TWI591108B - Polymer additives and composite materials - Google Patents

Description

Auxiliary composition and composite material for polymer

The present invention relates to an auxiliary composition, and more particularly to an auxiliary composition for a polymer.

Among polymer materials, polyolefins have become widely used polymer materials because of their excellent chemical resistance and mechanical properties. However, during the process of processing or the finished product made of the polyolefin, the polyolefin is susceptible to light, resulting in problems such as yellowing, aging or embrittlement.

U.S. Patent Publication No. 6051164 discloses a composition for protecting a polymer from ultraviolet light. The composition includes o-hydroxy-triaryl three Ortho hydroxy tris-aryl triazine light absorber and hindered amine light stabilizers (HALS) having a molecular weight of 500 or more, wherein the hindered amine light stabilizer and o-hydroxy-triaryl group three The weight ratio of the light absorber ranges from 3:1 to 20:1. Although the composition can improve the stability of the polymer to light and avoid the problem of polymer deterioration (such as embrittlement, yellowing or aging), the effect is still not in line with the industry.

In view of the above, it is a problem that those skilled in the art can break through to provide a material which can improve the stability of the polymer to light and avoid deterioration of the polymer.

Accordingly, a first object of the present invention is to provide a auxiliaries for polymers which prevent deterioration of the polymer after exposure to light.

Thus, the additive composition for a polymer of the present invention comprises three a light absorber (A), a component (B) having a polyisocyanate group, and a hindered amine component (C) having a reactive functional group, and the reactive functional group includes at least one group selected from the group consisting of Composition: hydroxyl group, thiol group and amine group.

The individual components will be described in detail below.

[three (triazine) is a light absorber (A)]

The three The light absorbing agent (A) may be used alone or in combination of two or more, and the three The light absorbing agent (A) is, for example but not limited to, the three shown in the formula (1) Compound, 2-(4-((2-hydroxy-3-dodecyloxypropyl)-oxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl) )-1,3,5-three [2-(4-((2-hydroxy-3-dodecyloxypropyl)-oxyl-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine], 2-(4 -((2-hydroxy-3,3,3-tris(decalkoxy)propyl)-oxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl) -1,3,5-three [2-(4-((2-hydroxy-3,3,3-tridecyloxypropyl)-oxyl-2hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine], or 2 -(4-((2-hydroxy-3-isooctyloxypropyl)-oxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3 , 5-three [2-(4-((2-hydroxy-3-isooctyloxypropyl)-oxyl-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine];

Each of W ¹ , W ² and W ³ is an aromatic group substituted with a substituent or an unsubstituted group; the substituent in the substituted aryl group is selected from hydrogen, hydroxyl, An alkyl group, an alkoxy group, a sulfonic acid group (-SO ₂ OH), a carboxyl group (-COOH, a carboxyl group), a halogen, a haloalkyl group or an acylamino group, wherein When W ¹ , W ² and W ^{3 are} the substituent-substituted aryl group, at least one substituent of at least one of W ¹ , W ² and W ³ is a hydroxyl group.

The three shown in the formula (1) The compound may be used alone or in combination of two or more, and the three compounds represented by the formula (1) The compound is, for example but not limited to, the three represented by the formula (1-1) A compound or the like.

W ⁴ , W ⁵ , W ⁶ and W ⁷ are each hydrogen, hydroxy, alkyl, alkoxy, sulphate, carboxylic acid, halogen, haloalkyl or guanamine; W ⁸ is hydrogen or C ₁ to An alkyl group of C ₁₈ . Preferably, each of W ⁴ , W ⁵ , W ⁶ and W ⁷ is hydrogen or methyl, and W ⁸ is hydrogen, hexyl or octyl.

The three shown in the formula (1-1) a compound such as, but not limited to, 2-(4,6-diphenyl-1,3,5-three 2-yl)-5-hexyloxy-phenol [2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxy-phenol], or 2-[4,6 - bis(2,4-dimethylphenyl)-1,3,5-three 2-yl]-5-octyloxyphenol {2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-octyloxy-phenol}.

[Component (B) having a polyisocyanate group]

The component (B) having a polyisocyanate group includes a diisocyanate compound represented by the formula (2).

O=C=N-Y-N=C=O Equation (2)

Y is a C ₁ to C ₈ alkylene group, a hydroxy substituted C ₅ to C ₂₀ cycloalkyl group, an unsubstituted C ₅ to C ₂₀ cycloalkyl group, ,or

Preferably, the Y is ,or

The diisocyanate compound represented by the formula (2) may be used singly or in combination of two or more, and the diisocyanate compound represented by the formula (2) is, for example, but not isophorone diisocyanate (IPDI), Phenylmethyl diisocyanate (4,4'-diphenylmethane Diisocyanate (MDI), or tolylene-2, 4-diisocyanate (TDI).

