CN101981068B - A method for producing a resin composition, a hard coating agent, film and molded - Google Patents

A method for producing a resin composition, a hard coating agent, film and molded Download PDF

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CN101981068B
CN101981068B CN 200980110485 CN200980110485A CN101981068B CN 101981068 B CN101981068 B CN 101981068B CN 200980110485 CN200980110485 CN 200980110485 CN 200980110485 A CN200980110485 A CN 200980110485A CN 101981068 B CN101981068 B CN 101981068B
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film
hard coat
resin composition
producing
coating
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CN 200980110485
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CN101981068A (en
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间濑晴彦
西野刚
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爱克工业株式会社
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Priority to JP2008075174 priority
Priority to JP2008-079668 priority
Priority to JP2008079668 priority
Priority to JP2008-224208 priority
Priority to JP2008-224189 priority
Priority to JP2008224189 priority
Priority to JP2008224208 priority
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Priority to PCT/JP2009/055833 priority patent/WO2009119588A1/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates

Abstract

本发明的树脂组合物的特征在于,含有具有两个以上丙烯酰基的多官能可聚合化合物以及可与丙烯酰基进行加成反应的化合物。 The resin composition of the present invention, polyfunctional compounds having two or more acryloyl groups and a polymerizable compound addition reaction with an acryloyl group contains a.

Description

树脂组合物、硬质涂覆剂、薄膜和成型体的制造方法 A method for producing a resin composition, a hard coating agent, film and molded

技术领域 FIELD

[0001] 本发明涉及树脂组合物、硬质涂覆剂、薄膜和成型体的制造方法。 [0001] A method for producing a resin composition, a hard coating agent, and forming a thin film of the present invention relates.

背景技术 Background technique

[0002] -直以来,在家电产品的薄膜开关(membrane switch)或者自动售货机的展示罐(义$-缶)等中,均在使用涂布了热固化型树脂的薄膜。 [0002] - straight since the membrane switch in household appliances (membrane switch) or of the vending machine can display ($ sense - pottery), etc., are coated with a thin film using a thermosetting resin.

[0003] 此外,涂布•固化了与热固化型树脂相比具有更好耐擦伤性的紫外线固化型树脂的成型用薄膜日渐普及。 [0003] In addition, the coating film formed • cured ultraviolet curable resin as compared to have better scratch resistance with a thermosetting resin increasingly popular. 特别是由于手机、便携式音乐播放器、触控面板等电子设备箱体和汽车内部装饰材料对硬度、耐擦伤性、耐污染性、光泽感等有要求,因此在这些用途中开始使用涂布•固化了紫外线固化型树脂的成型用薄膜(参见专利文献1-3)。 In particular, since a mobile phone, a portable music player, electronic device such as a touch panel and the housing interior automotive trim materials for hardness, scratch resistance, stain resistance, gloss and the like is required, so start using a coating for these purposes • a cured film formed of the ultraviolet curable resin (see Patent Document 1-3).

[0004] 现有技术文献 [0004] The prior art documents

[0005] 专利文献1 :国际公开第00/34396号文本 [0005] Patent Document 1: International Publication No. 00/34396 text

[0006] 专利文献2 :特开2005-8717号公报 [0006] Patent Document 2: Laid-Open Patent Publication No. 2005-8717

[0007] 专利文献3 :特开2004-305863号公报 [0007] Patent Document 3: Laid-Open Patent Publication No. 2004-305863

发明内容 SUMMARY

[0008] 发明要解决的问题 [0008] Problems to be solved

[0009] 涂布了热固化型树脂的薄膜的硬度和耐擦伤性低,容易产生伤痕,从而在外观上显著劣化。 [0009] The coating hardness and scratch resistance of the thermosetting resin film is low, easily scratched, so that significant deterioration in appearance. 另一方面,涂布•固化了紫外线固化型树脂的成型用薄膜由于刚性强而容易产生裂缝,因此成型性低,只能用于比较平坦的结构体的成型。 On the other hand, • applying the ultraviolet curable resin cured film is formed due to the high rigidity easily cracks, thus moldability is low, only for forming a relatively flat structure.

[0010] 本发明是鉴于以上问题而做出的,以提供硬度和耐擦伤性高且成型性良好的树脂组合物、硬质涂覆剂、薄膜和成型体的制造方法为目的。 [0010] The present invention is made in view of the above, to provide high abrasion resistance and hardness and good moldability resin composition, a hard coating agent, the film and a method for the purpose of producing a molded article.

[0011] 解决问题的手段 [0011] means to solve the problem

[0012] 以下,对本发明进行详细说明。 [0012] Hereinafter, the present invention will be described in detail.

[0013] (1)本发明的树脂组合物 [0013] (1) The resin composition of the present invention

[0014] 本发明的树脂组合物的特征在于,其含有具有两个以上丙烯酰基的多官能可聚合化合物以及可与丙烯酰基进行加成反应的化合物。 [0014] The resin composition of the present invention is characterized in that it contains a compound having two or more acryloyl groups and a polyfunctional polymerizable compound may be an addition reaction with acryloyl groups.

[0015] 本发明的树脂组合物在进行了一次固化的状态下,不仅具有成型时也不易产生裂缝的柔软性,还不易产生胶粘性。 Resin composition [0015] of the present invention is performed under a cured state, not only the flexibility of having a crack hardly occurs during molding, but also easy to produce tackiness. 此外,本发明的树脂组合物在进行了二次固化的状态下硬度和耐擦伤性均优良。 Further, the resin composition of the present invention performing the hardness and excellent in the scratch resistance of the secondary cured state.

