TWI591107B - Method for preparing composite material and composite material - Google Patents

Description

Method for preparing composite material and composite material

The present invention relates to a method of preparing a composite material, and more particularly to a method of producing a composite material having photostability.

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 method of making a stable polymeric article. The method comprises the steps of: polymerizing a polymer, o-hydroxy-triaryl An orthohydroxy tris-aryl triazine light absorber, a hindered amine light stabilizers having a molecular weight of 500 or more, wherein the hindered amine light stabilizer and the o-hydroxy-triaryl group III are mixed. The light absorbent has a weight ratio ranging from 3:1 to 20:1 to form a stable polymer composition, which is then formed into an extruded or film-formed article and a biaxially oriented tape or film. Although the method can improve the stability of the polymer material to light and avoid the problem of deterioration of the polymer material (such as embrittlement, yellowing or aging), the light stability of the polymer product prepared by the method is still not Meet the needs of the industry.

In view of the above, it is a subject that can be further broken by those skilled in the art to provide a preparation method which can improve the stability of the polymer material to light and avoid the deterioration of the polymer.

Accordingly, a first object of the present invention is to provide a method of preparing a composite.

Thus, the method for preparing a composite material according to the present invention comprises the steps of: mixing a polymer (A) and an auxiliary composition to form a mixture, wherein the auxiliary composition comprises a component (B) having a polyisocyanate group and a hindered amine-based component (C) having a reactive functional group, and the reactive functional group in the hindered amine-based component (C) having a reactive functional group includes at least one group consisting of a hydroxyl group, A thiol group and an amine group; then, the polyisocyanate group-containing component (B) and the hindered amine group component (C) having a reactive functional group in the mixture are subjected to an addition reaction.

The ratio of the total amount of the hindered amine-based component (C) having a reactive functional group to the total amount of the component (B) having a polyisocyanate group is in the range of 1 to 99.

The apparatus of the mixing step is for example but not limited to a twin screw extruder. The addition reaction is carried out by reacting a polyisocyanate group in the polyisocyanate group-containing component (B) with a reactive functional group in the hindered amine-based component (C) having a reactive functional group. The addition reaction step and the mixing step can be simultaneously performed in parallel, that is, the addition reaction is carried out while mixing. The addition product formed by the addition reaction is a compound or a polymer. Depending on the selected hindered amine component (C) having a reactive functional group, the product formed by the addition reaction, for example, an amine ester having a hindered amine group Material, amine thioester with hindered amine group Material, urea with hindered amine groups a material, or a urea amine ester having a hindered amine group and Department of materials. Preferably, the reaction temperature of the addition reaction ranges from 130 ° C to 300 ° C. The method of preparing a composite of the present invention further comprises a processing step. This processing step is, for example, a drying process or a molding process. This molding process is, for example but not limited to, granulation.

In order to provide better light stability of the formed composite, it is preferred to mix a portion of the polymer (A) with the auxiliary composition to form the mixture, and to have the polyisocyanate group in the mixture. The component (B) and the hindered amine component (C) having a reactive functional group are subjected to an addition reaction; subsequently, the remaining polymer (A) is added.

In order to increase the collision probability of the component (B) having a polyisocyanate group and the hindered amine component (C) having a reactive functional group, the addition reaction is preferably carried out, preferably, the polymer of the portion ( The amount of A) is less than the amount of the remaining polymer (A).

Preferably, in order to make the composite material more thermally stable, in the method for preparing a composite material according to the present invention, the auxiliary composition further comprises a diol compound (E), and the diol compound (E) has The polyisocyanate group component (B) and the hindered amine group component (C) having a reactive functional group are subjected to an addition reaction.

In the method for preparing a composite material of the present invention, the auxiliary composition further comprises three (triazine) is at least one of a light absorbing agent (D), an antioxidant (F), and a hindered amine light stabilizer (G).

