAOT-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)CC(C)(C)OOC(=O)C(C)(C)C MUOYRBYBTJDAOT-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- GIEGKXINITVUOO-UHFFFAOYSA-N 2-methylidenebutanedioic acid Chemical compound OC(=O)CC(=C)C(O)=O.OC(=O)CC(=C)C(O)=O GIEGKXINITVUOO-UHFFFAOYSA-N 0.000 description 2
- GQPUVGBTOXALMQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,2-triol Chemical compound CC(=C)C(O)=O.CC(O)(O)CO GQPUVGBTOXALMQ-UHFFFAOYSA-N 0.000 description 2
- SBWOBTUYQXLKSS-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propanoic acid Chemical compound CC(=C)C(=O)OCCC(O)=O SBWOBTUYQXLKSS-UHFFFAOYSA-N 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 2
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 2
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 2
- XFOFBPRPOAWWPA-UHFFFAOYSA-N 6-hydroxyhexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCO XFOFBPRPOAWWPA-UHFFFAOYSA-N 0.000 description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 2
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 2
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- WLUUTGIJNRNHRF-UHFFFAOYSA-N tert-butyl heptanoate Chemical compound CCCCCCC(=O)OC(C)(C)C WLUUTGIJNRNHRF-UHFFFAOYSA-N 0.000 description 1
- CSKKAINPUYTTRW-UHFFFAOYSA-N tetradecoxycarbonyloxy tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCC CSKKAINPUYTTRW-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JREYOWJEWZVAOR-UHFFFAOYSA-N triazanium;[3-methylbut-3-enoxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].CC(=C)CCOP([O-])(=O)OP([O-])([O-])=O JREYOWJEWZVAOR-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
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- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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Abstract
本发明涉及丙烯酸薄膜的制备方法及通过该方法制备的丙烯酸薄膜。本发明的丙烯酸薄膜的制备方法,包括以下步骤:由丙烯酸类树脂浆料进行制模的第一步骤;以及,向在第一步骤中制膜得到的丙烯酸类树脂浆料上照射紫外线,使之硬化的第二步骤。根据本发明,可以提供膜厚偏差小,且膜厚精度优异的薄膜。此外,根据本发明,鱼眼等薄膜缺陷以及在纵横方向上的物性之差控制到最小。因此,根据本发明制备的薄膜,可以适用于各种半导体工艺的保护薄膜、光学用粘接或粘贴产品、电子部件用粘接或粘贴产品等各种产业用片材或者多层结构的层压产品上,可发挥优异的效果。
Description
技术领域
本发明涉及丙烯酸薄膜的制备方法及丙烯酸薄膜。
背景技术
目前,如粘结薄膜或者粘结片的粘结产品,频繁用于如切割工艺或双面研磨工艺的半导体晶片加工工艺中的保护薄膜上,也用于广告用薄膜、清洁片、反射片、结构用粘结片、照片用粘结片、道路交通标志用粘结片、光学用粘结产品、电子部件用粘结产品、医疗用贴片等各种产业用片材或者多层结构的层压产品上。