[0016] 此外,所谓一次固化的含义是与丙烯酰基进行加成反应。 [0016] In addition, the meaning of a so-called primary curing is an addition reaction with an acryloyl group. 此外,所谓二次固化是通过照射紫外线、电子射线等活性能量射线来进行自由基聚合。 Furthermore, secondary curing is carried out so-called free radical polymerization by irradiation with ultraviolet rays, electron rays, active energy rays. 本发明涉及的具有两个以上丙烯酰基的多官能可聚合化合物由于自由基反应性非常高,并具有快速固化性和高硬度, 因此具有优势。 Polyfunctional having two or more acryloyl groups present invention relates to a radical polymerizable compound due to the very high reactivity and fast cure and high hardness, and therefore advantageous. 作为具有两个以上丙烯酰基的多官能可聚合化合物,可列举例如1,4_ 丁二醇二丙烯酸酯、1,6_己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、羟基三甲基乙酸新戊二醇二丙烯酸酯、二丙烯酸二环戊烯酯、己内酯改性二丙烯酸二环戊烯酯、 环氧乙烷改性磷酸二丙烯酸酯、烯丙基化二丙烯酸环己酯、异氰脲酸酯二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、二季戊四醇三丙烯酸酯、丙酸改性二季戊四醇三丙烯酸酯、季戊四醇三丙烯酸酯、环氧丙烷改性三羟甲基丙烷三丙烯酸酯、三(丙烯酰氧基乙基)异氰脲酸酯、二季戊四醇五丙烯酸酯、丙酸改性二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、己内酯改性二季戊四醇六丙烯酸酯等。 The polyfunctional acryloyl groups having two or more polymerizable compounds include, for example butanediol diacrylate 1,4_, 1,6_-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, diacrylate, dicyclopentenyl acrylate, caprolactone-modified diacrylate, dicyclopentenyl acrylate, ethylene oxide-modified phosphoric acid diacrylate, alkenyl di-propyl acrylate, cyclohexyl acrylate, isocyanurate diacrylate, trimethylol propane triacrylate, dipentaerythritol triacrylate, propionic acid-modified dipentaerythritol triacrylate, pentaerythritol triacrylate, epoxy oxide-modified trimethylol propane triacrylate, tris (acryloyloxyethyl) isocyanurate, dipentaerythritol pentaacrylate, propionic acid-modified dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, hexyl caprolactone-modified dipentaerythritol hexaacrylate.

[0017] 官能团数越多的丙烯酸酯表面硬度越高,因此是优选的。 [0017] the more the higher the number of acrylate functional surface hardness, which is preferable. 其可单独使用也可两种以上混合使用。 Which may be used alone or in combination of two or more. 具有两个以上丙烯酰基的多官能可聚合化合物可以为单体也可以为预聚物,此外,也可以为氨基甲酸酯丙烯酸酯、乙氧基丙烯酸酯、聚酯丙烯酸酯等。 The polyfunctional acryloyl groups having two or more polymerizable compounds may be monomers for the prepolymer, in addition, it may be a urethane acrylate, ethoxymethyl acrylate, polyester acrylate and the like.

[0018] 本发明中使用的可与丙烯酰基进行加成反应的化合物为可与具有两个以上丙烯酰基的多官能可聚合化合物进行加成反应的化合物。 Compound [0018] The addition reaction may be carried out in the present invention is carried out using the acryl compound can be an addition reaction of a polyfunctional polymerizable compound having two or more acryloyl groups. 通过该加成反应,对树脂组合物进行一次固化(B阶段化),因此树脂组合物的胶粘性消失或减少。 , The resin composition once cured (B-staged) by the addition reaction, the adhesive resin composition is removed or reduced. 利用这一特点,通过在将树脂组合物涂布在薄膜上之后施加促进加成反应的条件,可防止薄膜之间的粘结和成型时薄膜与铸模之间的粘结。 With this feature, by addition reaction promoting conditions applied after the resin composition is applied to the film, adhesion between the films and prevents adhesion between the film and the mold during molding. 可与丙烯酰基进行加成反应的化合物只要是具有亲核性的化合物即可,但具体优选胺化合物。 An addition reaction with a compound acryloyl group as long as it is a compound having a nucleophilic, but particularly preferably an amine compound.

[0019] 胺化合物为含有伯胺或仲胺的物质,可列举例如甲胺、乙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺、六亚甲基二胺、苯胺、苯乙胺、金刚胺、哌嗪、含氨基的硅烷偶联剂等低分子量胺。 [0019] amine compound is a substance containing a primary or secondary amine include, for example, methylamine, ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylenehexamine amine, hexamethylenediamine, aniline, phenethylamine, amantadine, piperazine, amino group-containing silane coupling agent, low molecular weight amines. 本发明中所述的低分子量胺的含义例如为DETA(二亚乙基三胺)、TETA(三亚乙基四胺)、PEHA (五亚乙基硫胺)等亚乙基二胺衍生物,其分子量在例如50-400的范围内是合适的。 Meaning low molecular weight amines in the present invention, for example of DETA (diethylene triamine), of TETA (triethylenetetramine), PEHA (pentaethylene thiamine) like ethylene diamine derivative, having a molecular weight in the range of 50-400, for example, is appropriate. 此外,作为胺化合物,也可使用具有重复的氨基结构的聚胺。 Further, as the amine compound, may also be used a polyamine having a repeating structure of the amino group. 通过结合使用低分子量胺和聚胺,可容易地调整树脂组合物的固化性。 By using low molecular weight amines and polyamines in combination, can be easily adjusted curable resin composition. 此外,如果结合使用低分子量胺与聚胺,则在树脂组合物处于一次固化的状态时,更难产生胶粘性。 Further, if combined with a low molecular weight amines and polyamines, the resin composition in a cured state, more difficult to produce tackiness. 聚胺的分子量在例如1万-20万的范围内是合适的。 The molecular weight of the polyamine is in the range of 10,000 to 200,000, for example, it is suitable.

[0020] 胺化合物的用量取决于所用的胺化合物的胺价态,相对于100重量份的具有两个以上丙烯酰基的多官能可聚合化合物,优选在〇. 1-50重量份的范围内,更优选在0. 5-30重量份的范围内,特别优选在5-25重量份的范围内。 [0020] The amount of amine compound depends on the valence of the amine compound used is an amine, the polyfunctional acryloyl groups having two or more parts by weight of the polymerizable compound 100, preferably in the square. 1-50 parts by weight, more preferably in the range of 0. 5 to 30 parts by weight, particularly preferably in the range of 5 to 25 parts by weight. 在树脂组合物的一次固化不充分的情况下,可通过增加胺化合物的配入量,或者提高聚胺在胺化合物中所占的比例,可改善固化性能。 In a case where the curable resin composition is insufficient, with the curable performance by increasing the amount of the amine compound, a polyamine or increase the proportion occupied in the amine compound, can be improved. 另一方面,在树脂组合物的贮存期(pot life)短的情况下,可通过减少胺化合物的配入量,或者降低聚胺在胺化合物中所占的比例,从而延长贮存期。 On the other hand, the pot life of the resin composition (pot life) is short, the by reducing the amount of the amine with the compound, or a decrease in the proportion occupied polyamine amine compound, thereby extending the shelf life. 此外,化合物的胺价态越高,胺化合物的反应性越高,可减少胺化合物的添加量而表面物理性质仍良好,因此是优选的。 Further, the higher the valence of the amine compound, the higher the reaction of the amine compound, the addition amount of the amine compound can be reduced while the surface is still good physical properties, which is preferable.

