TW201902870A - Ultraviolet absorber and plastic article having the ultraviolet absorber - Google Patents
Ultraviolet absorber and plastic article having the ultraviolet absorber Download PDFInfo
- Publication number
- TW201902870A TW201902870A TW106119443A TW106119443A TW201902870A TW 201902870 A TW201902870 A TW 201902870A TW 106119443 A TW106119443 A TW 106119443A TW 106119443 A TW106119443 A TW 106119443A TW 201902870 A TW201902870 A TW 201902870A
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- compound
- atom
- hydrogen atom
- formula
- Prior art date
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本發明係關於一種紫外線吸收劑,尤係關於一種用於塑膠製品的紫外線吸收劑。 The present invention relates to an ultraviolet absorber, and more particularly to an ultraviolet absorber for a plastic article.
光降解現象常發生於暴露光照下的有機合成樹脂產品、天然樹脂產品和可聚合的有機高分子產品(下文統稱為〝塑膠製品〞),特別是紫外線照射,容易造成該塑膠製品黃變及物理性能劣化的現象,影響該塑膠製品的耐用性,其中,尤以一些光敏感性有機材料之塑膠製品,如聚氨酯、聚苯乙烯等,所述的光降解作用導致產品變色和/或脫色並且使得產品物性下降。為了解決上述問題,在多種塑膠製品的製造過程或加工過程中加入紫外線吸收劑以達到抑制光降解作用及減緩塑膠製品的劣質化的效果。 Photodegradation often occurs in organic synthetic resin products, natural resin products and polymerizable organic polymer products (hereinafter collectively referred to as "plastic products") exposed to light, especially ultraviolet radiation, which easily causes yellowing and physicality of the plastic products. The phenomenon of deterioration of performance affects the durability of the plastic product, among which, in particular, some plastic products of light-sensitive organic materials, such as polyurethane, polystyrene, etc., the photodegradation causes discoloration and/or discoloration of the product and makes Product properties are declining. In order to solve the above problems, a UV absorber is added during the manufacturing process or processing of various plastic products to achieve the effect of inhibiting photodegradation and slowing down the deterioration of plastic products.
如今已知有多種甲脒類紫外線吸收劑相關的化合物。如US4021471美國專利公開了一種甲脒類(formamidine)化合物作為紫外線吸收劑,最為業界熟知的就是Givsorb UV-1[N-(Ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine ;N-(乙氧基羰基苯基)-N'-甲基-N'-苯基甲脒;CAS No.:57834-33-0],由於UV-1在常溫下為黏稠狀液體,操作使用與計量上很方便,因此常用於聚氨酯產業,不過UV-1有以下一些缺點,首先由於高純度的UV-1熔點約28~30℃,因此長時間保存容易造成結晶凝固,因此使用前還必須先預熱成液體後才能方便使用,其次,由於合成UV-1的原料之一為N-甲基苯胺,除了合成出的UV-1中會有微量N-甲基苯胺殘留外,將UV-1添加到塑膠製品中,不論在合成反應階段或塑膠製品的後段加工階段,都會有微量的N-甲基苯胺釋放出來,造成最終成形之塑膠製品中的N-甲基苯胺超標,對於一些對N-甲基苯胺有限制的應用,就不能使用UV-1當紫外線吸收劑,特別是歐盟頒布的玩具指令(2009/EC/48)已明文限制N-甲基苯胺與N-乙基苯胺用於兒童玩具中。針對以上UV-1會殘留N-甲基苯胺的缺陷,本發明揭露一種完全不含N-甲基苯胺的紫外線吸收劑,而且用於塑膠製品也不會產生N-甲基苯胺的甲脒類紫外線吸收劑。 A variety of compounds related to the formamidine ultraviolet absorber are known today. For example, U.S. Patent 4,012,471 discloses a formamidine compound as a UV absorber, the most well known in the art is Givsorb UV-1 [N-(Ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine; N-(ethoxy Carboxyl phenyl)-N'-methyl-N'-phenylformamidine; CAS No.: 57834-33-0], because UV-1 is a viscous liquid at normal temperature, it is convenient to use and measure. Therefore, it is often used in the polyurethane industry. However, UV-1 has the following disadvantages. Firstly, since the high-purity UV-1 melting point is about 28 to 30 ° C, it is easy to cause crystallization solidification after long-term storage, so it must be preheated into liquid before use. After that, it can be conveniently used. Secondly, since one of the raw materials for synthesizing UV-1 is N-methylaniline, in addition to the trace amount of N-methylaniline remaining in the synthesized UV-1, UV-1 is added to the plastic product. In the synthesis reaction stage or the processing stage of the plastic product, a small amount of N-methylaniline is released, resulting in excessive N-methylaniline in the final formed plastic product, for some pairs of N-methylaniline With limited application, you can't use UV-1 when UV absorption Agents, especially the EU directive issued Toys (2009 / EC / 48) has been expressly limit N- methylaniline and N- ethylaniline for children's toys. In view of the above defects of UV-1 remaining N-methylaniline, the present invention discloses an ultraviolet absorber completely free of N-methylaniline, and also does not produce N-methylaniline for the plastic article. UV absorber.