上述粘结薄膜或者粘结片中所包含的基材薄膜,主要使用聚对苯二甲酸乙二醇酯(polyethylene terephthalate,PET)、聚烯烃(polyolefin)、聚氨酯(polyurethane)、乙烯-醋酸乙烯酯(ethlylene vinyl acetate)、聚对苯二甲酸丁二醇酯(polybutylene terephthalate)、聚丙烯(polypropylene)或聚乙烯(polyethylene)等塑料薄膜。
上述的塑料薄膜可通过以下方法制备:将各种热塑性树脂熔融,熔融后的树脂通过使用T形模、抽吸挤压或者压延方法等制备得到。如上所述,通过挤压方法或者压延方法制备得到的薄膜,具有生产率优异、价格低廉的优点。
但是,就如上所述的制备方法而言,具有如下问题:在形成薄膜的过程中,会向树脂内混入不优选的外来物质,或者树脂内存在不溶性成分,因此,在薄膜上生成所谓鱼眼(fish eye)的突出部的可能性高。另外,按照上述方法制备的薄膜,则难以控制薄膜厚度的均匀性,此外,在制备过程中施加的应力,使薄膜在纵轴以及横轴方向上,产生很大的物性之差。
因此,按照现有的制备方法制备得到的薄膜,例如在切割工艺或双面研磨工艺等中使用的情况下,由于不均匀的压力而容易诱发晶片等的龟裂或者弯曲。此外,用于其他用途上时,也存在各种问题。
发明内容
技术问题
本发明的目的在于提供一种丙烯酸薄膜的制备方法及丙烯酸薄膜。
解决问题的手段
本发明为了解决上述问题,提供一种丙烯酸薄膜的制备方法,该丙烯酸薄膜的制备方法包括以下步骤:由丙烯酸类树脂浆料进行制模的第一步骤;以及,向在第一步骤中制膜得到的丙烯酸类树脂浆料上照射紫外线,使之硬化的第二步骤。
作为解决上述问题的另一手段,本发明还提供一种通过上述本发明的方法制备得到的丙烯酸薄膜。
发明的效果
根据本发明,可以提供膜厚偏差小,且膜厚精度优异的薄膜。此外,根据本发明,将鱼眼等薄膜缺陷以及在纵横方向上的物性之差控制到最小。因此,根据本发明制备的薄膜,可以适用于各种半导体工艺的保护薄膜、光学用粘接或粘贴产品、电子部件用粘接或粘贴产品等各种产业用片材或者多层结构的层压产品上,可发挥优异的效果。
具体实施方式
本发明涉及一种丙烯酸薄膜的制备方法,其特征在于,包括以下步骤:由丙烯酸类树脂浆料来进行制模的第一步骤;以及,向在第一步骤制膜得到的丙烯酸类树脂浆料照射紫外线,使其硬化的第二步骤。
下面,详细说明本发明的丙烯酸薄膜的制备方法。
对于在本发明的第一步骤中所使用的丙烯酸类树脂浆料的组成没有特别的限定。在本发明中,例如,可以使用包含丙烯酸类聚合物、反应性单体及光引发剂的丙烯酸类树脂浆料。
在本发明中,对于丙烯酸类树脂浆料中所包含的丙烯酸类聚合物的组成没有特别的限定。在本发明中,例如,从最终硬化物的玻璃化转变温度或粘着(tack)特性方面考虑,可以使用玻璃化转变温度为30℃以上的丙烯酸类聚合物。当丙烯酸类聚合物的玻璃化转变温度小于30℃时,所制备得到的薄膜的玻璃化转变温度过低或者粘着(tack)特性过高,具有限制薄膜用途的顾虑。
在本发明中,如上所述的丙烯酸类聚合物,例如,可以是包含选自由(甲基)丙烯酸烷基酯、(甲基)丙烯酸芳基酯、(甲基)丙烯酸烷氧基烷基酯、含羧基化合物、含羟基化合物、含氮化合物、含缩水甘油基的化合物、苯乙烯类化合物以及羧酸乙烯酯组成的组中的一种以上的单体混合物的聚合物。
上述(甲基)丙烯酸烷基酯的具体例,可以举出,(甲基)丙烯酸甲酯(methyl methacrylate)、(甲基)丙烯酸乙酯(ethyl methacrylate)、(甲基)丙烯酸丙酯(propyl methacrylate)、(甲基)丙烯酸丁酯(butylmethacrylate)、(甲基)丙烯酸己酯(hexyl methacrylate)、(甲基)丙烯酸环己酯(cyclohexyl methacrylate)、(甲基)丙烯酸-2-乙基己酯(2-Ethylhexyl methacrylate)、(甲基)丙烯酸月桂基酯(Laurylmethacrylate)、(甲基)丙烯酸硬脂酸酯(Stearyl Methacrylate)、(甲基)丙烯酸十八烷基酯(Octadecyl methacrylate)、(甲基)丙烯酸异辛酯(iso-Octyl methacrylate)、(甲基)丙烯酸异壬酯(isononylmethacrylate)、(甲基)丙烯酸异癸酯(Isodecyl methacrylate)或者(甲基)丙烯酸异冰片酯(Isobornyl methacrylate)等碳原子数为1至20的直链状或支链状或者具有非环形或环烷基的(甲基)丙烯酸烷基酯等。作为(甲基)丙烯酸芳基酯,可以举出,(甲基)丙烯酸苯酯(phenylmethacrylate)、(甲基)丙烯酸苄酯(benzyl methacrylate)或者(甲基)丙烯酸苯氧乙酯(phenoxyethyl methacrylate)等(甲基)丙烯酸芳基酯。作为(甲基)丙烯酸烷氧基烷基酯,可以举出,(甲基)丙烯酸甲氧基乙酯(Methoxyethyl methacrylate)、(甲基)丙烯酸乙氧基乙酯(Ethoxyethyl methacrylate)、(甲基)丙烯酸丙氧基乙酯(propoxyethylmethacrylate)、(甲基)丙烯酸丁氧基乙酯(butoxyethyl methacrylate)或者如同(甲基)丙烯酸乙氧基丙酯(ethoxypropyl methacrylate)等的烷氧基烷基甲基丙烯酸酯(alkoxyalkyl methacrylate)。