[0021] 通过将所述可与丙烯酰基进行加成反应的化合物与感温性催化剂配合,可容易地兼顾到一次固化性和树脂组合物的贮存期。 [0021] The compound may be carried out by the temperature-sensitive catalyst and addition reaction with an acryloyl group, can be readily take into account pot life and a curable resin composition. 即,由于感温性催化剂在常温下没有催化活性(或者催化活性低),因此可延长树脂组合物的贮存期,并且由于在高温可以迅速发挥活性,因此可改善一次固化性。 That is, since the temperature sensitivity of the catalyst at room temperature no catalytic activity (or catalytic activity is low), thereby extending pot life of the resin composition, and exert activity rapidly due to the high temperature, thus improving a curable. 此外,在与感温性催化剂配合时,在树脂组合物处于一次固化的状态时,更难产生胶粘性。 In addition, when used in conjunction with temperature-sensitive catalyst, the resin composition in a cured state, more difficult to produce tackiness.

[0022] 作为感温性催化剂的具体实例,特别优选作为强碱的DBU(1,8_二氮杂双环[5. 4. 0] i^一-7-烯)和DBN(1,5-二氮杂双环[4. 3. 0]壬-5-烯)的盐。 [0022] Specific examples of the catalyst temperature sensitivity, particularly preferred as the strong base DBU (1,8_-diazabicyclo [5. 4. 0] i ^ a 7-ene) and DBN (1,5- diazabicyclo [4. 3.0] non-5-ene) salts. DBU 和DBN 的盐与各种溶剂的互溶性均良好,与使用现有的叔胺或无机类碱性催化剂的情况相比,在更温和的条件下也可提高反应收率。 DBU and DBN salts miscibility with various solvents was good, as compared with the conventional case of using a tertiary amine or an inorganic basic catalyst, under milder conditions may also improve the reaction yield.

[0023] 作为DBU和DBN的盐,可列举例如DBU-苯酚盐、DBU-辛酸盐、DBU-油酸盐、DBU-对甲苯磺酸盐、DBU-甲酸盐、DBN-苯酚盐、DBN-辛酸盐、DBN-油酸盐、DBN-对甲苯磺酸盐、 DBN-甲酸盐甲胺等,此外,还可列举脒碱和胍碱的盐等。 [0023] As DBU salts and DBN, DBU-phenol salts include, for example, DBU-octylate salt, DBU-oleate, DBU-p-toluenesulfonate, DBU-formate salt, DBN-phenol salt, DBN - caprylate, DBN-oleate, DBN-toluenesulfonate, formate DBN-methylamine, in addition, may include guanidine salts and amidine bases like alkali. 此外,只要是可溶于有机溶剂而进行脱质子作用的强碱盐也可以使用。 Further, as long as it is soluble in an organic solvent for removal of alkali salts of proton effect it may also be used. 所述这些感温性催化剂可单独使用也可两种以上混合使用。 The temperature sensitivity of these catalysts may be used singly or two or more may be mixed. 进一步,只要是可促进与丙烯酰基进行加成反应的催化剂,则不限于上述感温性催化齐U,可与发挥催化剂活性的方法一起使用。 Further, as long as a catalyst for promoting an addition reaction with an acryloyl group is not limited to the temperature sensing homogeneous catalytic U, may be used with the method of the catalyst activity is exhibited.

[0024] 感温性催化剂的配入量相对于100重量份的具有两个以上丙烯酰基的多官能可聚合化合物,优选在5-20重量份的范围内。 [0024] with the amount of the temperature sensitivity of the multifunctional catalyst having two or more acryloyl group 100 parts by weight of the polymerizable compound, preferably in the range of 5 to 20 parts by weight. 通过在此范围内,树脂组合物在一次固化的状态时更难产生胶粘性。 By Within this range, the resin composition is more difficult to produce tackiness at a cured state.

[0025] 通过照射紫外线或电子射线等活性能量射线对本发明的树脂组合物进行二次固化。 [0025] The secondary curing of the resin composition of the present invention by irradiation with ultraviolet rays or electron rays, active energy rays. 在进行紫外线固化的情况下,可使用超高压水银灯、高压水银灯、低压水银灯、碳弧灯、 金属卤化物灯等,在100_400nm、优选200-400nm的波长范围内,照射具有50-300mJ/cm 2的能量的紫外线。 When performing an ultraviolet curable, ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, a carbon arc lamp, a metal halide lamp, etc., in the wavelength range of preferably 200-400nm 100_400nm, irradiation with 50-300mJ / cm 2 UV energy. 为了防止固化障碍,也可以用氮气等惰性气体进行照射。 In order to prevent curing inhibition, can be irradiated with an inert gas such as nitrogen.

[0026] 在通过紫外线进行固化的情况下,优选添加相对于100重量份的具有两个以上丙烯酰基的多官能可聚合化合物为3-10重量份的紫外线固化型引发剂。 [0026] In the case of curing by ultraviolet rays, preferably added with respect to 100 parts by weight of the polyfunctional acryloyl groups having two or more polymerizable compounds is 3-10 parts by weight of an ultraviolet-curable initiators. 通过使添加量在3 重量份以上,可使热固化后不易残留胶粘性,通过使添加量在10重量份以下,可抑制过度的固化反应,从而确保成型性。 By adding an amount of 3 parts by weight or more, can easily residual tackiness after thermal curing, by adding in an amount of 10 parts by weight or less, an excessive curing reaction can be suppressed, thereby ensuring moldability.

[0027] 作为紫外线固化型引发剂,可列举例如1-羟基环己基苯基甲酮、2,2_二甲氧基-2-苯基苯乙酮、咕吨酮、芴酮、苯甲醛、芴、蒽醌、三苯胺、咔唑、3-甲基苯乙酮、4-氯二苯甲酮、4,4' -二甲氧基二苯甲酮、4,4' -二氨基二苯甲酮、米希勒酮(Michler' s ketone)、苯偶姻丙醚、苯偶姻乙醚、苯偶酰二甲基缩酮(benzyl dimethyl ketal)、l_(4_异丙基苯基)-2-羟基-2-甲基丙-1-酮、l-[4-(2-羟基乙氧基)-苯基]-2-羟基-2-甲基-1-丙-1-酮、2-羟基-1- [4- [4- (2-羟基-2-甲基-丙酰基)-苯甲基]-苯基]-2-甲基-丙-1-酮、2-羟基-2-甲基-1-苯基丙-1-酮、噻吨酮、二乙基噻吨酮、2-异丙基噻吨酮、2-氯噻吨酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉基-丙-1-酮、2,4,6_三甲基苯甲酰基二苯基氧化膦、二-(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基戊基氧化膦等,作为市售商品可列举Irgacurel27、184、369、651、500、819、907 [0027] as an ultraviolet curing initiator include, for example, 1-hydroxy cyclohexyl phenyl ketone, 2,2_-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chloro benzophenone, 4,4 '- dimethoxy benzophenone, 4,4' - diaminodiphenyl methanone, Michler's ketone (Michler 's ketone), benzoin propyl ether, benzoin ethyl ether, benzil dimethyl ketal (benzyl dimethyl ketal), l_ (4_ isopropylphenyl) - hydroxy-2-methylpropan-1-one, l- [4- (2- hydroxyethoxy) - phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2 - hydroxy-1- [4- [4- (2-hydroxy-2-methyl - propionyl) - benzyl] - phenyl] -2-methyl - propan-1-one, 2-hydroxy-2 - methyl-1-phenyl-propan-1-one, thioxanthone, diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2-methyl-1- [4 - (methylthio) phenyl] -2-morpholino-yl - propan-1-one, diphenyl phosphine oxide 2,4,6_ trimethyl benzoyl, di - (2,6-dimethoxy yl) -2,4,4-trimethylpentyl phosphine oxide and the like, as commercially available products include Irgacurel27,184,369,651,500,819,907 、2959(以上均为^ 八· '7'\ 八>公司制造,商品名)等。 , 2959 (all of which are ^ August '7' \ eight> Inc., trade name) and so on. 这些紫外线固化型引发剂也可两种以上共同使用。 These ultraviolet-curing initiator or two or more may be used together.