[Hindered amine component (C) having a reactive functional group]

The hindered amine-based component (C) having a reactive functional group includes at least one of the hindered amine-based compounds having a reactive functional group represented by the formula (3) to the formula (6).

<Hindered amine compound having a reactive functional group represented by formula (3)>

X ¹ and X ² are each hydrogen, a C ₁ to C ₂₀ alkyl group, ,or , provided that at least one of X ¹ and X ² is ,or Each of M ¹ to M ¹⁶ is hydrogen, phenyl, a C ₁ to C ₂₀ linear alkyl group, a C ₃ to C ₂₀ branched alkyl group, a C ₄ to C ₇ cycloalkyl group, ,or , provided that at least one of M ¹ to M ⁴ is ,or , at least one of M ⁵ to M ⁸ is ,or , at least one of M ⁹ to M ¹² is ,or , at least one of M ¹³ to M ¹⁶ is ,or R ¹ and R ⁸ are each hydrogen, phenyl, C ₂ to C ₃ hydroxyalkyl, C ₁ to C ₂₀ linear alkyl, C ₃ to C ₂₀ branched alkyl, C ₄ to a cycloalkyl group of C ₇ or an oxyl group; R ² to R ⁵ , R ⁹ to R ¹² , R ¹³ to R ¹⁶ and R ²⁰ to R ²³ each being a C ₁ to C ₈ alkyl group, benzyl group Benzyl, Or R ² and R ⁴ together form a C ₅ to C ₁₀ cycloalkyl group, or R ³ and R ⁵ together form a C ₅ to C ₁₀ cycloalkyl group, or R ⁹ and R ¹¹ together form C ₅ a cycloalkyl group to C ₁₀ , or R ¹⁰ and R ¹² together form a C ₅ to C ₁₀ cycloalkyl group, or R ¹³ and R ¹⁴ together form a C ₅ to C ₁₀ cycloalkyl group, or R ¹⁵ and R ¹⁶ Co-formed a C ₅ to C ₁₀ cycloalkyl group, or R ²⁰ and R ²¹ together form a C ₅ to C ₁₀ cycloalkyl group, or R ²² and R ²³ together form a C ₅ to C ₁₀ cycloalkyl group; R ⁷ And each of R ¹⁸ is hydrogen, a C ₁ to C ₈ alkyl group, a benzyl group, Or a C ₅ to C ₁₀ cycloalkyl group; each of R ⁶ and R ¹⁷ is hydrogen, a C ₁ to C ₈ alkyl group, or a benzyl group; each of R ¹⁹ and R ₂₄ is hydrogen, phenyl, C ₁ to C a linear alkyl group of ₂₀ , a C ₃ to C ₂₀ branched alkyl group, a C ₄ to C ₇ cycloalkyl group, or a benzyl group; and Z ¹ is a C ₂ to C ₂₀ straight chain alkyl group ( alkylene), C branched (branched) ₂ to C ₂₀ alkylene group, at least one -CH ₂ - is oxygen (-O-) C-substituted straight chain alkylene of ₂ to C _20, at least one -CH ₂ - a sulfur (-S-) substituted linear C ₂ to C ₂₀ alkylene group, and at least one hydrogen is nitro (nitro, -NO ₂₎ substituted by straight-chain C ₂ to C ₂₀ alkylene group, and at least a -CH ₂ -C ₂ to C ₂₀ branched alkyl group substituted by oxygen, at least one -CH ₂ -C ₂ -C ₂₀ branched alkyl group substituted by sulfur, or at least one hydrogen nitro group Substituted C ₂ to C ₂₀ branched alkyl groups.

Preferably, X ¹ and X ² are each ,or . Preferably, at least one of the M ¹³ to M ¹⁶ is . Preferably, R ¹ is hydrogen or a C ₁ to C ₂₀ linear alkyl group. Preferably, R ² to R ⁵ and R ¹³ to R ¹⁶ are each a C ₁ to C ₈ alkyl group. Preferably, R ¹⁹ is a C ₄ to C ₇ cycloalkyl group. Preferably, Z ¹ is a C ₂ to C ₂₀ linear alkylene group.

The hindered amine compound having a reactive functional group represented by the formula (3) is, for example but not limited to, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6 -Hexanediamine, N,N'-bis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,6-hexanediamine, ,or Wait.