此外,作为含羧基化合物,可以举出,(甲基)丙烯酸(methacrylicacid)、2-(甲基)丙烯酰氧基乙酸(2-methacryloyloxy acetic acid)、3-(甲基)丙烯酰氧基丙酸(3-methacryloyloxy propionic acid)、4-(甲基)丙烯酰氧基丁酸(4-methacryloyloxy butyric acid)、丙烯酸二聚体(acrylic acid dipolymer)、衣康酸(Itaconic Acid)、马来酸(maleic acid)或者马来酸酐(maleic anhydride)等。作为含羟基化合物,可以举出,(甲基)丙烯酸-2-羟乙酯(2-hydroxyethyl methacrylate)、(甲基)丙烯酸-2-羟丙酯(2-hydroxypropyl methacrylate)、(甲基)丙烯酸-4-羟丁酯(4-hydroxybutyl methacrylate)、(甲基)丙烯酸-6-羟己酯(6-hydroxyhexyl methacrylate)、(甲基)丙烯酸-8-羟辛酯(8-hydroxyoctyl methacrylate)、(甲基)丙烯酸-2-羟基乙二醇酯(2-Hydroxy ethylene glycol methacrylate)或者(甲基)丙烯酸-2-羟基丙二醇酯(2-hydroxy propylene glycol methacrylate)等。作为含氮单体,可以举出,(甲基)丙烯酰胺(Methacrylamide)、或者n-羟甲基(甲基)丙烯酰胺(N-Methylol methacrylamide)等,作为含缩水甘油基化合物,可以举出,(甲基)丙烯酸缩水甘油酯(glycidyl methacrylate)等。作为苯乙烯类化合物,可以举出,苯乙烯(styrene)、或者α-甲基苯乙烯(α-Methylstyrene)等。作为羧酸乙烯酯,可以举出,乙酸乙烯酯(vinylacetate)等,但并不限于此。
在本发明中,如上所述的各种单体中,在单体混合物中所含有的具体单体的种类以及组合两种以上单体时,其比率等没有特别的限定,可以从所需的玻璃化转变温度以及其他聚合物的特性考虑,可自由选择。
在本发明中,对于含有上述各个组分的丙烯酸类聚合物,对其制备方法没有特别的限定。例如,可以通过溶液聚合、光聚合、本体聚合、悬浮聚合或者乳液聚合等常规的聚合方法制备得到。在本发明中,特别优选使用溶液聚合方法。在这里,就溶液聚合而言,优选是在各个单体均匀混合的状态下,混合引发剂,并在50℃至140℃的聚合温度下进行。这时,作为可使用的引发剂,可以举出,偶氮二异丁腈(azobis-isobutyronitrile)或者偶氮二环己腈(azobis-cyclohexanecarbonitrile)等偶氮类聚合引发剂和/或如过氧化苯甲酰(Benzoyl Peroxide)或过氧化乙酰(acetyl peroxide)的过氧化物等通常使用的引发剂。
在本发明中,树脂浆料中所包含的上述丙烯酸类聚合物,相对于下述反应性单体100重量份,优选为5重量份至80重量份。当上述含量不小于5重量份时,导致丙烯酸类薄膜的软性过大或者存在对于外部冲击容易受到损伤的顾虑。另外,当上述含量超过80重量份时,则存在薄膜的硬化度下降而难以维持薄膜的形状或者浆料的粘度过大而导致加工工艺的效率下降的顾虑。
本发明的树脂浆料,包含上述丙烯酸类聚合物的同时,还包含可稀释上述聚合物的反应性单体。
如上所述,可以使用的反应性单体的种类,只要是在分子内具有光聚合性双键的化合物则没有特别的限定。例如,可以使用丙烯酸类单体。在这里,作为丙烯酸类单体的种类,可以举出,(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯(n-propyl methacrylate)、(甲基)丙烯酸异丙酯(isopropyl methacrylate)、(甲基)丙烯酸正丁酯(n-butyl methacrylate)、(甲基)丙烯酸叔丁酯(t-butyl methacrylate)、(甲基)丙烯酸仲丁酯(sec-Butyl methacrylate)、(甲基)丙烯酸戊酯(pentyl methacrylate)、(甲基)丙烯酸-2-乙基己酯(2-ethylhexylmethacrylate)、(甲基)丙烯酸-2-乙基丁酯(2-ethylbutyl methacrylate)、(甲基)丙烯酸正辛酯(n-Octyl methacrylate)、(甲基)丙烯酸异辛酯(Isooctyl methacrylate)、(甲基)丙烯酸异冰片酯(Isobornylmethacrylate)、(甲基)丙烯酸异壬酯(isononyl methacrylate)、(甲基)丙烯酸月桂酯(Lauryl methacrylate)、(甲基)丙烯酸金刚烷酯(adamantylmethacrylate)以及(甲基)丙烯酸十四酯(tetradecyl methacrylate)等含有碳原子数为1至12的烷基的(甲基)丙烯酸烷基酯;如甲基丙烯酸二环戊烯基酯(dicyclopentenyl methacrylate)或者(甲基)丙烯酸二环戊烯基氧烷酯(dicyclopentenyloxy methacrylate)的脂环族(甲基)丙烯酸酯;苯基羟基丙基(甲基)丙烯酸酯(phenyl hydroxypropylmethacrylate)或者(甲基)丙烯酸苄酯(benzyl methacrylate)、芳香族(甲基)丙烯酸酯;甲基丙烯酸四氢糠基酯(Tetrahydrofurfurylmethacrylate)或者(甲基)丙烯酸吗啉基酯(morpholinyl methacrylate)的杂环族(甲基)丙烯酸酯等,但并不限于此。