本發明提供一種式(1)所示化合物,
該式(1)所示化合物可以在材料合成時添加,或在後段產品加工時添加,在塑膠製品中作為紫外線吸收劑用。 The compound represented by the formula (1) can be added during the synthesis of the material, or added during the processing of the latter product, and used as a UV absorber in a plastic product.
本發明另提供一種塑膠製品,係包含該式(1)所示化合物作為紫外線吸收劑。本發明之塑膠製品因包含該式(1)所示化合物,使得該塑膠製品具有高抗紫外線性能而增加其在需要曝曬在紫外線環境下的耐用性,且不會釋出有毒的N-甲基苯胺,因此能擴展該紫外線吸收劑及含有該紫外線吸收劑的塑膠製品的用途。 The present invention further provides a plastic article comprising the compound represented by the formula (1) as an ultraviolet absorber. The plastic product of the present invention contains the compound represented by the formula (1), so that the plastic article has high ultraviolet resistance and increases its durability in the need of exposure to ultraviolet rays, and does not release toxic N-methyl groups. Aniline can therefore extend the use of the ultraviolet absorber and the plastic article containing the ultraviolet absorber.
以下係藉由特定的具體實施例說明本發明之實施方式,熟習此技藝之人士可由本說明書所揭示之內容輕易地瞭解本發明之優點及功效。本發明亦可藉由其它不同之實施方式加以施行或應用,本說明書中的各項細節亦可基於不同觀點與應用,在不悖離本發明所揭示之精神下賦予不同之修飾與變更。 The embodiments of the present invention are described by way of specific examples, and those skilled in the art can readily understand the advantages and functions of the present invention from the disclosure. The present invention may be embodied or applied by other different embodiments, and the various details of the present invention may be variously modified and changed without departing from the spirit and scope of the invention.
本發明提供一種式(1)所示化合物,
本發明之式(1)所示化合物係透過以下合成路徑合成:
於一具體實施例中,該式(1)所示化合物中,R1為乙氧基羰基,R2、A與B皆為氫原子,X為氧原子,且R3為乙基。 In a specific embodiment, in the compound of the formula (1), R 1 is an ethoxycarbonyl group, R 2 , A and B are each a hydrogen atom, X is an oxygen atom, and R 3 is an ethyl group.
例如,本發明之式(1)所示化合物具有下式(A-1)至(A-5)之結構:
於一具體實施例中,該式(1)所示化合物中,R1為乙氧基羰基,R2、A與B皆為氫原子,X為氮原子,且R3為乙基。例如,本發明之式(1)所示化合物具有下式(B-1)至(B-3)之結構:
於一具體實施例中,該式(1)所示化合物中,R1為乙氧基羰基,R2、A與B皆為氫原子,X為氧原子,且R3為異丙基。例如,本發明之式(1)所示化合物具有下式(C-1)至(C-5)之結構:
於一具體實施例中,該式(1)所示化合物中,R1為乙氧基羰基,R2、A與B皆為氫原子,X為氧原子,且R3為正丙基。例如,本發明之式(1)所示化合物具有下式(D-1)至(D-4)之結構:
於一具體實施例中,該式(1)所示化合物中,R1表示甲氧基羰基,R2、A與B為氫原子,X為氧原子,且R3為乙基。例如,本發明之式(1)所示化合物具有下式(E-1)至(E-5) 之結構:
於一具體實施例中,該式(1)所示化合物中,R1表示甲氧基羰基,R2、A與B為氫原子,X為氧原子,且R3為異丙基。例如,本發明之式(1)所示化合物具有下式(F-1)至(F-5)之結構:
於一具體實施例中,該式(1)所示化合物中,R1表示甲氧基羰基,R2、A與B為氫原子,X為氧原子,且R3為正丙基。例如,本發明之式(1)所示化合物具有下式(G-1)至(G-4)之結構:
於一具體實施例中,該式(1)所示化合物中,R1表示甲氧基羰基,R2、A與B為氫原子,X為氧原子,且R3為乙基。例如,本發明之式(1)所示化合物具有下式(H-1)至(H-9)之結構:
於一具體實施例中,該式(1)所示化合物中,R1表示甲氧基羰基,R4、A與B為氫原子,X為氧原子,且R3為乙基。例如,本發明之式(1)所示化合物具有下式(I-1)至(I-5)之結構:
於一具體實施例中,該式(1)所示化合物中,R1表示甲 氧基羰基,R4、R2為氫原子,A、B為氯原子,X為氧原子,且R3為乙基。例如,本發明之式(1)所示化合物具有下式(J-1)至(J-4)之結構i
於一具體實施例中,該式(1)所示化合物中,R1表示甲氧基羰基,R4、R2為氫原子,A為甲氧基、B為氯原子,X為氧原子,且R3為乙基。例如,本發明之式(1)所示化合物具有下式(K-1)至(K-4)之結構:
於一具體實施例中,該式(1)所示化合物中,R1、R2為乙氧基羰基,A與B皆為氫原子,X為氧原子,且R3為乙基。例如,本發明之式(1)所示化合物具有下式(L-1)至(L-5)之結構:
本發明另提供一種塑膠製品,係包含該式(1)所示化合物作為紫外線吸收劑。該塑膠製品可為聚氨酯(PU)製得之產品。該紫外線吸收劑的添加方式可在材料合成時添加,或在後段產品加工時添加於塑膠製品。於本發明提供之塑膠製品中,該紫外線吸收劑之添加量占整體塑膠製品為0.1至10.0重量百分比。 The present invention further provides a plastic article comprising the compound represented by the formula (1) as an ultraviolet absorber. The plastic article can be a product made of polyurethane (PU). The method of adding the ultraviolet absorber may be added during material synthesis or added to the plastic product during processing of the latter product. In the plastic product provided by the present invention, the ultraviolet absorber is added in an amount of 0.1 to 10.0% by weight based on the entire plastic product.