<Hindered amine compound having a reactive functional group represented by formula (4)>

X ³ and X ⁴ are each hydrogen, a C ₁ to C ₂₀ alkyl group, ,or , provided that at least one of X ³ and X ⁴ is ,or Each of M ¹ to M ¹⁶ is hydrogen, phenyl, a C ₁ to C ₂₀ linear alkyl group, a C ₃ to C ₂₀ branched alkyl group, a C ₄ to C ₇ cycloalkyl group, ,or , provided that at least one of M ¹ to M ⁴ is ,or , at least one of M ⁵ to M ⁸ is ,or , at least one of M ⁹ to M ¹² is ,or , at least one of M ¹³ to M ¹⁶ is ,or R ¹ and R ⁸ are each hydrogen, phenyl, C ₂ to C ₃ hydroxyalkyl, C ₁ to C ₂₀ linear alkyl, C ₃ to C ₂₀ branched alkyl, C ₄ to C ₇ a cycloalkyl group, or an oxygen radical; R ² to R ⁵ , R ⁹ to R ¹² , R ¹³ to R ¹⁶ and R ²⁰ to R ²³ are each a C ₁ to C ₈ alkyl group, a benzyl group, Or R ² and R ⁴ together form a C ₅ to C ₁₀ cycloalkyl group, or R ³ and R ⁵ together form a C ₅ to C ₁₀ cycloalkyl group, or R ⁹ and R ¹¹ together form C ₅ to C ₁₀ a cycloalkyl group, or R ¹⁰ and R ¹² together form a C ₅ to C ₁₀ cycloalkyl group, or R ¹³ and R ¹⁴ together form a C ₅ to C ₁₀ cycloalkyl group, or R ¹⁵ and R ¹⁶ together form C ₅ to C ₁₀ cycloalkyl, or R ²⁰ and R ²¹ together form a C ₅ to C ₁₀ cycloalkyl group, or R ²² and R ²³ together form a C ₅ to C ₁₀ cycloalkyl group; R ⁷ and R ¹⁸ Each is hydrogen, C ₁ to C ₈ alkyl, benzyl, Or a C ₅ to C ₁₀ cycloalkyl group; each of R ⁶ and R ¹⁷ is hydrogen, a C ₁ to C ₈ alkyl group, or a benzyl group; each of R ¹⁹ and R ₂₄ is hydrogen, phenyl, C ₁ to C a linear alkyl group of ₂₀ , a C ₃ to C ₂₀ branched alkyl group, a C ₄ to C ₇ cycloalkyl group, or a benzyl group.

Preferably, at least one of X ³ and X ⁴ is . Preferably, R ¹ is hydrogen or a C ₁ to C ₂₀ linear alkyl group. Preferably, each of R ² to R ⁵ is a C ₁ to C ₈ alkyl group.

The hindered amine compound having a reactive functional group represented by the formula (4) is, for example but not limited to, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, or 2,2,6 , 6-tetramethyl-4-piperidinamine and the like.

<Hindered amine-based compound having a reactive functional group represented by formula (5)>

X ⁵ -T ¹ -T ² (5)

T ¹ is oxygen (-O-) or sulfur (-S-); X ⁵ is ,or Each of M ¹ to M ¹⁶ is hydrogen, phenyl, a C ₁ to C ₂₀ linear alkyl group, a C ₃ to C ₂₀ branched alkyl group, a C ₄ to C ₇ cycloalkyl group, ,or , provided that at least one of M ¹ to M ⁴ is ,or , at least one of M ⁵ to M ⁸ is ,or , at least one of M ⁹ to M ¹² is ,or , at least one of M ¹³ to M ¹⁶ is ,or R ¹ and R ⁸ are each hydrogen, phenyl, C ₂ to C ₃ hydroxyalkyl, C ₁ to C ₂₀ linear alkyl, C ₃ to C ₂₀ branched alkyl, C ₄ to C ₇ a cycloalkyl group, or an oxygen radical; R ² to R ⁵ , R ⁹ to R ¹² , R ¹³ to R ¹⁶ and R ²⁰ to R ²³ are each a C ₁ to C ₈ alkyl group, a benzyl group, Or R ² and R ⁴ together form a C ₅ to C ₁₀ cycloalkyl group, or R ³ and R ⁵ together form a C ₅ to C ₁₀ cycloalkyl group, or R ⁹ and R ¹¹ together form C ₅ to C ₁₀ a cycloalkyl group, or R ¹⁰ and R ¹² together form a C ₅ to C ₁₀ cycloalkyl group, or R ¹³ and R ¹⁴ together form a C ₅ to C ₁₀ cycloalkyl group, or R ¹⁵ and R ¹⁶ together form C ₅ to C ₁₀ cycloalkyl, or R ²⁰ and R ²¹ together form a C ₅ to C ₁₀ cycloalkyl group, or R ²² and R ²³ together form a C ₅ to C ₁₀ cycloalkyl group; R ⁷ and R ¹⁸ Each is hydrogen, C ₁ to C ₈ alkyl, benzyl, Or a C ₅ to C ₁₀ cycloalkyl group; each of R ⁶ and R ¹⁷ is hydrogen, a C ₁ to C ₈ alkyl group, or a benzyl group; each of R ¹⁹ and R ₂₄ is hydrogen, phenyl, C ₁ to C a linear alkyl group of ₂₀ , a C ₃ to C ₂₀ branched alkyl group, a C ₄ to C ₇ cycloalkyl group, or a benzyl group; T ² is hydrogen or -Z ² -OH; and Z ² is C ₂ to C ₂₀ linear alkylene, branched chain C ₂ to C ₂₀ alkylene group, and at least one -CH ₂ - is oxo substituted linear C ₂ to C ₂₀ alkylene group, and at least one -CH ₂ - is sulfur substituted C ₂ to C ₂₀ straight chain alkylene group, nitro group at least one hydrogen is substituted C ₂ to C ₂₀ straight chain alkylene group, at least one -CH ₂ - is oxo substituted C ₂ to C ₂₀ of branched alkylene, at least one -CH ₂ - is replaced by a sulfur branched C ₂ to C ₂₀ alkylene group, a nitro group or at least one hydrogen is substituted with a C ₂ to C ₂₀ branched alkylene group.