另外,在本发明中,作为上述反应性单体,可以举出,(甲基)丙烯酸-2-羟乙酯(2-hydroxyethyl methacrylate)、(甲基)丙烯酸-2-羟丙酯(2-hydroxypropyl methacrylate)、(甲基)丙烯酸-4-羟丁酯(4-hydroxybutyl methacrylate)、(甲基)丙烯酸-6-羟己酯(6-hydroxyhexyl methacrylate)、(甲基)丙烯酸-8-羟辛酯(8-hydroxyoctyl methacrylate)、(甲基)丙烯酸-2-羟基乙二醇酯(2-Hydroxy ethylene glycol methacrylate)或者(甲基)丙烯酸-2-羟基丙二醇酯(2-hydroxy propylene glycol methacrylate)等含羟基单体;(甲基)丙烯酸(methacrylic acid)、2-(甲基)丙烯酰氧基乙酸(2-methacryloyloxy acetic acid)、3-(甲基)丙烯酰氧基丙酸(3-methacryloyloxy propionic acid)、4-(甲基)丙烯酰氧基丁酸(4-methacryloyloxy butyric acid)、丙烯酸二聚体(acrylic aciddipolymer)、衣康酸(Itaconic Acid)、马来酸(maleic acid)或者马来酸酐(maleic anhydride)等含羧基单体;(甲基)丙烯酰胺(Methacrylamide)、N-乙烯基吡咯烷酮(N-vinylpyrrolidone)或者N-乙烯基己内酰胺(N-vinylcaprolactam)等含氮单体等极性单体单独或者与上述组分一起使用。通过适当使用如上所述的极性单体,可以给制备得到的丙烯酸薄膜赋予凝集力,并且有效控制其机械强度。
在本发明中,树脂浆料除了包含上述组分以外,还包含光引发剂。这样的光引发剂,根据使用量,可以控制树脂浆料的聚合度。在本发明中,上述光引发剂,例如,相对于上述反应性单体100重量份,可以使用0.01重量份至30重量份。可以通过浆料的聚合度以及薄膜的物性等方面考虑来进行控制,但并不限于上述范围。
在本发明中,作为光引发剂,只要是通过照射紫外线等引发聚合反应的化合物则可以使用任何一种。在本发明中,可使用的光引发剂的种类没有特别的限定。例如,α-羟基酮类化合物(α-hydroxyketone)(例如:IRGACURE 184、IRGACURE 500、IRGACURE 2959、DAROCUR 1173;汽巴特殊化学(制));苯甲酰甲酸酯类化合物(phenylglyoxylate)(例如:IRGACURE 754、DAROCUR MBF;汽巴特殊化学(制));二甲基苄基酮类化合物(Benzyl Dimethyl Ketal)(例如:IRGACURE 651;汽巴特殊化学(制));α-氨基酮类化合物(α-amino-ketone)(例如:IRGACURE 369、IRGACURE 907、IRGACURE1300;汽巴特殊化学(制));单酰基膦类化合物(MAPO)(例如:DAROCUR TPO;汽巴特殊化学(制));二酰基膦类化合物(BAPO)(例如:IRGACURE 819、IRGACURE 819DW;汽巴特殊化学(制));氧化膦类化合物(phosphine oxide)(例如:IRGACURE 2100;汽巴特殊化学(制));茂金属类化合物(metallocene)(例如:IRGACURE 784;汽巴特殊化学(制));碘鎓盐(iodonium salt)(例如:IRGACURE 250;汽巴特殊化学(制));以及上述的一种以上混合物(例如:DAROCUR4265、IRGACURE 2022、IRGACURE 1300、IRGACURE 2005、IRGACURE 2010、IRGACURE 2020;汽巴特殊化学(制))等。在本发明中,可以使用上述化合物中一种或两种以上,但并不限于此。
本发明的第一步骤中所使用的树脂浆料,根据需要还包含热引发剂。如上所述的热引发剂,根据其使用量,可进一步提高树脂浆料的转换率,特别是,即便最终制备得到的丙烯酸薄膜非常厚,也能够制备具有均匀的物性的薄膜。
在本发明中可以使用的热引发剂的种类,没有特别的限定。在本发明中,例如可以举出,2,2′-偶氮二(2-甲基丁腈)(2,2′-azobis(methylbutyronitrile))、2,2′-偶氮二(异丁腈)(2,2′-azobis(isobutyronitrile))、2,2′-偶氮二(2,4-二甲基戊腈)(2,2′-azobis(2,4-dimethylvaleronitrile))、4,4-偶氮二(4-氰基戊酸)(4,4’-azobis(4-cyanovaleric Acid))、1,1′-偶氮二(环己甲腈)(1,1′-azobis(cyclohexane-carbonitrile))以及2,2′-偶氮二(4-甲氧基-2,4-二甲基戊腈)(2,2′-azobis(4-methoxy-dimethylvaleronitrile))等偶氮类化合物;四甲基丁基过氧化新癸酸酯(TetramethylbutylPeroxyneodecanoate)(例如:Perocta ND,NOF社(制))、双(4-丁基环己基)过氧化二碳酸酯(bis(4-butylcyclohexyl)peroxydicarbonate)(例如:Peroyl