本發明之塑膠製品因包含該式(1)所示化合物,使該塑膠製品具有高抗紫外線性能而增加其在需要曝曬在紫外線環境下的耐用性,並且具有該紫外線吸收劑之塑膠製品不會釋放出有毒的N-甲基苯胺,因此能提升該塑膠製品的價值。 The plastic product of the present invention contains the compound represented by the formula (1), so that the plastic product has high ultraviolet resistance and increases its durability in the need of exposure to ultraviolet rays, and the plastic product having the ultraviolet absorbent does not The release of toxic N-methylaniline can increase the value of the plastic product.
合成實施例1:N-(乙氧基羰基苯基)-N'-(2'-羥基乙基)-N'-苯基甲脒之合成(HEMP) Synthesis Example 1: Synthesis of N-(ethoxycarbonylphenyl)-N'-(2'-hydroxyethyl)-N'-phenylformamidine (HEMP)
將6.41克N-(2-羥基乙基)苯胺與10.34克的4-(乙氧基亞甲基)胺基苯甲酸乙酯(ethyl 4-((ethoxymethylene)amino)benzoate,以下簡稱NE)加到反應瓶中,緩慢升溫到65℃,持溫反應16小時,降溫減壓濃縮後,以管柱分離得到7.00克淡黃色固體,產率48%。 6.41 g of N-(2-hydroxyethyl)aniline and 10.34 g of ethyl 4-((ethoxymethylene)aminobenzoate, hereinafter referred to as NE) Into the reaction flask, the temperature was slowly raised to 65 ° C, the temperature was reacted for 16 hours, and the mixture was cooled under reduced pressure, and then separated by a column to obtain 7.00 g of pale yellow solid, yield 48%.
1H-NMR(CDCl3,300MHz)δ:1.36(t,3H,J=7.2Hz),3.39(t,2H,J=6.0Hz),4.09(t,2H,J=6.0Hz),4.31(q,2H,J=7.2Hz),4.61(br s,1H),6.50(d,2H,J=8.7Hz),7.16(d,2H,J=7.2Hz),7.30-7.45(m,3H),7.84(d,2H,J=8.7Hz),8.41(s,1H) 1 H-NMR (CDCl 3 , 300 MHz) δ: 1.36 (t, 3H, J = 7.2 Hz), 3.39 (t, 2H, J = 6.0 Hz), 4.09 (t, 2H, J = 6.0 Hz), 4.31 ( q, 2H, J = 7.2 Hz), 4.61 (br s, 1H), 6.50 (d, 2H, J = 8.7 Hz), 7.16 (d, 2H, J = 7.2 Hz), 7.30-7.45 (m, 3H) , 7.84 (d, 2H, J = 8.7 Hz), 8.41 (s, 1H)
合成實施例2:N-(乙氧基羰基苯基)-N'-(2'-乙醯氧基乙基)-N'-苯基甲脒之合成(AEMP) Synthesis Example 2: Synthesis of N-(ethoxycarbonylphenyl)-N'-(2'-acetoxyethyl)-N'-phenylformamidine (AEMP)
將8.37克N-(2-乙醯氧基乙基)苯胺與10.34克的NE加到反應瓶中,緩慢升溫到65℃,持溫反應16小時,降溫減壓濃縮後,以管柱分離得到15.39克淡黃色油狀物,產率93%。 8.37 g of N-(2-acetoxyethyl)aniline and 10.34 g of NE were added to the reaction flask, and the temperature was slowly raised to 65 ° C. The reaction was held for 16 hours under temperature, and the mixture was cooled under reduced pressure and then separated by a column. 15.39 g of light yellow oil in 93% yield.