Preferably, X ⁵ is . Preferably, R ¹ is hydrogen or an oxygen radical. Preferably, each of R ² to R ⁵ is a C ₁ to C ₈ alkyl group.

The hindered amine compound having a reactive functional group represented by the formula (5) is, for example but not limited to, 2,2,6,6-tetramethyl-4-piperidinol, or 4-hydroxy-2,2,6, 6-tetramethyl-piperidin-1-oxyl radicals and the like.

<Hindered amine-based compound having a reactive functional group represented by formula (6)>

X ⁶ is ,or Each of M ¹ to M ¹⁶ is hydrogen, phenyl, a C ₁ to C ₂₀ linear alkyl group, a C ₃ to C ₂₀ branched alkyl group, a C ₄ to C ₇ cycloalkyl group, ,or , provided that at least one of M ¹ to M ⁴ is ,or , at least one of M ⁵ to M ⁸ is ,or , at least one of M ⁹ to M ¹² is ,or , at least one of M ¹³ to M ¹⁶ is ,or R ¹ and R ⁸ are each hydrogen, phenyl, C ₂ to C ₃ hydroxyalkyl, C ₁ to C ₂₀ linear alkyl, C ₃ to C ₂₀ branched alkyl, C ₄ to C ₇ a cycloalkyl group, or an oxygen radical; R ² to R ⁵ , R ⁹ to R ¹² , R ¹³ to R ¹⁶ and R ²⁰ to R ²³ are each a C ₁ to C ₈ alkyl group, a benzyl group, Or R ² and R ⁴ together form a C ₅ to C ₁₀ cycloalkyl group, or R ³ and R ⁵ together form a C ₅ to C ₁₀ cycloalkyl group, or R ⁹ and R ¹¹ together form C ₅ to C ₁₀ a cycloalkyl group, or R ¹⁰ and R ¹² together form a C ₅ to C ₁₀ cycloalkyl group, or R ¹³ and R ¹⁴ together form a C ₅ to C ₁₀ cycloalkyl group, or R ¹⁵ and R ¹⁶ together form C ₅ to C ₁₀ cycloalkyl, or R ²⁰ and R ²¹ together form a C ₅ to C ₁₀ cycloalkyl group, or R ²² and R ²³ together form a C ₅ to C ₁₀ cycloalkyl group; R ⁷ and R ¹⁸ Each is hydrogen, C ₁ to C ₈ alkyl, benzyl, Or a C ₅ to C ₁₀ cycloalkyl group; each of R ⁶ and R ¹⁷ is hydrogen, a C ₁ to C ₈ alkyl group, or a benzyl group; each of R ¹⁹ and R ₂₄ is hydrogen, phenyl, C ₁ to C a linear alkyl group of ₂₀ , a C ₃ to C ₂₀ branched alkyl group, a C ₄ to C ₇ cycloalkyl group, or a benzyl group; Z ³ is a C ₂ to C ₂₀ linear alkyl group, C ₂ to _{20 is} a branched alkylene of C, at least one -CH ₂ - is oxo substituted linear C ₂ to C ₂₀ alkylene group, and at least one -CH ₂ - is extending sulfur substituted C ₂ to C ₂₀ straight chain of An alkyl group, a C ₂ to C ₂₀ linear alkyl group substituted with at least one hydrogen by a nitro group, a C ₂ to C ₂₀ branched alkyl group substituted with at least one —CH ₂ — by oxygen, at least one —CH ₂ a branched alkyl group of C ₂ to C ₂₀ substituted by sulfur, or a C ₂ to C ₂₀ branched alkyl group substituted with at least one hydrogen by a nitro group.