[0028] 此外,在通过电子射线对树脂组合物进行固化的情况下,可使用公知的电子射线照射装置。 [0028] Further, in the case where the resin composition is cured by electron beams, a known electron beam irradiation devices may be used. 电子射线的照射量优选为10_200kGy,更优选30-100kGy。 The electron beam irradiation amount is preferably 10_200kGy, more preferably 30-100kGy. 通过使用10kGy以上的照射量,可确保树脂组合物被固化,通过使用200kGy以下的照射量,可降低电子射线照射装置的负荷,是经济的。 By using more than 10 kGy irradiation amount, to ensure the resin composition is cured by irradiation with an amount of less than 200kGy, can reduce the load on the electron beam irradiation apparatus, it is economical.

[0029] (2)本发明的硬质涂覆剂 [0029] (2) a hard coating agent of the present invention

[0030] 本发明的硬质涂覆剂的特征为含有上述(1)的树脂组合物。 [0030] The hard coat agent of the present invention is the above features (1) comprising a resin composition. 使用本发明的硬质涂覆剂形成的硬质涂层在进行了一次固化后的状态下,不仅具有成型时也不易产生裂缝的柔软性,还不易产生胶粘性。 Hard coat layer using the hard coat agent of the present invention is formed in a state after performing the primary curing not only has flexibility but also less likely to crack during molding, but also easy to produce tackiness. 此外,使用本发明的硬质涂覆剂形成的硬质涂层在进行了二次固化后的状态下,硬度和耐擦伤性均优良。 Further, the hard coat layer using the hard coat agent of the present invention is formed by performing the second state after curing, hardness and excellent in scratch resistance.

[0031] 本发明的硬质涂覆剂可以为上述(1)的树脂组合物本身,也可适当添加其他成分。 [0031] The hard coat agent of the present invention may be (1) a resin composition itself, other components may be appropriately added.

[0032] (3)本发明的薄膜(成型用薄膜) [0032] The film (3) of the present invention (forming a film)

[0033] 本发明的薄膜的特征在于,在薄膜基材上形成有由上述(1)的树脂组合物形成的硬质涂层。 [0033] The film of the invention is characterized in that there is formed is formed from the resin composition of the above (1) in the hard coating film on a substrate.

[0034] 本发明的薄膜可为例如硬质涂层处于进行了一次固化后的状态的形式。 [0034] The film of the invention may be, for example, hard coat is made in the form of a state after the primary curing. 构成本发明的薄膜的硬质涂层具有不易产生裂缝的柔软性。 Constituting the hard coat film of the invention has a flexibility less likely to crack. 因此,本发明的薄膜在硬质涂层上不会产生裂缝,并且可成型为设计性优良的深冲或复杂的构造。 Accordingly, the film of the present invention does not generate cracks in the hard coat layer, and excellent in design can be formed as a deep-drawn or complex configuration.

[0035] 此外,构成本发明的薄膜的硬质涂层即使处于没有进行二次固化的状态也不易产生胶粘性,因此可防止薄膜之间的粘结和成型时薄膜与铸模之间的粘结。 [0035] Further, the present invention constituting the film is not even in the hard coat layer cured state secondary tackiness hardly occurs, so the adhesion between the adhesive film and the mold and the molding is prevented between the film knot. 进一步,二次固化后的硬质涂层的硬度和耐擦伤性均优良。 Further, hardness and abrasion resistance of the hard coat layer excellent in the secondary curing.

[0036] 本发明的薄膜优选在硬质涂层上方的层中具有保护层。 Film invention preferably [0036] This layer has a protective layer over the hard coating. 即使处于进行了一次固化后的状态的硬质涂层不具有足够的硬度,通过具备保护层,在例如薄膜成型时也不易在硬质涂层上产生伤痕。 It carried out even in a state where the cured hard coat layer does not have sufficient hardness, by providing the protective layer is less likely scratched on the hard coat layer, for example, when the film formation. 保护层可通过例如将溶解或分散在溶剂中的树脂涂布在硬质涂层上之后使所述溶剂挥发掉而形成。 The protective layer may be applied by, for example, a resin dissolved or dispersed in a solvent causes the solvent to evaporate after the hard coat layer is formed. 由此,不用担心会如使用由施用了粘合剂的薄膜等形成的保护层的情况那样,粘合剂残留在硬质涂层的表面,从而产生外观问题。 Thus, do not worry about the use of such protective layer is applied by a film forming binder such as adhesive remaining on the surface of the hard coat layer, resulting in appearance defects.

[0037] 用于形成保护层的树脂优选这样的树脂,即所述树脂具有尽可能保护一次固化状态的硬质涂层的硬度,与硬质涂层的密合性良好,并且在从硬质涂层上剥离时不在表面残留。 [0037] The protective layer is preferably a resin for forming such a resin, i.e. the resin has a protective hard coat is cured state as hardness, good adhesion to the hard coat layer, and the hard peeling remaining on the surface is not coated. 作为这样的树脂,可列举例如聚乙烯醇(PVA)、聚环氧乙烷(ΡΕ0)、聚乙烯醇改性的聚乙烯缩醛树脂、聚丙烯酸钠等,作为分散在溶剂中的树脂,可列举乙酸乙烯酯乳液、乙烯-乙酸乙烯酯(EVA)乳液、丙烯酸乳液、丙烯酸苯乙烯乳液、1,1_二氯乙烯乳液、氨基甲酸酯乳液、分散型氟树脂等。 Examples of such resins include such as polyvinyl alcohol (PVA), polyethylene oxide (ΡΕ0), polyvinyl acetal resin modified polyvinyl alcohol, sodium polyacrylate, as the resin is dispersed in a solvent, can be include vinyl acetate emulsion, ethylene - vinyl acetate (EVA) emulsion, acrylic emulsion, acrylic styrene emulsion, 1,1_ chloride emulsion, urethane emulsion, dispersion-type fluororesin. 其中优选聚乙烯醇。 Wherein preferably polyvinyl alcohol.