1H-NMR(CDCl3,300MHz)δ:1.38(t,3H,J=7.2Hz),1.91(s,1H),3.96(t,2H,J=5.7Hz),4.24(t,2H,J=5.7Hz),4.40(q,2H,J=6.9Hz),7.03(d,2H,J=8.4Hz)7.15-7.25(m,3H),7.35-7.43(m,2H),7.98(d,2H,J=8.4Hz),8.00(s,1H) 1 H-NMR (CDCl 3 , 300 MHz) δ: 1.38 (t, 3H, J = 7.2 Hz), 1.91 (s, 1H), 3.96 (t, 2H, J = 5.7 Hz), 4.24 (t, 2H, J =5.7 Hz), 4.40 (q, 2H, J = 6.9 Hz), 7.03 (d, 2H, J = 8.4 Hz) 7.15-7.25 (m, 3H), 7.35-7.43 (m, 2H), 7.98 (d, 2H, J = 8.4Hz), 8.00(s, 1H)
合成實施例3:N-(乙氧基羰基苯基)-N'-(2'-苯醯氧基乙基)-N'-苯基甲脒(式2-3)之合成(BEMP) Synthesis Example 3: Synthesis of N-(ethoxycarbonylphenyl)-N'-(2'-benzomethoxyethyl)-N'-phenylformamidine (Formula 2-3) (BEMP)
將11.27克N-(2-苯醯氧基乙基)苯胺與10.34g的NE加到反應瓶中,緩慢升溫到65℃,持溫反應16小時,降溫減壓濃縮後,以管柱分離得到17.12克淡黃色油狀物,產率88%。 11.27 g of N-(2-phenoxyethyl)aniline and 10.34 g of NE were added to the reaction flask, and the temperature was slowly raised to 65 ° C, and the reaction was held for 16 hours under temperature, and the mixture was cooled under reduced pressure and then separated by a column. 17.12 g of light yellow oil in 88% yield.
1H-NMR(CDCl3,300MHz)δ:1.39(t,3H,J=7.2Hz),4.36(t,2H,J=7.2Hz),4.45(t,2H,J=5.4Hz),4.67(t,2H,J=5.4Hz),7.02(d,2H,J=8.4Hz),7.19(m,1H),7.25(d,2H,J=7.5Hz),7.32-7.40(m,4H),7.52(t,1H,J=7.5Hz),7.82(d,2H,J=7.2Hz),7.98(d,2H,J=8.7Hz),8.04(s,1H) 1 H-NMR (CDCl 3 , 300 MHz) δ: 1.39 (t, 3H, J = 7.2 Hz), 4.36 (t, 2H, J = 7.2 Hz), 4.45 (t, 2H, J = 5.4 Hz), 4.67 ( t, 2H, J = 5.4 Hz), 7.02 (d, 2H, J = 8.4 Hz), 7.19 (m, 1H), 7.25 (d, 2H, J = 7.5 Hz), 7.32-7.40 (m, 4H), 7.52 (t, 1H, J = 7.5 Hz), 7.82 (d, 2H, J = 7.2 Hz), 7.98 (d, 2H, J = 8.7 Hz), 8.04 (s, 1H)
合成實施例4:N-(乙氧基羰基苯基)-N'-(2'-乙醯氨基乙基)-N'-苯基甲脒之合成(N-AEMP) Synthesis Example 4: Synthesis of N-(ethoxycarbonylphenyl)-N'-(2'-acetamidoethyl)-N'-phenylformamidine (N-AEMP)
將8.35克N-(2-乙醯氨基乙基)苯胺與10.34克的NE加到反應瓶中,緩慢升溫到65℃,持溫反應16小時,降溫減壓濃縮後,以管柱分離得到14.86克淡黃色油狀物,產率90%。 8.35 g of N-(2-acetamidoethyl)aniline and 10.34 g of NE were added to the reaction flask, and the temperature was slowly raised to 65 ° C, and the reaction was held for 16 hours under temperature, and the mixture was cooled under reduced pressure, and then separated by a column to obtain 14.86. A light yellow oil with a yield of 90%.
1H-NMR(CDCl3,300MHz)δ:1.39(t,3H,J=7.2Hz),1.94(s,1H),3.58(t,2H,J=6.0Hz),4.20(t,2H,J=6.0Hz),4.36(q,2H,J=7.2Hz),7.02(br s,1H),7.03(d,2H,J=8.4Hz)7.15-7.25(m,3H),7.35-7.45(m,2H),8.00(d,2H,J=8.4Hz),8.06(s,1H) 1 H-NMR (CDCl 3 , 300 MHz) δ: 1.39 (t, 3H, J = 7.2 Hz), 1.94 (s, 1H), 3.58 (t, 2H, J = 6.0 Hz), 4.20 (t, 2H, J =6.0 Hz), 4.36 (q, 2H, J = 7.2 Hz), 7.02 (br s, 1H), 7.03 (d, 2H, J = 8.4 Hz) 7.15-7.25 (m, 3H), 7.35-7.45 (m , 2H), 8.00 (d, 2H, J = 8.4 Hz), 8.06 (s, 1H)
合成實施例5:N-(4-乙氧基羰基苯基)-N'-(2'-羥基乙基)-N'-(4’-乙氧基羰基苯基)甲脒之合成(HEET) Synthesis Example 5: Synthesis of N-(4-ethoxycarbonylphenyl)-N'-(2'-hydroxyethyl)-N'-(4'-ethoxycarbonylphenyl)formamidine (HEET) )
將9.78克N-(2’-羥基乙基)-N'-(4-乙氧基羰基)苯胺與10.34克的NE加到反應瓶中,緩慢升溫到65℃,持溫反應16小時,降溫減壓濃縮後,以管柱分離得到9.34克淡黃色固體,產率52%。 9.78 g of N-(2'-hydroxyethyl)-N'-(4-ethoxycarbonyl)aniline and 10.34 g of NE were added to the reaction flask, and the temperature was slowly raised to 65 ° C, and the reaction was held for 16 hours while maintaining the temperature. After concentration under reduced pressure, a white solid was obtained.