Preferably, X ⁶ is . Preferably, at least one of the M ¹³ to M ¹⁶ is . Preferably, each of R ¹³ to R ¹⁶ is a C ₁ to C ₈ alkyl group. Preferably, R ¹⁹ is a C ₄ to C ₇ cycloalkyl group. Preferably, Z ³ is a C ₂ to C ₂₀ linear alkylene group.

The hindered amine compound having a reactive functional group represented by the formula (6) is, for example but not limited to Wait.

[Antioxidant (D)]

The antioxidant (D) may be used singly or in combination of two or more, and the antioxidant is, for example but not limited to, [tris(2,4-di-t-butylphenyl) phosphite] (hereinafter referred to as antioxidant 168), four [ Β-(3,5-Di-t-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester (hereinafter referred to as antioxidant 1010), triethylene glycol ether-bis(3-tert-butyl-4-hydroxyl) -5-methylphenyl)propionate (hereinafter referred to as antioxidant 245), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxyl Benzyl) benzene (hereinafter referred to as antioxidant 1330), 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanuric acid (hereinafter referred to as antioxidant 3114), and tris(butyl group) Phenolic)butane, tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol) 4,4'-butylidene bis(6-t-butyl-m-cresol) (hereinafter referred to as antioxidant AO-30), N,N'-bis[β(3,5-di-t-butyl-4) -hydroxyphenyl)propanoid]indole (hereinafter referred to as antioxidant 1024), N,N'-bis-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl) Amine, 2,2'-methylenebis-(4-methyl-6-tert-butylphenol (hereinafter referred to as antioxidant 1098), 3, 5-di-tert-butyl-4-hydroxyphenylpropionic acid isooctyl ester (hereinafter referred to as antioxidant 1135), or an antioxidant represented by formula (7);

W ⁹ is methyl or tert-butyl; W ¹⁰ is hydrogen or ; W ¹¹ is a methyl group or a tributyl group.

[hindered amine-based light stabilizer]

The hindered amine light stabilizer (E) may be used singly or in combination of two or more, and the hindered amine light stabilizer (E) is, for example but not limited to, azelaic acid bis(1,2,2,6,6-penta 4-piperidinyl) ester (hereinafter referred to as light stabilizer 292), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (hereinafter Referred to as light stabilizer 523), bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (hereinafter referred to as light stabilizer 770), 1,5,8,12-four [ 4,6-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-three -2-yl]-1,5,8,12-tetraazadodecane (hereinafter referred to as light stabilizer 119), polysuccinic acid (4-hydroxy-2,2,6,6-tetramethyl- 1-piperidinylethanolate (hereinafter referred to as light stabilizer 622), poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-three -2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imido]-1,6-hexanediyl[(2,2,6,6- Tetramethyl-4-piperidinyl)imine]](poly{[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazi ne-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino]} hereinafter referred to as light stabilizer 944) , N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-N,N'-dialdehyde hexamethylenediamine (hereinafter referred to as light stabilizer 945), [[3 ,5-di-t-butyl-4-hydroxyphenyl]methyl]butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl) ester (hereinafter referred to as light) Stabilizer 5144), 2,9,11,13,15,22,24,26,27,28,-azatricyclo(21.3.1.110.14) octadecane-1(27),10,12 ,14(28),23,25-hexaene-12,25-diamine, N,N'-bis(1,1,3,3-tetramethylbutyl)-2,9,15,22- Tetrakis(2,2,6,6-tetramethyl-4-piperidinyl) (hereinafter referred to as light stabilizer 966), 2-methyl-2-acrylic acid-1,2,2,4,6-penta 4--4-piperidyl ester (hereinafter referred to as light stabilizer LA82), poly[(6-morpholinyl-1,3,5-three -2,4-yl)-((2,2,6,6-tetramethyl-4-piperidyl)imino)hexane-((2,2,6,6-tetramethyl-4-) Piperidinyl)imine)] (hereinafter referred to as light stabilizer 3346), 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole (below) Referred to as light stabilizer 327), or an amine stabilizer as shown in formula (8);

W ¹² and W ¹³ are each hydrogen or a C ₁ to C ₂₀ alkyl group; W ¹⁴ is OH or H.

The method for preparing the auxiliary composition for a polymer is not particularly limited as long as the components in the auxiliary composition for a polymer can be uniformly mixed.

Preferably, the weight ratio of the hindered amine component (C) having a reactive functional group to the component (B) having a polyisocyanate group is in the range of 1 to 99.

Preferably, the total weight of the component (B) having a polyisocyanate group and the hindered amine component (C) having the reactive functional group and the three The weight ratio of the light absorbing agent (A) ranges from 1 to 99.

In order to add the auxiliary composition for the polymer to the polymer to make the formed composite more thermally stable, preferably, the auxiliary composition for the polymer further contains the diol compound (F).