[0038] 此外,形成保护层的树脂中也可添加染料、颜料、消光剂、防静电剂、消泡剂、流平齐U、增粘剂、PH调节剂、耐水合剂、交联剂等。 [0038] Further, the resin forming the protective layer may be added dyes, pigments, matting agents, antistatic agents, antifoaming agents, flow flush U, tackifiers, PH adjusting agents, water resistance agents, crosslinking agents. 在硬质涂层上形成的保护层可在二次固化前适宜地除去。 A protective layer formed on the hard coat layer can be suitably removed prior to secondary curing.

[0039] 对于本发明的薄膜而言,例如,对薄膜基材进行助脱模处理(離型処理),其可成为能够转印硬质涂层的转印薄膜。 [0039] For the film according to the present invention, for example, the film base material co-mold releasing treatment (release treatment), it may be possible to transfer the transfer film hard coat layer. 在这种情况下,可在其他部件(也可为其他薄膜)的表面转印硬质涂层。 In this case, the other components (which may be other thin film) of the hard coat layer surface of the transfer. 作为助脱模处理,可列举例如硅氧烷处理等。 As a co-releasing treatment include a treatment such as silicone.

[0040] 本发明的薄膜也可以是例如在型材中压制成型的薄膜。 [0040] The film of the invention may be formed, for example, a film press in the profile. 构成本发明的薄膜的硬质涂层即使在成型时也不易产生裂缝。 Constituting the hard coat film according to the present invention, even when the molding is less likely to crack.

[0041] 本发明的薄膜也可以为硬质涂层处于通过活性能量射线进行了二次固化的状态。 [0041] The film of the invention may also be in a secondary ray by an active energy-cured state hard coat layer. 在此状态下时,硬质涂层的硬度和耐擦伤性均优良。 In this state, hardness and abrasion resistance of the hard coat layer excellent in both.

[0042] 作为本发明的薄膜中的薄膜基材,可列举例如聚对苯二甲酸乙二酯薄膜、聚对苯二甲酸丁二酯薄膜、聚萘二甲酸乙二酯薄膜、聚乙烯薄膜、聚丙烯薄膜、玻璃纸、二乙酰基纤维素薄膜、三乙酰基纤维素薄膜、乙酰基纤维素丁酸酯薄膜、聚氯乙烯薄膜、聚偏1,1-二氯乙烯薄膜、聚乙烯醇薄膜、乙烯-乙酸乙烯酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚甲基戊烯薄膜、聚砜薄膜、聚醚醚酮薄膜、聚醚砜薄膜、聚醚酰亚胺薄膜、聚酰亚胺薄膜、氟树脂薄膜、尼龙薄膜、丙烯酸树脂薄膜等。 [0042] The base film as a film of the present invention include, for example, polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate, polyethylene terephthalate film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene - vinyl acetate copolymer film, a polystyrene film, a polycarbonate film, a polymethylpentene film, a polysulfone film, a polyether ether ketone film, polyether sulfone film, polyether imide film, polyimide imide film, fluororesin film, nylon film, an acrylic resin film or the like.

[0043] 此外,为了改善薄膜基材与树脂组合物的密合性,也可对薄膜基材通过喷砂法或溶剂处理法等进行表面凹凸化处理,或进行电晕放电处理、铬酸处理、火焰处理、热风处理、 臭氧·紫外线照射处理等表面氧化处理等的表面处理。 [0043] Further, in order to improve the adhesion of the film substrate with the resin composition, but also on the film substrate by a sand blast method or a solvent treatment method, the surface roughening treatment, or corona discharge treatment, chromic acid treatment , a flame surface treatment surface oxidation treatment, hot air treatment, ozone-ultraviolet irradiation treatment and the like.

[0044] 对于向薄膜基材上涂布树脂组合物的方法没有特别限制,可使用公知的方法,例如照相凹版涂覆法、棒涂法、刮刀涂覆法、辊涂法、刮板涂覆法、捋涂法等。 [0044] For no particular limitation to the method of the film substrate coated with a resin composition, a known method may be used, for example, a gravure coating method, bar coating method, a blade coating method, a roll coating method, blade coating method, a coating method stroke. 例如以干燥•固化处理后的膜厚为1-200 μ m的方式进行涂布、干燥•固化处理。 For example, the film thickness after drying • curing treatment is 1-200 μ m coating manner, • curing drying process.

[0045] (4)本发明的成型体的制造方法 [0045] The method of manufacturing a molded body (4) of the present invention

[0046] 本发明的成型体的制造方法的特征在于,将所述(3)的薄膜在型材上进行压制, 并在脱模后用活性能量射线使所述硬质涂层进行二次固化。 A method for producing a molded article wherein [0046] the present invention, the (3) a film is pressed on the profile, and the active energy ray hard coat secondary cured after demolding.

[0047] 根据本发明,在成型时硬质涂层不易产生裂缝。 [0047] According to the present invention, when forming a hard coat hard to crack. 此外,硬质涂层即使处于没有进行二次固化的状态下也不易产生胶粘性,因此可防止薄膜之间的粘结和成型时薄膜与铸模之间的粘结。 Further, even if the hard coating is in a state not subjected to secondary curing adhesive is less likely to occur, thereby preventing adhesion between the film and the adhesion between the film and the mold during molding. 进一步,二次固化后的硬质涂层的硬度和耐擦伤性均优良。 Further, hardness and abrasion resistance of the hard coat layer excellent in the secondary curing.

[0048] 基于图1 (a)-(d),对本发明涉及的薄膜成型体(成型体)6的制造方法的具体实例进行说明。 [0048] (a) to FIG. 1 - (d), specific examples of the manufacturing method of the present invention relates to 6 film molded (molded body) will be described. 首先,在薄膜基材9上涂布树脂组合物1(图1(a))。 First, a substrate film 9 on the coating resin composition 1 (FIG. 1 (a)). 此时,树脂组合物1为液态。 In this case, the resin composition is a liquid. 然后,通过加热•干燥树脂组合物1使其热固化,形成硬质涂层2,从而获得成型用薄膜5(图1(b))。 Then, by heating the resin composition was dried • thermally cured to form a hard coating layer 2, thereby obtaining the molded film 5 (FIG. 1 (b)). 此时,硬质涂层2为固体,处于一次固化的状态。 At this time, the hard coat layer 2 is a solid, in a cured state. 接着,在型材上(图中未示出)挤压成型用薄膜5,并在脱模后(图1(c))对其照射紫外线,从而使硬质涂层2进行二次固化,获得薄膜成型体6 (图1 (d))。 Next, on the profile (not shown) extruded film 5, and exposed to ultraviolet rays, so that the hard coat layer after demolding (FIG. 1 (c)) 2 for secondary curing to obtain a film body 6 (FIG. 1 (d)).