1H-NMR(CDCl3,300MHz)δ:1.38(m,6H),3.42(t,2H,J= 6.0Hz),4.13(t,2H,J=6.0Hz),4.31(t,2H,J=6.9Hz),4.39(q,2H,J=6.9Hz),6.50(d,2H,J=8.7Hz),7.21(d,2H,J=8.7Hz),7.85(d,2H,J=8.7Hz),8.08(d,2H,J=8.7Hz),8.52(s,1H) 1 H-NMR (CDCl 3 , 300 MHz) δ: 1.38 (m, 6H), 3.42 (t, 2H, J = 6.0 Hz), 4.13 (t, 2H, J = 6.0 Hz), 4.31 (t, 2H, J =6.9 Hz), 4.39 (q, 2H, J = 6.9 Hz), 6.50 (d, 2H, J = 8.7 Hz), 7.21 (d, 2H, J = 8.7 Hz), 7.85 (d, 2H, J = 8.7) Hz), 8.08 (d, 2H, J = 8.7 Hz), 8.52 (s, 1H)
試驗例1:聚氨酯泡棉之耐黃變測試Test Example 1: Yellowing resistance test of polyurethane foam
將上述合成實施例1至4之紫外線吸收劑添加於聚氨酯泡棉,同時與N-(乙氧基羰基苯基)-N'-甲基-N'-苯基甲脒(NEMP,和新化工)及不添加任何紫外線吸收劑之空白組作比較,以相同製備方法下進行聚氨酯泡棉之耐黃變測試,有關之試驗步驟及結果敘述如下。 The ultraviolet absorbers of the above Synthesis Examples 1 to 4 were added to a polyurethane foam while being combined with N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine (NEMP, and New Chemicals). And the blank group without adding any ultraviolet absorber is compared, and the yellowing resistance test of the polyurethane foam is carried out by the same preparation method, and the relevant test steps and results are described below.
1.聚氨酯泡棉配方比例(如表1所示):
2.聚氨酯泡棉之製作步驟: 2. Polyurethane foam production steps:
2-1 將6.1克二異氰酸甲苯(TDI-80)與12克多元醇(PP-3000)分別置於兩個A、B燒杯中。 2-1 6.1 g of toluene diisocyanate (TDI-80) and 12 g of polyol (PP-3000) were placed in two A, B beakers, respectively.
2-2 取計量好的0.02克二胺觸媒(33LV)、0.04克有機錫觸媒(T-9)、0.12克整泡劑(SZ-580)、0.48克蒸餾水及0.188克紫外線吸收劑依序加入B燒杯中。 2-2 Take 0.02 g of diamine catalyst (33LV), 0.04 g of organic tin catalyst (T-9), 0.12 g of foam stabilizer (SZ-580), 0.48 g of distilled water and 0.188 g of UV absorber. Add to the B beaker.
2-3 調整高速攪拌機轉速3000rpm,以轉子攪拌B燒杯的混合物,攪拌30秒後停止攪拌。 2-3 Adjust the speed of the high-speed mixer at 3000 rpm, stir the mixture of the B beaker with the rotor, and stir for 30 seconds before stopping the stirring.
2-4 將A燒杯的二異氰酸甲苯倒入B燒杯中,調整高速攪拌機轉速3000rpm,攪拌15秒後停止攪拌,迅速將混合物倒入模具內自然發泡。 2-4 Pour the toluene di-isocyanate in the A beaker into the B beaker, adjust the high-speed mixer rotation speed to 3000 rpm, stir for 15 seconds, stop the stirring, and quickly pour the mixture into the mold to naturally foam.
2-5 經室溫靜置24小時熟成後,將聚氨酯泡棉取出後製成厚度20mm,直徑60mm泡棉測試片供耐黃變測試用。 2-5 After standing at room temperature for 24 hours, the polyurethane foam was taken out to prepare a foam test piece having a thickness of 20 mm and a diameter of 60 mm for the yellowing resistance test.