[diol compound (F)]

The diol compound (F) may be used singly or in combination of two or more, and the diol compound (F) is, for example but not limited to, a diol compound represented by the formula (9).

<diol compound represented by formula (9)>

HO-Z ⁴ -OH formula (9)

Z ⁴ is a C ₂ to C ₂₀ linear alkylene, branched chain C ₂ to C ₂₀ alkylene group, and at least one -CH ₂ - is oxo substituted linear C ₂ to C ₂₀ alkylene group, and at least a -CH ₂ -C ₂ to C ₂₀ linear alkyl group substituted by sulfur, at least one C ₂ to C ₂₀ linear alkyl group substituted by a nitro group, at least one -CH ₂ - is substituted by oxygen a C ₂ to C ₂₀ branched alkyl group, at least one -CH ₂ -sulfonate substituted C ₂ to C ₂₀ branched alkyl group, or at least one hydrogen substituted by a nitro group C ₂ to C ₂₀ Branched alkyl.

The diol compound represented by the formula (9) is, for example but not limited to, propylene glycol or butylene glycol.

A second object of the invention is to provide a composite.

Thus, the composite of the present invention is composed of a polymer and the above The additive composition for a polymer is formed by heating, wherein the polymer is added with a component (B) having a polyisocyanate group and a hindered amine component (C) having a reactive functional group in the auxiliary agent composition. In the reaction, or the component (B) having a polyisocyanate group, a hindered amine component (C) having a reactive functional group, and a diol compound (F) in the auxiliary composition for a polyolefin polymer Into a reaction.

The auxiliary composition for the polymer is as described above, and therefore will not be described again. The polymer may be used alone or in combination of two or more, and the polymer is, for example but not limited to, a polyolefin, an acrylonitrile-butadiene-styrene copolymer (hereinafter referred to as ABS), styrene- Acrylonitrile-styrene copolymer (hereinafter referred to as SAN), polyoxymethylene (POM), polyamine 6,6 (polyamide 6,6, hereinafter referred to as PA6,6), or polycarbonate (polycarbonate) , hereinafter referred to as PC). The polyolefin is, for example, but not limited to, polyethylene (hereinafter referred to as PE) or polypropylene (hereinafter referred to as PP).

Preferably, the auxiliary component for the polymer is used in an amount ranging from 0.01 part by weight to 5 parts by weight based on 100 parts by total of the total amount of the polymer.

The preparation method of the composite material is, for example but not limited to, the following method. Method 1: First, the above-mentioned auxiliary composition for a polymer is provided, and the polymer auxiliary composition is mixed with a polymer and heated. The second method is to polymer, three a light absorber (A), the component (B) having a polyisocyanate group, the hindered amine component (C) having a reactive functional group, the antioxidant (D), and the hindered amine light stabilizer ( E) and the diol compound (F) are mixed and heated. The third method is to provide a polymer, a part of the polymer, three a light absorber (A), the component (B) having a polyisocyanate group, the hindered amine component (C) having a reactive functional group, the antioxidant (D), and the hindered amine light stabilizer ( E) and the diol compound (F) are mixed and heated, and then the remaining polymer is added. The heating step may carry out an addition reaction of the component (B) having a polyisocyanate group, the hindered amine component (C) having a reactive functional group, and the diol compound (F) to form an addition product. And the addition product is a compound or a polymer. Depending on the reactive functional group of the hindered amine component (C) having the reactive functional group selected, the addition product such as an amine ester having a hindered amine group ( a material, an amine thioester having a hindered amine group ( a material, urea having a hindered amine group ( a material, or a urea amine ester having a hindered amine group ( and ) is a material. The mixing step and the heating step may be carried out simultaneously, or the mixing step may be performed first followed by the heating step. The apparatus of the mixing step is for example but not limited to a twin screw extruder. Further, the processing step can be carried out after mixing and heating. This processing step is, for example, a drying process or a molding process. This molding process is, for example but not limited to, granulation.

The composite material can be used as a material for agricultural films, packaging films, protective films, and the like.

The effect of the invention is that the invention passes through three The use of a light absorbing agent (A), a component (B) having a polyisocyanate group, and a hindered amine component (C) having a reactive functional group, which are added to the polymer and mixed with the polymer At the same time, the components react to form an addition product, and the addition product is uniformly dispersed in the polymer, which in turn effectively protects the polymer, making the formed composite light stable and not susceptible to deterioration.

Example 1 Composite material

0.005 parts by weight of 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-three -2-yl]-5-octyloxyphenol, 0.001 parts by weight of isophorone diisocyanate, 0.004 parts by weight of N,N'-di(1,2,2,6,6-pentamethyl-4 - Piperidinyl-1,6-hexanediamine, and 100 parts by weight of PP were uniformly mixed, and extruded by a twin-screw extruder at a temperature of 180 ° C and a main screw rotation speed of 100 rpm.