附图说明 BRIEF DESCRIPTION

[0049] 图l(a)_(d)为显示薄膜成型体的制造方法的说明图。 [0049] FIG. L (a) _ (d) is an explanatory view showing a manufacturing method of a thin film formed body.

[0050] 符号说明 [0050] Description of Symbols

[0051] 1...树脂组合物;2...硬质涂层;5...成型用薄膜;6...薄膜成型体;9...薄膜基材 [0051] The resin composition 1 ...; ... hard coat layer 2; ... 5 formed film; molded film 6 ...; ... the film substrate 9

具体实施方式 Detailed ways

[0052] 说明本发明的实施方式。 [0052] The embodiments of the present invention.

[0053] 实施例1 [0053] Example 1

[0054] (a)树脂组合物(硬质涂覆剂)的制造 [0054] (a) producing a resin composition (hard coat agent)

[0055] 配入表1至表3所示的各成分,制造实施例1-1至1-18以及比较例1至2的树脂组合物。 [0055] Table 1 with the ingredients shown in Table 3, Examples 1-1 to 1-18 and manufacturing the resin composition of Comparative Example 1-2 embodiment. 此外,表1至表3显示了以固体成分换算的配入量。 In addition, Table 1 to Table 3 show the amount of ligand in solid content equivalent. 树脂组合物为A剂、B剂的二剂形式,分别制造A剂、B剂。 A resin composition agent, two agents of Form B, respectively, for producing the A agent, B agent. A剂含有表1至表3中A剂一栏所记载的成分,是以MEK(甲乙酮)为溶剂的固体成分为40重量%的溶液。 A agent containing 3 ingredients A described in Table 1 to a table column, is MEK (methyl ethyl ketone) as solvent a solid content of 40% by weight of the solution. B剂含有表1至表3中B剂一栏所记载的成分,是以甲苯为溶剂的溶液。 B B agent containing 3 ingredients described in Table 1 to a table column, solvent solution is toluene.

[0056] 使用树脂组合物时,将A剂与B剂以重量比1 : 1混合。 [0056] When using the resin composition, the A agent and the B agent is in a weight ratio of 1: 1. 此外,B剂的固体成分比例设定为:将A剂与B剂以重量比1 : 1混合时,按固体成分换算,树脂组合物的配入比例为表1至表3所示的配入比例。 In addition, the solid content ratio of B agent is set as follows: the A agent and the B agent is in a weight ratio of 1: 1 mixture, in terms of solid content, with the proportion of the resin composition is shown in Table 1 to Table 3 was formulated into proportion.

[0057] 表1 [0057] TABLE 1

[0058] [0058]

Figure CN101981068BD00081

[0059] 表2 [0059] TABLE 2

[0060] [0060]

Figure CN101981068BD00091

[0061] 表3 [0061] TABLE 3

[0062] [0062]

Figure CN101981068BD00101

[0063] 一次二次 [0063] a secondary

[0064] 固化固化 [0064] The curing of the curable

[0065] 后后 After [0065]

[0066] 此外,在表1至表3中,U-15HA为新中村化学工业(株)社制造的氨基甲酸酯丙烯酸酯的商品名。 [0066] Further, in Table 1 to Table 3, the new U-15HA urethane-Nakamura Chemical Industries (Co., Ltd.) trade name, manufactured by acrylate ester. e - 7卜371为荒川化学工业(株)社制造的丙烯酰基丙烯酸酯的商品名。 e - 7 371 BU to Arakawa Chemical Industries (Co., Ltd.) acryloyl tradename, manufactured by acrylate. 7 口= 7 M7300K为东亚合成(株)社制造的聚酯丙烯酸酯的商品名。 7 = 7 M7300K of Toagosei (Co., Ltd.) trade name of polyester acrylate, manufactured by.

[0067] DPHA(二季戊四醇六丙烯酸酯)、U-15HA、匕一A七V卜371和7 口二V夕义M7300K各自相当于具有两个以上丙烯酰基的多官能可聚合化合物。 [0067] DPHA (dipentaerythritol hexaacrylate), U-15HA, a dagger Bu 371 V A seven and two V 7 corresponding to the respective Xi Yi M7300K polyfunctional acryloyl groups having two or more polymerizable compounds.

[0068] 此外,irg2959为^八· '7' \>制造的UV引发剂的商品名。 [0068] In addition, irg2959 as ^ eight · '7' \> UV initiator manufactured under the trade name agent. BYK310为匕' V夕夂S - · \パ>公司制造的流平剂的商品名。 BYK310 is a dagger 'V Xi Fan S - · \ SUPER> tradename leveling agent manufactured.

[0069] 此外,DETA(二亚甲基三胺)、TETA(三亚甲基四胺)以及PETA(五亚甲基六胺) 各自相当于低分子量胺。 [0069] Further, DETA (dimethylene triamine), TETA (trimethylene tetramine) and of PETA (pentamethylene hexamine) each corresponding to a low molecular weight amine.

[0070] 此夕卜,*。 [0070] BU this evening, *. UJ >卜NK-350以及*。 UJ> NK-350 and Pu *. UJ >卜NK-380各自为(株)日本触媒社制造的聚胺的商品名。 UJ> Bu NK-380 are each (strain) manufactured by Nippon Shokubai Co., trade name polyamine.

[0071] 此外,U-CAT SA 1为寸> 7 7''口(株)社制造的DBU-苯酚盐的商品名。 [0071] In addition, U-CAT SA 1 inch of> 77 trade name 'opening (strain) phenol, manufactured by DBU- salt. U-CAT SA 102为寸> 7 7''口(株)社制造的CBU-辛酸盐的商品名。 U-CAT SA 102 to inch> trade name 77 '' opening (strain), manufactured by CBU- octanoate. U-CAT 1102为寸> 7 7''口(株) 社制造的DBN-辛酸盐的商品名。 As U-CAT 1102 inches> 77 '' opening (Co., Ltd.) trade name, manufactured by DBN- octanoate.

[0072] U-CAT SA 1、U-CAT SA 102和U-CAT 1102各自相当于感温性催化剂。 [0072] U-CAT SA 1, U-CAT SA 102 and U-CAT 1102 corresponding to the respective temperature-sensitive catalyst.