3.耐黃變測試: 3. Yellowing resistance test:
將上述各測試片放入加速老化測試箱(QUV儀器,ASTM G154只有照射,Q-Lab,Q-Basic;燈源:UVB-313;溫度:60℃)中進行老化測試,歷時12小時後取出,做黃度(Yi)與黃變指數(鎠Yi)測試。所得結果如表2所示:
表2中所表示的鎠Yi值越小時,表示該聚氨酯試片抗黃變的情形越佳。包含本發明之紫外線吸收劑的聚氨酯泡棉測試片其鎠Yi值相較於空白組之聚氨酯泡棉測試片的鎠Yi值低,顯示經添加本發明之紫外線吸收劑能明顯提升聚氨酯抗黃變的效果。 The smaller the value of 鎠Yi shown in Table 2, the better the case where the polyurethane test piece is resistant to yellowing. The polyurethane foam test piece comprising the ultraviolet absorbent of the present invention has a lower 鎠Yi value than the blank group of the polyurethane foam test piece, indicating that the ultraviolet absorbent of the present invention can significantly enhance the anti-yellowing of the polyurethane. Effect.
試驗例2:熱塑性聚氨酯膜之耐黃變測試Test Example 2: Yellowing resistance test of thermoplastic polyurethane film
將上述合成實施例1至4之紫外線吸收劑添加於熱塑性聚氨酯膜,同時與N-(乙氧基羰基苯基)-N'-甲基-N'-苯基甲脒(NEMP,和新化工)及不添加任何紫外線吸收劑之空白組作比較,以相同製備方法下進行熱塑性聚氨酯膜之耐黃變測試,有關之試驗步驟及結果敘述如下。 The ultraviolet absorbers of the above Synthesis Examples 1 to 4 were added to a thermoplastic polyurethane film while being combined with N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine (NEMP, and New Chemicals). And the blank group without adding any ultraviolet absorber is compared, and the yellowing resistance test of the thermoplastic polyurethane film is carried out by the same preparation method, and the relevant test steps and results are described below.
1.熱塑性聚氨酯(TPU)膜之製作步驟: 1. Manufacturing steps of thermoplastic polyurethane (TPU) film:
1-1 將TPU塑料(拜耳,Desmopan-385SX)以二甲基甲醯胺溶解,在45℃溫度控制下配製10% w/w TPU溶液。 1-1 TPU plastic (Bayer, Desmopan-385SX) was dissolved in dimethylformamide and a 10% w/w TPU solution was prepared under the control of 45 °C.
1-2 取30g上述溶液,添加1.0% w/w紫外線吸收劑,攪拌均勻。 1-2 Take 30 g of the above solution, add 1.0% w/w UV absorber, and mix well.
1-3 將步驟(2)配置好的溶液以塗佈器施於玻璃板上並設定塗佈器濕膜厚度為1毫米。 1-3 The solution prepared in the step (2) was applied to a glass plate by an applicator and the wet film thickness of the applicator was set to 1 mm.
1-4 塗佈後將步驟(3)濕膜置於80℃熱風循環烘箱中烘乾30分鐘,待溶劑揮發即得到約15微米厚度的薄膜。 1-4 After coating, the wet film of step (3) is dried in a hot air circulating oven at 80 ° C for 30 minutes, and a film having a thickness of about 15 μm is obtained after the solvent is volatilized.
2.耐黃變測試: 2. Yellowing resistance test:
將上述各測試片放入加速老化測試箱(QUV儀器,ASTM G154只有照射,Q-Lab,Q-Basic;燈源:UVB-313;溫度:60℃)中進行老化測試,歷時24與48小時後取出,做黃度(Yi)與黃變指數(鎠Yi)測試。所得結果如表3所示。 The above test pieces were placed in an accelerated aging test box (QUV instrument, ASTM G154 only irradiation, Q-Lab, Q-Basic; light source: UVB-313; temperature: 60 ° C) for aging test, which lasted 24 hours and 48 hours. After taking out, do the yellowness (Yi) and yellowing index (鎠Yi) test. The results obtained are shown in Table 3.
測試時間越長,試片所接收的能量就越多,相對其黃變的影響就較為明顯。由表3結果可見,包含本發明之紫外線吸收劑的熱塑性聚氨酯膜測試片其鎠Yi值相較於空白組之熱塑性聚氨酯膜測試片的鎠Yi值低,顯示經添加本發明之紫外線吸收劑能明顯提升聚氨酯抗黃變的效果。 The longer the test time, the more energy the test piece receives, and the effect on the yellowing is more obvious. As can be seen from the results of Table 3, the thermoplastic polyurethane film test piece comprising the ultraviolet absorbent of the present invention has a lower 鎠Yi value than that of the blank thermoplastic thermoplastic film test piece, and shows that the ultraviolet absorbent of the present invention can be added. Significantly enhance the anti-yellowing effect of polyurethane.
試驗例3:N-甲基苯胺(NMA)殘留測試Test Example 3: N-methylaniline (NMA) residue test
將各50克的AEMP、N-AEMP與N-(乙氧基羰基苯基)-N'-甲基-N'-苯基甲脒(NEMP,和新化工)分別置於不同燒杯中,放入熱風循環烘箱進行90℃老化,老化時間36小時, 取出後攪拌均勻,取樣以氣相層析儀(GC)檢測N-甲基苯胺殘留,有關之試驗步驟及結果敘述如下。 Each 50 g of AEMP, N-AEMP and N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine (NEMP, and New Chemical) were placed in separate beakers and placed in separate beakers. Into the hot air circulating oven for aging at 90 ° C, the aging time is 36 hours, after stirring, the mixture is evenly stirred. The sample is sampled by gas chromatography (GC) to detect the residue of N-methylaniline. The relevant test procedures and results are described below.