TCP,NOF社(制))、二(2-乙基己基)过氧化碳酸酯(di-(2-ethylhexyl)peroxycarbonate)、过氧化新癸酸丁酯(butylPeroxyneodecanoate)(例如:Perbutyl ND,NOF社(制))、过氧化二碳酸二丙基酯(dipropyl peroxydicarbonate)(例如:Peroyl NPP,NOF社(制))、过氧化二碳酸二异丙酯(diisopropyl peroxydicarbonate)(例如:Peroyl IPP,NOF社(制))、过氧化二碳酸二乙氧乙酯(diethoxyethylperoxydicarbonate)(例如:Peroyl EEP,NOF社(制))、过氧化二碳酸二乙氧己酯(diethoxyhexyl peroxydicarbonate)(例如:Peroyl OEP,NOF社(制))、过氧化二碳酸己酯(hexyl peroxydicarbonate)(例如:Perhexyl ND,NOF社(制))、过氧化二碳酸二甲氧丁酯(dimethoxybutylperoxydicarbonate)(例如:Peroyl MBP,NOF社(制))、双(3-甲氧基-3-甲氧基丁基)过氧化二碳酸酯(bis(3-methoxy-3-methoxybutyl)-peroxydicarbonate)(例如:Peroyl SOP,NOF社(制))、过氧化二碳酸二丁基酯(dibutyl peroxydicarbonate)、过氧化二(十六烷基)二碳酸酯(dicetyl peroxydicarbonate)、过氧化二碳酸双十四烷基酯(dimyristyl peroxydicarbonate)、1,1,3,3-四甲基丁基过氧化新戊酸酯(1,1,3,3-Tetramethylbutyl peroxypivalate)、过氧化新戊酸己酯(hexylperoxypivalate)(例如:Perhexyl PV,NOF社(制))、过氧化新戊酸丁酯(butyl peroxypivalate)(例如:Perbutyl,NOF社(制))、三甲基己酰过氧化物(trimethyl hexanoyl peroxide)(例如:Peroyl 355,NOF社(制))、二甲基羟丁基过氧化新癸酸酯(dimethyl hydroxybutylPeroxyneodecanoate)(例如:Luperox 610M75,阿托菲纳公司(制))、过氧化新癸酸戊酯(Amyl peroxyneodecanoate)(例如:Luperox 546M75,阿托菲纳公司(制))、过氧化新癸酸丁酯(butyl peroxyneodecanoate)(例如:Luperox 10M75,阿托菲纳公司(制))、过氧化新庚酸叔丁酯(t-butyl peroxyneoheptanoate)、过氧化新戊酸戊酯(Amylperoxypivalate)(例如:Luperox 546M75,阿托菲纳公司(制))、过氧化新戊酸叔丁酯(t-butyl peroxypivalate)、过氧化(2-乙基)己酸叔戊酯(t-Amyl peroxy-2-Ethyl hexanoate)、过氧化月桂基(Lauryl peroxide)、过氧化二月桂酰(dilauroyl peroxide)、过氧化二癸酰(Didecanoylperoxide)、过氧化苯甲酰(benzoyl peroxide)、过氧化二苯甲酰(dibenzoylperoxide)、2,2-双(叔丁基过氧基)丁烷(2,2-bis(tert-butylperoxy)butane)、1,1-双(叔丁基过氧基)环己烷(1,1-bis(tert-butylperoxy)cyclohexane)、2,5-双(丁基过氧基)-2,5-二甲基己烷(2,5-bis(butylperoxy)-2,5-dimethylhexane)、2,5-双(叔丁基过氧基)-1-甲基乙基)苯(2,5-bis(tert-butylperoxy)-1-methylethyl)benzene)、1,1-双(叔丁基过氧基)-3,3,5-三甲基环己烷(1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane)、过氧化氢叔丁基(tert-butyl hydroperoxide)、叔丁基过氧化物(tert-butyl peroxide)、过氧化苯甲酸叔丁酯(tert-butyl peroxybenzoate)、叔丁基过氧异丙基甲酸酯(tert-butylperoxy isopropyl carbonate)、氢过氧化枯烯(cumenehydroxyperoxide)、过氧化二异丙苯(Dicumyl peroxide)、过氧化月桂酰(Lauroyl peroxide)或2,4-戊二酮过氧化物(2,4-pentanedione peroxide)等过氧化类化合物;过氧化乙酸叔丁酯(tert-butyl peracetate);过氧乙酸(peracetic acid)或者过硫酸钾(potassium persulfate)等,但并不限于此。在本发明中,可以使用上述热引发剂的其中一种或者两种以上的混合物。
在本发明中,树脂浆料中所包含的热引发剂,相对于100重量份的反应性单体,包含0.01重量份至10重量份的量。但是,上述热引发剂的含量仅作为本发明的一例示出,可以根据所需的转换率的改善效果等自由选择。