[0073] (b)薄膜及成型体的制造 [0073] Production of (b) and a film molded article

[0074] 将上述(a)中制造的树脂组合物在厚100 μ m的PET薄膜(东洋纺绩(株)社制造,商品名:^ 7 \ ^ > A4300-188)上以固化后膜厚度为5μπι的方式进行涂布。 [0074] In the above (a) producing a resin composition in a 100 μ m thick PET film (manufactured by Toyobo (strain) Co., Ltd., trade name: ^ 7 \ ^> A4300-188) to the film thickness after curing coating is 5μπι way.

[0075] 然后,将涂布后的树脂组合物在110°C干燥3分钟(一次固化),形成固体的硬质涂层,从而得到成型用薄膜。 [0075] Then, after coating the resin composition was dried at 110 ° C 3 minutes (curing time), the hard coat layer to form a solid, thereby obtaining a film molding. 然后,将该成型用薄膜在型材上进行压制脱模。 Then, this molded film is pressed on the release profile. 然后使用紫外线照射机,照射强度为200mJ/cm 2的紫外线,进行硬质涂层的紫外线固化(二次固化),从而制成薄膜成型体。 Then using an ultraviolet irradiation apparatus, the irradiation intensity of ultraviolet 200mJ / cm 2, the ultraviolet curing hard coat layer (secondary hardening), thereby producing a film forming material.

[0076] (c)对树脂组合物以及成型用薄膜的评价 [0076] (c) Evaluation of resin composition and molding the film

[0077] 对于所述(a)至(b)中制造的树脂组合物以及成型用薄膜,检验其外观、贮存期、 胶粘性、成型性以及铅笔硬度。 [0077] For the (a) to (b) of producing a resin composition and a molded film, the appearance inspection, storage period, adhesiveness, pencil hardness and moldability. 检验方法以及评价标准如下所示。 Test method and evaluation criteria are shown below.

[0078] (外观)以目视观察涂膜外观。 [0078] (appearance) was visually observed appearance of the coating. 涂膜澄清则评价为〇,白化则评价为X。 Clarification film was rated as square, albino evaluated as X.

[0079] (贮存期)测定树脂组合物在常温下直到凝胶化所用的时间。 [0079] (pot life) determination of the resin composition at room temperature until gelation time used.

[0080] (胶粘性)在PET薄膜上涂布树脂组合物,在110°C干燥3分钟后,以食指触碰树脂组合物进行判断。 [0080] (adhesive) resin composition was applied on the PET film, was dried at 110 ° C after three minutes, the index finger touching the resin composition is determined. 判断标准如下所示。 Criterion shown below. 此外,仅对于比较例2,在树脂组合物二次固化后也进行同样的检验。 Moreover, only Example 2 for comparison, the secondary curing resin composition subjected to the same test.

[0081] 5:完全不胶粘 [0081] 5: completely non-stick

[0082] 4 :几乎不胶粘 [0082] 4: almost no tackiness

[0083] 3 :大致不胶粘 [0083] 3: a substantially non-stick

[0084] 2 :略微胶粘 [0084] 2: slightly tacky

[0085] 1 :残留胶粘 [0085] 1: Adhesive residue

[0086] (成型性)将成型用薄膜(硬质涂层处于一次固化的状态)在成型用铸模上压制, 不产生裂纹则评价为〇,产生裂纹则评价为X。 [0086] (moldability) for molding the film (hard coat layer is in a cured state) in a casting mold press, no cracks was rated as square, cracks was evaluated as X. 此外,仅对于比较例2,对二次固化后的成型用薄膜也进行同样的检验。 Further, only for Comparative Example 2, the molded film after secondary cure subjected to the same test.

[0087](铅笔硬度)对于成型用薄膜(硬质涂层处于二次固化的状态),根据JIS K5400 进行铅笔硬度试验。 [0087] (Pencil hardness) for forming a thin film (hard coat layer is post-cured state), a pencil hardness test according to JIS K5400. 试验在铅笔硬度为2H和Η的情况下进行。 Test was carried out in a case where the pencil hardness of 2H and Η. 此外,在各个铅笔硬度中进行5次试验。 Further, in each of five tests in pencil hardness. 将在5次中硬质涂层上没有产生伤痕的次数记载在上述表1至表3中。 The number of scratches is not generated in the hard coat layer 5 in the above described Table 1 to Table 3.

[0088] 评价结果显示在上述表1至表3中。 [0088] The evaluation results are shown in Table 1 to Table 3. 如表1至表3所示,实施例1-1至1-18的硬质涂层外观良好,树脂组合物的贮存期长,一次固化后的状态下的硬质涂层不产生胶粘性, 成型用薄膜的成型性也良好。 As shown in Table 1 to Table 3, the hard coat Example 1-1 to 1-18 good appearance, long shelf life of the resin composition, a hard coat layer in a state after curing does not produce tackiness , molding the film moldability was also good. 此外,在二次固化后的状态下的硬质涂层的硬度高。 Further, high hardness at a state after secondary curing hard coat layer.

[0089] 特别是,结合使用低分子量胺和聚胺的实施例1-1与仅配入低分子量胺和聚胺之一的实施例1-8至1-9相比,更不易产生胶粘性。 [0089] In particular, embodiments in conjunction with low molecular weight amines and polyamines Example 1-1 with only one of the low molecular weight amines and polyamines 1-8 to 1-9 compared to the more difficult to produce adhesive sex. 此外,配入了感温性催化剂的实施例1-1 与没有配入感温性催化剂的实施例1-10相比,更不易产生胶粘性。 Further, with an embodiment of the temperature sensitivity of the catalyst of example 1-1 not blended with the catalyst temperature sensitivity compared to 1-10, and more difficult to produce tackiness.

[0090] 实施例2 [0090] Example 2

[0091] 基本上与上述实施例1的(a)至(b)同样地制造成型用薄膜。 [0091] substantially the same manner as the above-described film molding of Example 1 (a) to (b). 但本实施例2中, 在形成硬质涂层并在使其进行了一次固化后,在硬质涂层上涂布PVA,形成保护层。 Example 2 In the present embodiment, after forming the hard coat and a curing it, in the PVA coating on the hard coat layer, a protective layer. 然后,与上述实施例1同样地获得薄膜成型体。 Then, the above-described film formation obtained in the same manner in Example 1. 最后,剥离保护层。 Finally, the protective layer is peeled off. 本实施例2中,由于是在硬质涂层上形成了保护层的状态下进行成型,因此不易在硬质涂层上产生伤痕。 Example 2 In the present embodiment, since the formation of a protective layer is molded in a state where the hard coat layer, it is not easy to produce flaw on the hard coat layer. 此外,剥离保护层后,硬质涂层的表面上完全没有残留痕迹。 Further, after peeling the protective layer, there is no residual traces on the surface of the hard coat layer.