1.氣相層析儀分析方法: 1. Gas chromatograph analysis method:
使用溶劑及儀器: Use solvents and instruments:
2.檢驗流程: 2. Inspection process:
2-1 配製N-甲基苯胺標準品:分別精秤N-甲基苯胺50mg、100mg、200mg,分別加入氰甲烷100mL,配製成500ppm、1000ppm、2000ppm的濃度。 2-1 Preparation of N-methylaniline standard: Separately weighed 50 mg, 100 mg, and 200 mg of N-methylaniline, respectively, and added 100 mL of cyanide to prepare a concentration of 500 ppm, 1000 ppm, and 2000 ppm.
2-2 固定標準品注入體積為10微升(μL),進行檢測。 2-2 The fixed standard injection volume is 10 μL (μL) for testing.
2-3 將此3個標準品結果進行檢量線之線性回歸分析,X軸為濃度,Y軸為積分面積;並檢驗線性相關係數 值(R2)是否達0.995以上(若未達此標準須重新配製)。 2-3 Perform linear regression analysis of the three standard results on the calibration curve, the X-axis is the concentration, and the Y-axis is the integrated area; and check whether the linear correlation coefficient value (R 2 ) is above 0.995 (if this standard is not met) Must be reconstituted).
2-4 分別取NEMP、AEMP與N-AEMP樣品各1g並加入氰甲烷10mL。 2-4 Take 1 g of each of NEMP, AEMP and N-AEMP samples and add 10 mL of cyanamide.
2-5 進行各樣品N-甲基苯胺含量分析(注射量為3.0微升)。 2-5 The N-methylaniline content of each sample was analyzed (injection amount was 3.0 μl).
2-6 將所得結果放入檢量線之線性回歸公式求出其殘留濃度。 2-6 The linear regression formula of the obtained result is placed in the calibration curve to determine the residual concentration.
3.檢測步驟: 3. Detection steps:
3-1 檢查譜圖基線:是否有不穩以及雜訊產生(穩定性±1mAU)。 3-1 Check the spectral baseline: Is there any instability and noise generation (stability ± 1 mAU).
3-2 檢測空白試驗。 3-2 Test blank test.
3-3 檢測樣品,連續檢測三次,以3次數值做平均,吸收面積之相對標準偏差值(RSD)必須小於2.0%。 3-3 Detect the sample and test it three times in succession. The average value of the three times is averaged. The relative standard deviation (RSD) of the absorption area must be less than 2.0%.
表4將氣相層析儀檢測N-甲基苯胺殘留所得結果敘述如下。 Table 4 shows the results obtained by gas chromatography to detect N-methylaniline residues as described below.
表4中可見,由於NEMP在一般常溫中就會產生N- 甲基苯胺,因此經長時間高溫老化測試,可見該N-甲基苯胺的含量明顯提升,相較於NEMP產品,本發明提供之紫外線吸收劑,即便經過高溫老化亦不會有N-甲基苯胺的形成,因此可符合歐盟對N-甲基苯胺限制之要求。 It can be seen from Table 4 that since NEMP produces N-methylaniline at normal room temperature, the content of the N-methylaniline is significantly improved after prolonged high temperature aging test, and the present invention provides the same as NEMP products. UV absorbers, even after high temperature aging, will not form N-methylaniline, so it can meet the EU requirements for N-methylaniline.
試驗例4:UV吸收率測試Test Example 4: UV absorption rate test
將表5中各樣品(上述合成實施例1至5之紫外線吸收劑;N-(乙氧基羰基苯基)-N'-甲基-N'-苯基甲脒(NEMP,和新化工)取相同重量以二氯甲烷溶解後稀釋配製成2.0毫克/升的溶液,以UV光譜儀(Shimadzu,UV-1700,量測皿寬度:1公分;掃瞄範圍:200至800奈米;溫度:25度)進行UV吸收率測試。所得結果如表5所示。 Each sample in Table 5 (the ultraviolet absorber of the above Synthesis Examples 1 to 5; N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine (NEMP, and New Chemicals) The same weight was dissolved in dichloromethane and diluted to prepare a solution of 2.0 mg / liter, using a UV spectrometer (Shimadzu, UV-1700, measuring the width of the dish: 1 cm; scanning range: 200 to 800 nm; temperature: The UV absorbance test was carried out at 25 degrees. The results obtained are shown in Table 5.
表5中可見,本發明所提供之紫外線吸收劑在近紫外光區(波長為200至380奈米)皆有吸收效果,顯示本發明 所提供之紫外線吸收劑添加於塑膠製品上由於該紫外線吸收劑具吸收紫外光能量之效果,故能提升該塑膠製品在紫外線環境下的耐用性。 As can be seen from Table 5, the ultraviolet absorber provided by the present invention has an absorption effect in the near ultraviolet region (wavelength of 200 to 380 nm), and shows that the ultraviolet absorber provided by the present invention is added to the plastic article due to the ultraviolet absorption. The agent absorbs the ultraviolet light energy, so it can improve the durability of the plastic product in the ultraviolet environment.