在本发明的第一步骤中所使用的树脂浆料,相对于上述反应性单体100重量份,还包含0.05重量份至50重量份的交联剂。这样的交联剂,根据其使用量,可以改善丙烯酸薄膜的拉伸特性等物性。
在本发明中可以使用的上述交联剂种类,没有特别的限制,例如,可以使用多官能团丙烯酸酯。在这种情况下,可使用的多官能团丙烯酸酯的种类,没有特别的限定。在本发明中,例如可以举出1,4-丁二醇二(甲基)丙烯酸酯(1,4-butanediol dimethacrylate)、1,6-己二醇二(甲基)丙烯酸酯(1,6-hexanediol dimethacrylate)、新戊二醇二(甲基)丙烯酸酯(Neopentyl Glycol dimethacrylate)、聚乙二醇二(甲基)丙烯酸酯(polyethylene glycol dimethacrylate)、己二酸新戊二醇二(甲基)丙烯酸酯(neopentylglycol adipate dimethacrylate)、羟基新戊酸酯二甲基丙烯酸新戊二醇酯(hydroxypivalate neopentylglycol dimethacrylate)、二环戊烯基二(甲基)丙烯酸酯(dicyclopentenyl dimethacrylate)、己内酯改性二环戊烯基二(甲基)丙烯酸酯(Caprolactone Modifieddicyclopentenyl dimethacrylate)、环氧乙烷改性二(甲基)丙烯酸酯(ethyleneoxide Modified dimethacrylate)、二(甲基)丙烯酰氧乙基异氰酸酯(dimethacryloxy ethyl isocyanurate)、烯丙基化环己基二(甲基)丙烯酸酯(allylated cyclohexyl dimethacrylate)、三环癸二甲醇(甲基)丙烯酸酯(Tricyclodecanedimethanol methacrylate)、二羟甲基二环戊烷二(甲基)丙烯酸酯(Dimethylol dicyclopentane dimethacrylate)、环氧乙烷改性六氢化邻苯二甲酸二(甲基)丙烯酸酯(ethyleneoxide ModifiedHexahydrophthalic acid dimethacrylate)、新戊二醇改性三甲基丙烷二(甲基)丙烯酸酯(neopentylglycol Modified trimethylpropanedimethacrylate)、金刚烷二(甲基)丙烯酸酯(adamantane dimethacrylate)或者9,9-双[4-(2-丙烯酰氧基乙氧基)苯基]氟(fluorine)(9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorine)等2官能团丙烯酸酯;三羟甲基丙烷三(甲基)丙烯酸酯(trimethylolpropane trimethacrylate)、二季戊四醇三(甲基)丙烯酸酯(Dipentaerythritol trimethacrylate)、丙酸改性二季戊四醇三(甲基)丙烯酸酯(propionic acid ModifiedDipentaerythritol trimethacrylate)、季戊四醇三(甲基)丙烯酸酯(pentaerythritol trimethacrylate)、环氧丙烷改性三羟甲基丙烷三(甲基)丙烯酸酯(propylene oxide Modified trimethylolpropane trimethacrylate)、三官能团氨基甲酸酯(甲基)丙烯酸酯(three-functional group urethanemethacrylate)或者三(甲基)丙烯酰氧乙基异氰酸酯(trismethacryloxyethyl isocyanurate)等三官能团丙烯酸酯;二甘油四(甲基)丙烯酸酯(diglycerin tetramethacrylate)或者季戊四醇四(甲基)丙烯酸酯(pentaerythritol tetramethacrylate)等四官能团丙烯酸酯;丙酸改性二季戊四醇五(甲基)丙烯酸酯(propionic acid Modified Dipentaerythritolpentamethacrylate)等五官能团丙烯酸酯;以及二季戊四醇六(甲基)丙烯酸酯(Dipentaerythritol hexamethacrylate)、己内酯改性二季戊四醇六(甲基)丙烯酸酯(Caprolactone Modified Dipentaerythritolhexamethacrylate)或者氨基甲酸酯(甲基)丙烯酸酯(urethanemethacrylate)(例如:异氰酸酯(isocyanate)单体及三羟甲基丙烷三(甲基)丙烯酸酯(trimethylpropane trimethacrylate)的反应产物)等六官能团丙烯酸酯等,但并不限于此。
在本发明中,上述多官能团丙烯酸酯,相对于上述反应性单体100重量份,可以使用0.05重量份至50重量份。但是,上述含量仅作为一例示出,在本发明中,从工艺效率或者薄膜物性(例如:玻璃化转变温度等)方面考虑,可以自由控制多官能团丙烯酸酯的含量。
本发明的树脂浆料中,根据需要在上述组分中适当添加选自由导热性添加剂、阻燃剂、颜料、抗氧化剂、紫外线稳定剂、分散剂、消泡剂、增粘剂、可塑剂以及硅烷偶联剂组成的组中的一种以上添加剂。