Examples 2 to 18

Examples 2 to 18 were prepared in the same manner as in Example 1 except that the kind of the raw material and the amount thereof were changed. The types of the raw materials and the amounts thereof used are shown in Table 1.

Comparative example 1

0.2 part by weight of the light stabilizer 944 and 100 parts by weight of PP were uniformly mixed, and extruded by a twin-screw extruder at a temperature of 180 ° C and a main screw rotation speed of 100 rpm.

Comparative example 2

Comparative Example 2 was prepared in the same manner as in Comparative Example 1, except that the species of the hindered amine light stabilizer (E) was changed. class. The types of the hindered amine light stabilizer (E) are shown in Table 2.

Comparative example 3

0.04 parts by weight of 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-three 2-yl]-5-octyloxyphenol, 0.16 parts by weight of light stabilizer 944, and 100 parts by weight of PP were uniformly mixed, and extruded by a twin-screw extruder at a temperature of 180 ° C, and the main screw rotation speed was 100 rpm.

Comparative example 4

Comparative Example 4 was prepared in the same manner as in Comparative Example 3 except that the kind of the hindered amine-based light stabilizer (E) was changed. The types of the hindered amine light stabilizer (E) are shown in Table 2.

Comparative Example 5

0.001 parts by weight of isophorone diisocyanate, 0.004 parts by weight of N,N'-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,6-hexane The amine, and 100 parts by weight of PP were uniformly mixed, and extruded by a twin-screw extruder at a temperature of 180 ° C and a main screw rotation speed of 100 rpm.

Comparative Examples 6 to 19

Comparative Examples 6 to 19 were prepared in the same manner as in Comparative Example 5, except that the kind of the raw material and the amount thereof were changed. The types of the raw materials and the amounts thereof used are shown in Table 2.

Comparative Example 20

20 parts by weight of isophorone diisocyanate and 80 parts by weight of N,N'-bis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,6-hexanediamine The mixture was mixed and extruded by a twin-screw extruder at a temperature of 180 ° C and a main screw rotation speed of 100 rpm to form an addition product. The addition product The drying process was carried out by air cooling at room temperature, pelletizing at 60 rpm, and drying at 100 ° C for 4 hours. 0.2 parts by weight of the dried product was uniformly mixed with 100 parts by weight of PP, and extruded by a twin-screw extruder at a temperature of 180 ° C and a main screw rotation speed of 100 rpm.

Comparative Examples 21 to 33

Comparative Examples 21 to 33 were prepared in the same manner as in Comparative Example 20 except that the kind of the raw material and the amount thereof were changed. The types of the raw materials and the amounts thereof used are shown in Table 3.

Evaluation project

Elongation at break elongation value (%): The composites of Examples 1 to 18 and Comparative Examples 1 to 33 were respectively tested to a test piece having a thickness of 2 mm by ASTM D638 IV test, and placed in a tensile tester (equipment). : High-speed Railway Technology Co., Ltd.; Model: AI-7000 S) The tensile strength is measured, and the tensile speed is 100 mm/min, and the obtained elongation at break is T0. The waiting test pieces were placed in an ATLAS Model Ci3000 Xenon Fadeometer and subjected to 5,000 hours of illuminating by ASTM G155 standard test method. After the irradiation, the waiting test pieces were placed in a tensile tester to measure the elongation at break, and the tensile speed was 100 mm/min, and the obtained elongation at break was T1. The elongation loss value of the elongation at break was [(T0 - T1)] × 100% / T0.

From the experimental data of Tables 1 and 2, it is understood that the composite materials of Examples 1 to 18 have a loss elongation loss rate of 20.14% to 45.76% after 5,000 hours of calender irradiation, and the composite materials of Comparative Examples 1 to 19 After 5,000 hours of calendering, the elongation at break was 55.48% to 92.25%. As can be seen from the above, compared to the unused three Light stability of a composite formed by any one of a light absorbing agent (A), a component (B) having a polyisocyanate group, and a hindered amine component (C) having a reactive functional group, the present invention transmits three The use of the light absorbing agent (A), the component (B) having a polyisocyanate group, and the hindered amine component (C) having a reactive functional group, the resulting composite material has a low loss rate of elongation at break after irradiation. It has better light stability.

From the experimental data of Table 3, it was found that the composite materials of Comparative Examples 20 to 33 had a loss elongation loss rate of 62.28% to 99.40% after 5,000 hours of calender irradiation. From the above, it can be seen that the composite of the present invention is formed by mixing the polymer auxiliary composition with the polymer and performing an addition reaction as compared with the light stability of the composite formed by directly mixing the addition product and the polymer. The material has a low elongation loss rate after illuminating, and has better light stability.