綜上所述,本發明之塑膠製品因包含該式(1)所示化合物,使得該塑膠製品具有高抗紫外線性能而增加其在需要曝曬在紫外線環境下的耐用性,並且具有該紫外線吸收劑之塑膠製品不會釋放出有毒的N-甲基苯胺,因此能擴展該紫外線吸收劑及含有該紫外線吸收劑的塑膠製品的用途。 In summary, the plastic article of the present invention contains the compound of the formula (1), so that the plastic article has high ultraviolet resistance and increases its durability in the need of exposure to ultraviolet rays, and has the ultraviolet absorber. The plastic product does not release toxic N-methylaniline, thereby expanding the use of the ultraviolet absorber and the plastic article containing the ultraviolet absorber.
Claims (15)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW106119443A TWI633079B (en) | 2017-06-12 | 2017-06-12 | Ultraviolet absorber and plastic article having the ultraviolet absorber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW106119443A TWI633079B (en) | 2017-06-12 | 2017-06-12 | Ultraviolet absorber and plastic article having the ultraviolet absorber |
Publications (2)
Publication Number | Publication Date |
---|---|
TWI633079B TWI633079B (en) | 2018-08-21 |
TW201902870A true TW201902870A (en) | 2019-01-16 |
Family
ID=63960005
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW106119443A TWI633079B (en) | 2017-06-12 | 2017-06-12 | Ultraviolet absorber and plastic article having the ultraviolet absorber |
Country Status (1)
Country | Link |
---|---|
TW (1) | TWI633079B (en) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4021471A (en) * | 1974-04-18 | 1977-05-03 | Givaudan Corporation | Formamidines useful as ultraviolet light absorbers |
JP3821544B2 (en) * | 1997-07-02 | 2006-09-13 | ケミプロ化成株式会社 | Formamidine compound and ultraviolet absorber using the same |
KR100562428B1 (en) * | 2004-05-27 | 2006-03-17 | 주식회사 지코 | Benzylformamidine compound |
TWI518058B (en) * | 2014-12-15 | 2016-01-21 | 和新化學工業股份有限公司 | Ultraviolet absorber and plastic article having the ultraviolet absorber |
-
2017
- 2017-06-12 TW TW106119443A patent/TWI633079B/en active
Also Published As
Publication number | Publication date |
---|---|
TWI633079B (en) | 2018-08-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102455597B (en) | X-ray sensitive resin composition, cured film and forming method thereof, liquid crystal display cells array base palte and forming method thereof | |
EP1438352B1 (en) | Low color, low sodium benzoxazinone uv absorbers and process for making same | |
JP2021120762A (en) | Optical film, and flexible device obtained by using the same | |
CN105339340B (en) | Generated base alkaline agent, the alkali reactive composition containing the generated base alkaline agent and production alkali method | |
JP6991802B2 (en) | Coloring compositions, coloring curable compositions, color filters, liquid crystal displays, and compounds | |
CN104995219A (en) | Polymerizable compound, polymerizable composition, polymer, and optically anisotropic body | |
US10927087B2 (en) | Method for producing polymerizable compound | |
JP2009080452A5 (en) | ||
KR102206028B1 (en) | New compound, poly(imide-amide) copolymer using same, and article including poly(imide-amide)copolymer | |
KR101876524B1 (en) | Polyimide film | |
US8927619B2 (en) | Color-stabilized iodopropynyl butylcarbamate | |
TWI633079B (en) | Ultraviolet absorber and plastic article having the ultraviolet absorber | |
Daglar et al. | Acetylene dicarboxylic acid diallyl ester: a versatile monomer for thiol–ene photocured networks | |
CN109651275B (en) | Triazine compound, composition and preparation method thereof | |
JP6999039B2 (en) | Fluorine-containing fluorene oxime ester-based photoinitiator, photo-curing composition containing it, and its application | |
CN110615801B (en) | Preparation method and application of triazine compound with polyvinyl chloride light stabilization effect | |
CN110256730A (en) | Light stabilizer and the preparation method and application thereof for weather-proof pvc material | |
JP7331860B2 (en) | Photosensitive insulating film composition | |
JP2023156304A (en) | Photosensitive insulation film composition | |
JP6897907B2 (en) | Colorant compounds and coloring compositions containing them | |
KR100562428B1 (en) | Benzylformamidine compound | |
TWI669298B (en) | Antioxidant agent and plastic article having the same | |
JP7150465B2 (en) | Polyimide precursor composition, polyamic acid, polyimide resin, polyimide film, and optical device | |
TWI746831B (en) | Polyimide film and display device | |
Raditoiu et al. | Synthesis, characterization and photoisomerization behavior of some organic modified silica—Azo dye hybrid films |