Preferably, the auxiliary agent is used in an amount ranging from 0.01 part by weight to 70 parts by weight based on 100 parts by total of the total amount of the polymer.

The individual components will be described in detail below.

[Polymer (A)]

The polymer (A) 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), Acrylonitrile-styrene copolymer (hereinafter referred to as SAN), polyoxymethylene (POM), polyamine 6,6 (hereinafter referred to as PA6,6), or polycarbonate Polyester (hereinafter referred to as PC) and the like. The polyolefin is, for example, but not limited to, polyethylene (hereinafter referred to as PE) or polypropylene (hereinafter referred to as PP).

[Component (B) having a polyisocyanate group]

The component (B) having a polyisocyanate group includes a diisocyanate compound represented by the formula (1).

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 diisocyanate compound represented by the formula (1) may be used singly or in combination, and the diisocyanate compound represented by the formula (1) is, for example, but not limited to, isophorone diisocyanate (IPDI).

[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 (2) to the formula (5).

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

<Hindered amine-based compound having a reactive functional group represented by formula (2)> 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 a branched alkyl group to C ₂₀ , a C ₄ to C ₇ cycloalkyl group, M ¹ to M ¹⁶ are each hydrogen, phenyl, C ₁ to C ₂₀ linear alkyl, C ₃ ,or , provided that at least one of M ¹ to M ⁴ is 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.

The hindered amine compound having a reactive functional group represented by the formula (2) 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-piperidinyl)-1,6-hexanediamine, Formula (2-1), or Formula (2-2) and the like.

<Hindered amine compound having a reactive functional group represented by formula (3)> X ³ and X ⁴ are each hydrogen, a C ₁ to C ₂₀ alkyl group, , 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.

The hindered amine compound having a reactive functional group represented by the formula (3) 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.

<The hindered amine compound having a reactive functional group represented by the formula (4)>X ⁵ -T ¹ -T ² Formula (4) T ¹ is oxygen (-O-) or sulfur (-S-); X ⁵ is ,or a branched alkyl group to C ₂₀ , a C ₄ to C ₇ cycloalkyl group, M ¹ to M ¹⁶ are each hydrogen, phenyl, C ₁ to C ₂₀ linear alkyl, C ₃ ,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 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.

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

<Hindered amine-based compound having a reactive functional group represented by formula (5)> 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 and 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 hindered amine compound having a reactive functional group represented by the formula (5) is, for example but not limited to Equation (5-1) and so on.

[three Light absorber (D)]

The three The light absorbing agent (D) may be used alone or in combination of two or more, and the three The light absorbing agent (D) is, for example but not limited to, the three shown in the formula (6) 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-hydroxyphe nyl)-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 (6) The compound may be used alone or in combination of two or more, and the three compounds represented by the formula (6) The compound is, for example but not limited to, the three shown in the formula (6-1) 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 (6-1) 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-triaziu-2-yl]-5-octyloxy-phenol}.

[diol compound (E)]

The diol compound (E) may be used singly or in combination of two or more, and the diol compound (E) is, for example but not limited to, a diol compound represented by the formula (7).

<Glycol compound represented by formula (7)>HO-Z ⁴ -OH Formula (7)

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 (7) is, for example but not limited to, propylene glycol or butylene glycol.

[Antioxidant (F)]

The antioxidant (F) may be used singly or in combination of two or more, and the antioxidant (F) is, for example but not limited to, [tris(2,4-di-t-butylphenyl) phosphite] (hereinafter referred to as antioxidant 168) , tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (hereinafter referred to as antioxidant 1010), triethylene glycol ether-bis(3-tert-butyl-4) -hydroxy-5-methylphenyl)propionate (hereinafter referred to as antioxidant 245), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4- Hydroxybenzyl)benzene (hereinafter referred to as antioxidant 1330), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid (hereinafter referred to as antioxidant 3114), and tris(butyl group) Phenyl)butane, tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), 4 , 4'-butylidene bis(6-tert-butylm-cresol) (hereinafter referred to as antioxidant AO-30), N,N'-bis[β(3,5-di-tert-butyl-4-hydroxyphenyl) ) 醯 醯 肼 以下 (hereinafter referred to as antioxidant 1024), N, N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanyl) hexamethylene diamine, 2, 2 '-Methylene bis-(4-methyl-6-tert-butylphenol (hereinafter referred to as antioxidant 1098), 3,5-di-tert-butyl-4-hydroxyl Isooctyl propionate (hereinafter referred to as antioxidant 1135), or Formula (8) shown antioxidants;