[0092] 实施例3 [0092] Example 3

[0093] 基本上与上述实施例1的(a)至(b)同样地制造成型用薄膜。 [0093] substantially the same manner as the above-described film molding of Example 1 (a) to (b). 但本实施例3中, 在形成硬质涂层并在使其进行了一次固化后,在硬质涂层之上粘附施用了粘合剂的薄膜, 形成保护层。 However, in Example 3 embodiment, after forming a hard coat and a curing it, on the hard coat film adhesive of the adhesive applied to form a protective layer. 然后,与上述实施例1同样地获得薄膜成型体。 Then, the above-described film formation obtained in the same manner in Example 1. 最后,剥离保护层。 Finally, the protective layer is peeled off. 本实施例3中,由于是在硬质涂层上形成了保护层的状态下进行成型,因此不易在硬质涂层上产生伤痕。 Example 3 In this embodiment, since the formation of a protective layer is molded in a state where the hard coat layer, it is not easy to produce flaw on the hard coat layer. 但是,剥离保护层后,硬质涂层的表面上略微残留了粘合剂。 However, after peeling the protective layer, adhesive slightly remaining on the surface of the hard coat layer.

[0094] 实施例4 [0094] Example 4

[0095] 基本上与上述实施例1的(a)至(b)同样地制造成型用薄膜。 [0095] substantially the same manner as the above-described film molding of Example 1 (a) to (b). 但本实施例中,作为涂布树脂组合物的薄膜基材,使用助脱模(離型)PET薄膜(东洋纺绩(株)制造,商品名:TN110)。 In the present embodiment, as a thin film substrate is coated with a resin composition, a co-releasing (release) the PET film (Toyobo Co. (Ltd.), trade name: TN110). 已对该助脱模PET薄膜进行了助脱模处理,然后,可使由树脂组合物形成的层(硬质涂层)容易地脱模。 The release PET film has been co-promoter to release treatment, and then, make layer (hard coat layer) is formed of a resin composition easily demolded.

[0096] 本实施例的成型用薄膜可用作转印薄膜。 [0096] Example embodiments of the present film formed may be used as a transfer film. 转印薄膜例如可如下所述进行使用。 The transfer film can be used, for example, as follows. 首先,使成型用薄膜中形成了硬质涂层的一侧与成型材料侧抵接,进行成型。 First, the film for forming the hard coat layer side is formed with side abutting the molding material, molding. 此时,硬质涂层处于一次固化后的状态。 At this time, the hard coat layer is in a state after the primary curing. 然后,取下助脱模PET薄膜。 Then, to help remove the release PET film. 此时,在成型材料的表面粘附着硬质涂层。 At this time, the surface of the molding material of the hard coat layer adhered thereto. 然后照射紫外线,使硬质涂层进行二次固化。 UV irradiation, the hard coat secondary curing. 此外,本实施例的成型用薄膜也可用于模内(in mold)注入成型。 Further, film forming embodiment of the present embodiment may also be used for in-mold (in mold) injection molding.

[0097] 此外,本发明不限于上述实施例,在不偏离本发明的范围内当然可以各种方式实施本发明。 [0097] Further, the present invention is not limited to the above-described embodiments, of course, the present invention may be embodied in various ways within the scope not departing from the present invention.

Claims (9)

1. 成型体的制造方法,具有以下步骤: (i) 将包含具有两个以上丙烯酰基的多官能可聚合化合物以及可与丙烯酰基进行加成反应的化合物的树脂组合物涂布在薄膜基材上的步骤; (ii) 将经涂布薄膜加热从而进行一次固化的步骤; (iii) 通过将经过一次固化的所述薄膜在型材上压制,并将该型材脱模从而对所述薄膜进行成型加工的步骤; (iv) 对经过成型加工的所述薄膜照射紫外线,将所述薄膜进行二次固化的步骤。 1. A method for producing a molded article, comprising the following steps: (i) the resin composition containing a polyfunctional compound coating having two or more acryloyl groups and a polymerizable compound addition reaction with acryloyl film substrate the step of; (ii) heating the coated film to perform a step of curing; (iii) by pressing on the profile passing through the primary cured film, and thus the release profile of the thin film forming the step of processing; (iv) the film is irradiated with ultraviolet rays after molding, the film is a secondary curing step.
2. 权利要求1的成型体的制造方法,其特征在于在硬质涂层上方的层中具有保护层。 The method of producing a molded article according to claim 1, characterized in that the layer has a protective layer over the hard coating.
3. 权利要求1中的成型体的制造方法中使用的薄膜。 A method for producing a thin film in the molded body used in the claim.
4. 权利要求3所述的薄膜,其特征在于,在所述硬质涂层上方的层中具有保护层。 4. A film according to claim 3, characterized in that the layer has a protective layer over the hard coating.
5. 权利要求4所述的薄膜,其特征在于,所述保护层是通过将溶解或分散在溶剂中的树脂涂布在所述硬质涂层上之后使所述溶剂挥发掉而形成的。 5. A film according to claim 4, characterized in that the protective layer is formed by dissolving or dispersing a coating resin in a solvent such that the solvent evaporates after formed on the hard coat layer.
6. 权利要求5所述的薄膜,其特征在于,形成所述保护层的树脂选自聚乙烯醇、聚环氧乙烷、聚乙烯醇改性的聚乙烯缩醛树脂、聚丙烯酸钠、乙酸乙烯酯乳液、乙烯-乙酸乙烯酯乳液、丙烯酸乳液、丙烯酸苯乙烯乳液、1,1-二氯乙烯乳液、氨基甲酸酯乳液、分散型氟树脂。 6. A film according to claim 5, characterized in that the resin forming said protective layer is selected from polyvinyl alcohol, polyethylene oxide, polyvinyl alcohol-modified polyvinyl acetal resin, sodium polyacrylate, acetate vinyl acetate emulsion, ethylene - vinyl acetate emulsion, acrylic emulsion, styrene acrylic emulsion, vinylidene chloride emulsion, urethane emulsion, dispersion-type fluororesin.
7. 权利要求3所述的薄膜,其特征在于,对所述薄膜基材进行助脱模处理,可转印所述硬质涂层。 7. The film according to claim 3, wherein said film substrate for a release processing aid, may be transferred to the hard coat.
8. 权利要求4所述的薄膜,其特征在于,对所述薄膜基材进行助脱模处理,可转印所述硬质涂层。 The film of claim 4, wherein said film substrate for a release process aid, may be transferred to the hard coat.
9. 权利要求5或6所述的薄膜,其特征在于,对所述薄膜基材进行助脱模处理,可转印所述硬质涂层。 9. The film of claim 5 or claim 6, wherein said film substrate for a release process aid, may be transferred to the hard coat.
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