在本发明的第一步骤中所使用的树脂浆料,可以通过该技术领域中公知的方法,适当调配上述组分而制备得到。在本发明中,这一步骤的树脂浆料,其固体成分浓度为100%时,具体而言,上述树脂浆料优选为无溶剂类型。如上所述,树脂浆料为无溶剂类型时,可以改善工艺效率,没有突出部(fish eye)等缺陷,并且能够制备膜厚偏差均匀的薄膜。此外,不使用溶剂,因此,容易制备厚度厚的薄膜,并且不需要溶剂挥发步骤,在实际设备中可以省略干燥烘箱等干燥机。此外,由于省略了溶剂挥发步骤,因此不需要设置溶剂挥发引发的环保设备,也不引发工艺环境污染问题或者工艺后环境污染问题。
并且,在本发明中,在上述过程中丙烯酸类树脂浆料的粘度优选控制在约为100cps至10000cps的范围。通过将上述树脂浆料的粘度控制在上述范围内,能够进行更为有效的工艺。
在本发明的第一步骤中,由通过上述方法制备得到的树脂浆料进行制膜。此时,由树脂浆料进行制膜的方法,没有特别的限定,例如可以采用浇注(casting)法。具体而言,在本发明的第一步骤中,采用棒涂、刮涂、辊涂、喷涂、凹印、帘式淋涂、点涂和/或边缘涂敷等常规方法,在适当的工艺基材上涂敷上述树脂浆料,从而实施制膜工艺。通过如上所述方法实施制膜,通过下述的紫外线照射步骤,可以制得膜厚均匀、高温尺寸稳定性、切割性以及透明性等物性得以提高的薄膜。具体来说,本发明通过以下方法制备丙烯酸薄膜:将上述树脂浆料以液态在适当工艺基材上浇添加(casting)后,将其薄膜化,除去工艺基材。通过使用这种方法,使成膜时施加在树脂上的应力最小化,随着时间经过或者加热引起的尺寸不发生变化。另外,容易除去固形杂质,抑制了制膜后的薄膜上发生突出部(fish eye)等,因此,可以提高膜厚的均匀性以及膜厚的精度。此外,在适用上述方法的情况下,薄膜的应力缓和性得以提高,从而附着在粘附体上时,可以迅速解除残余应力。
另一方面,对于在上述制膜工艺中可以使用的工艺基材,其种类没有特别的限定。例如,可以使用常规的塑料基材(例如:PET基材)、纸、无纺布、玻璃或者金属性基材。并且,在本发明中,还可以在上述的工艺基材上实施适当的脱模处理后使用。
本发明的第二步骤是,向在第一步骤中制膜的树脂浆料上照射紫外线而使其硬化,由此对树脂浆料进行聚合的步骤。在本发明的第二步骤中,对于照射紫外线的方法没有特别的限定。例如,通过使用高压水银灯、无电极灯或氙气灯(xenon lamp)等来进行。
此外,本发明的第二步骤,例如,将照度为5mW/cm2至200mW/cm2的紫外线(波长:230nm至400nm)照射约2秒钟至20分钟来进行实施。此外,在上述步骤中,紫外线的光量可以控制在4mJ/cm2至2000mJ/cm2的范围内。
但是,上述紫外线的照射条件,仅为本发明的一例示出。即,在本发明中,在不损坏诸多物性的前提下,使树脂浆料充分硬化的范围内,可以自由改变第二步骤的紫外线照射条件。
另一方面,在本发明中,树脂浆料包含光引发剂的同时,还包含热引发剂的情况下,在如上所述的UV照射过程中,通过在反应体系内产生的热,上述热引发剂可以发生聚合反应。在这种情况下,UV硬化反应时产生的热,不足以引发热引发剂的聚合反应,则在上述的UV照射过程中或者该UV照射过程之后,通过热风或者红外线加热等手段,向树脂浆料施加适当的热量。
在本发明中,通过上述方法将树脂浆料硬化后,通过适当的方法除去工艺基材,从而能够制备丙烯酸薄膜。
本发明还涉及通过上述本发明的方法制备得到的丙烯酸薄膜。
如上所述,在本发明中,将液态树脂浆料优选为固体成分浓度为100%的树脂浆料浇注,使之硬化而制备薄膜,从而能够制得膜厚均匀、高温尺寸稳定性、切割性、应力缓和性及透明性等物性得以提高的薄膜。
因此,根据本发明制备的丙烯酸薄膜,既可以用于切割工艺(dicing)或双面研磨工艺(back grinding)等的各种半导体工艺中的保护薄膜上,同时可用于保护薄膜、广告用薄膜、清洁片、反射片、结构用粘结片、照片用粘结片、道路交通标志用粘结片、光学用粘结产品或者电子部件用粘结产品等各种产业用片材上。另外,本发明的薄膜可以有效用于多层结构的层压产品,例如,普通的商业用粘结产品、医疗用贴片或者加热活性粘接剂(heat activated pressure-sensitiveadhesive)等上。
如上所述,本发明的薄膜的膜厚等物性,可根据适用薄膜的用途选择,并没有特别的限定。例如,本发明的薄膜,其厚度可以适当控制在0.02mm至3.0mm,优选为0.05mm至1.0mm的范围内。当上述薄膜的厚度小于0.02mm时,存在膜厚均匀度下降的顾虑。当膜厚超过3.0mm而形成厚膜的情况下,用于树脂浆料的硬化所必须的UV照射量或热量过分增加。此外,存在所制备的薄膜受损或薄膜内部以及薄膜表面的物性不均匀的顾虑。
实施例
下面,通过本发明的实施例以及不属于本发明的比较例来更详细说明本发明,但本发明的范围并不限于下面要公开的实施例。
实施例1.
相对于作为反应性单体的甲基丙烯酸甲酯100重量份,分散作为丙烯酸类聚合物的重均分子量为100000的聚(甲基)丙烯酸酯50重量份,搅拌30分钟以上。然后,在混合后的混合物中加入作为光引发剂的(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO,2,4,6-trimethylbenzoyl)diphenylphosphine oxide)5重量份,继续搅拌30分钟以上,制备固体成分含量为100%的树脂浆料。接着,利用刮涂机来涂敷在厚度为38μm的PET基材上制备得到的树脂浆料(涂敷厚度:150μm)。进而,将经制膜后的树脂浆料置于金属卤化物灯下,将10mW/cm2的紫外线照射3分钟,使之硬化而制备了丙烯酸薄膜。
实施例2.