In summary, the present invention is through three The use of a light absorbing agent (A), a component (B) having a polyisocyanate group, and a hindered amine component (C) having a reactive functional group, which are added to the polymer and mixed with the polymer At the same time, the components will react to form an addition product, and the addition product will be uniformly dispersed in the polymer, which in turn effectively protects the polymer, so that the formed composite material has light stability and is not easily deteriorated. It is indeed possible to achieve the object of the invention.

However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the equivalent equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still The scope of the invention is covered.

Claims (4)

A auxiliaries for polymers, comprising: three a light absorbing agent; a component having a polyisocyanate group; and a hindered amine component having a reactive functional group; the hindered amine component having a reactive functional group comprising a hindered amine having a reactive functional group represented by the formula (6) Compound X ⁶ is , , , , , , ,or ; M ¹ to M ¹⁶ are each hydrogen, phenyl, C ₁ to C ₂₀ linear alkyl, C ₃ to C ₂₀ branched alkyl, C ₄ to C ₇ cycloalkyl, , , ,or , provided that at least one of M ¹ to M ⁴ is , , ,or , at least one of M ⁵ to M ⁸ is , , ,or , at least one of M ⁹ to M ¹² is , , ,or , at least one of M ¹³ to M ¹⁶ is , , ,or R ¹ and R ⁸ are each hydrogen, phenyl, C ₂ to C ₃ hydroxyalkyl group, C ₁ to C ₂₀ linear alkyl group, C ₃ to C ₂₀ branched alkyl group, C ₄ to C ₇ a cycloalkyl group, or an oxygen radical; R ² to R ⁵ , R ⁹ to R ¹² , R ¹³ to R ¹⁶ and R ²⁰ to R ²³ are each a C ₁ to C ₈ alkyl group, a benzyl group, Or R ² and R ⁴ together form a C ₅ to C ₁₀ cycloalkyl group, or R ³ and R ⁵ together form a C ₅ to C ₁₀ cycloalkyl group, or R ⁹ and R ¹¹ together form C ₅ to C ₁₀ a cycloalkyl group, or R ¹⁰ and R ¹² together form a C ₅ to C ₁₀ cycloalkyl group, or R ¹³ and R ¹⁴ together form a C ₅ to C ₁₀ cycloalkyl group, or R ¹⁵ and R ¹⁶ together form C ₅ to C ₁₀ cycloalkyl, or R ²⁰ and R ²¹ together form a C ₅ to C ₁₀ cycloalkyl group, or R ²² and R ²³ together form a C ₅ to C ₁₀ cycloalkyl group; R ⁷ and R ¹⁸ Each is hydrogen, C ₁ to C ₈ alkyl, benzyl, Or a C ₅ to C ₁₀ cycloalkyl group; each of R ⁶ and R ¹⁷ is hydrogen, a C ₁ to C ₈ alkyl group, or a benzyl group; each of R ¹⁹ and R ₂₄ is hydrogen, phenyl, C ₁ to C a linear alkyl group of ₂₀ , a C ₃ to C ₂₀ branched alkyl group, a C ₄ to C ₇ cycloalkyl group, or a benzyl group; Z ³ is a C ₂ to C ₂₀ linear alkyl group, C ₂ to _{20 is} a branched alkylene of C, at least one -CH ₂ - is oxo substituted linear C ₂ to C ₂₀ alkylene group, and at least one -CH ₂ - is extending sulfur substituted C ₂ to C ₂₀ straight chain of An alkyl group, a C ₂ to C ₂₀ linear alkyl group substituted with at least one hydrogen by a nitro group, a C ₂ to C ₂₀ branched alkyl group substituted with at least one —CH ₂ — by oxygen, at least one —CH ₂ a branched alkyl group of C ₂ to C ₂₀ substituted by sulfur, or a C ₂ to C ₂₀ branched alkyl group substituted with at least one hydrogen by a nitro group. The additive composition for a polymer according to claim 1, wherein the component having a polyisocyanate group comprises a compound having a polyisocyanate group represented by the formula (2); O=C=NYN=C=O (2) Y is a C ₁ to C ₈ alkylene group, a substituted C ₅ to C ₂₀ cycloalkyl group, an unsubstituted C ₅ to C ₂₀ cycloalkyl group, The additive composition for a polymer according to claim 1, wherein the total weight of the component having a polyisocyanate group and the hindered amine component having the reactive functional group and the third The light absorber has a weight ratio ranging from 1 to 99. A composite material obtained by heating a polymer composition according to any one of claims 1 to 3, wherein the polymer auxiliary composition has a polyisocyanate group. The component and the hindered amine component having a reactive functional group are subjected to an addition reaction.