除了使用相对于作为反应性单体的甲基丙烯酸甲酯(methylmethacrylate)50重量份及丙烯酸丁酯(butyl acrylate)50重量份,除了调配聚(甲基)丙烯酸酯(polymethyl methacrylate)50重量份以及(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)5重量份制备树脂浆料之外,其余与按照实施例1相同的方法制备了丙烯酸薄膜。
实施例3.
除了使用相对于作为反应性单体的丙烯酸丁酯100重量份,调配聚(甲基丙烯酸甲酯)50重量份以及(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)5重量份制备树脂浆料之外,其余与按照实施例1相同的方法制备了丙烯酸薄膜。
实施例4.
除了使用相对于作为反应性单体的丙烯酸丁酯100重量份,调配聚(甲基丙烯酸甲酯)50重量份、作为光引发剂的(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)3重量份以及作为热引发剂的过氧化苯甲酰(BPO,Benzoyl Peroxide)2重量份制备树脂浆料之外,其余与按照实施例1相同的方法进行UV硬化。接着,向UV硬化物施加110℃温度的热3分钟,使之热固化而制备了丙烯酸薄膜。
1.转换率的测定
将在实施例中制备得到的丙烯酸薄膜以10cm×10cm的大小切割而制备试样,测定其体重。接着,将制备得到的试样放置于110℃的热风烘箱中1小时。其后,测定置于热风烘箱中的丙烯酸薄膜的重量,将减重值换算为百分比,测定转换率。
将上述实施例的结果,整理并记载在以下表1中。
(表1)
从上述表1的结果可知,通过本发明,将固体成分浓度为100%的树脂浆料,经涂敷、制膜以及硬化而制备薄膜的情况下,可以制备膜厚均匀度优异,纵轴及横轴没有物性偏差,且转换率为95%以上的薄膜。特别是,在树脂浆料中同时包含光引发剂及热引发剂,采用双重硬化方法的情况下,可以确认到转换率更加得以提高的结果。
Claims (17)
1.一种丙烯酸薄膜的制备方法,其特征在于,包括以下步骤:
第一步骤:由丙烯酸类树脂浆料进行制膜,所述丙烯酸类树脂浆料包含丙烯酸类聚合物、稀释所述聚合物的反应性单体、光引发剂和热引发剂;以及
第二步骤:向在第一步骤制膜得到的丙烯酸类树脂浆料照射紫外线并向所述树脂浆料进一步施加50℃至140℃的热,使其双重硬化,其中所述树脂浆料的固体成分浓度为100%;
其中所制备的膜厚度均匀。
2.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,丙烯酸类聚合物的玻璃化转变温度为30℃以上。
3.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,丙烯酸类聚合物是包含选自由(甲基)丙烯酸烷基酯、(甲基)丙烯酸芳基酯、(甲基)丙烯酸烷氧基烷基酯、含羧基化合物、含羟基化合物、含氮化合物、含缩水甘油基化合物、苯乙烯类化合物以及羧酸乙烯酯组成的组中的一种以上的单体混合物的聚合物。
4.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,树脂浆料,相对于反应性单体100重量份,包含5重量份至80重量份的丙烯酸类聚合物。
5.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,反应性单体包含选自由(甲基)丙烯酸烷基酯、脂环族(甲基)丙烯酸酯、芳香族(甲基)丙烯酸酯以及杂环族(甲基)丙烯酸酯组成的组中的一种以上。
6.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,反应性单体包含选自由含羟基单体、含羧基单体以及含氮单体组成的组中的一种以上极性单体。
7.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,树脂浆料,相对于100重量份的反应性单体,包含0.01重量份至30重量份的光引发剂。
8.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,光引发剂为选自由α-羟基酮类化合物、苯甲酰甲酸酯类化合物、二甲基苄基酮类化合物、α-氨基酮类化合物、单酰基膦类化合物、二酰基膦类化合物、氧化膦类化合物以及茂金属类化合物组成的组中的一种以上化合物。
9.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,热引发剂为选自由偶氮类化合物以及过氧化类化合物组成的组中的一种以上化合物。
10.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,热引发剂为选自过氧化乙酸叔丁酯、过氧乙酸以及过硫酸钾组成的组中的一种以上化合物。
11.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,树脂浆料还包含交联剂。
12.根据权利要求11所述的丙烯酸薄膜的制备方法,其特征在于,交联剂为多官能团丙烯酸酯。
13.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,树脂浆料的粘度在100cps至10000cps范围内。
14.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,将树脂浆料涂敷在基材上来实施第一步骤。
15.根据权利要求1所述的丙烯酸薄膜的制备方法,其特征在于,将照度为5mW/cm2至200mW/cm2的紫外线照射2秒钟至20分钟来实施第二步骤。
16.一种丙烯酸薄膜,其特征在于,通过权利要求1至15中任一项所述的方法制备得到。
17.根据权利要求16所述的丙烯酸薄膜,其特征在于,厚度在0.02mm至3.0mm的范围内。
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TW201107383A (en) | 2011-03-01 |
TWI500666B (zh) | 2015-09-21 |
US8710112B2 (en) | 2014-04-29 |
CN102471508A (zh) | 2012-05-23 |
KR20110021276A (ko) | 2011-03-04 |
EP2471849A2 (en) | 2012-07-04 |
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