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 (G) may be used alone or in combination of two or more, and the hindered amine light stabilizer (G) 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-triazine-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-tert-butyl-4-hydroxyphenyl]methyl]butylmalonate di(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,-azatricyclic (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-tetra ( 2,2,6,6-tetramethyl-4-piperidinyl) (hereinafter referred to as light stabilizer 966), 2-methyl-2-acrylic acid-1,2,2,4,6-pentamethyl- 4-piperidinyl 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 (9);

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

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

Thus, the composite of the present invention is obtained by the above method for preparing a composite.

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

The effect of the present invention is to make the polyisocyanate group-containing component (B) and the reactive functional group hindered amine component (C) in the mixture while mixing the auxiliary agent composition with the polymer (A). Addition Should, an addition product is formed, and the addition product is uniformly dispersed in the polymer (A), which in turn effectively protects the polymer (A), so that the formed composite material is light stable and is not easily deteriorated. .

Example 1 Composite material

0.002 parts by weight of isophorone diisocyanate, 0.008 parts by weight of N,N'-bis(1,2,2,6,6-pentamethyl-piperidinyl)-1,6-hexanediamine, And 100 parts by weight of PP was uniformly mixed, and extruded by a twin-screw extruder, and the extrusion temperature was 180 ° C, and the main screw rotation speed was 100 rpm.

Examples 2 to 9

Examples 2 to 9 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.

Example 10

4 parts by weight of isophorone diisocyanate, 16 parts by weight of N,N'-bis(1,2,2,6,6-pentamethyl-piperidinyl)-1,6-hexanediamine, and 80 parts by weight of PP was uniformly 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 extrudate. The extrudate was again subjected to room temperature air cooling, 60 rpm pelleting, and 4 hour 100 ° C drying to form a dried product. 1 part by weight of the dried product and 100 parts by weight of PP are uniformly mixed, and extruded by a twin-screw extruder. The temperature was 180 ° C and the main screw speed was 100 rpm.

Examples 11 to 18

Examples 11 to 18 were prepared in the same manner as in Example 10 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 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.

In Comparative Example 2, the composite material was prepared in the same manner as in Comparative Example 1, except that the kind of the hindered amine light stabilizer (G) was changed. The types of the hindered amine light stabilizer (G) are shown in Table 3.

Comparative example 3

1 part by weight of the master batch is uniformly mixed with 100 parts by weight of PP, and extruded by a twin-screw extruder, the extrusion temperature is 180 ° C, the main screw rotation speed is 100 rpm, wherein the master batch is 20 parts by weight. The light stabilizer 944 was uniformly mixed with 80 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 example 4

Comparative Example 4 was prepared in the same manner as in Comparative Example 3 except that the kind of the polymer (A) was changed. The type of the polymer (A) is shown in Table 3.

Comparative Example 5

20 parts by weight of isophorone diisocyanate and 80 parts by weight a portion of N,N'-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,6-hexanediamine mixed and extruded by a twin-screw extruder The temperature was 180 ° C and the main screw was rotated at 100 rpm to form an addition product. The addition product was further subjected to room temperature air cooling, pelletizing at 60 rpm, and drying at 100 ° C for 4 hours to form a dried product. 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 6 to 18 were prepared in the same manner as in Comparative Example 5 except that the kind of the raw material was changed, and the kind of the raw material and the amount 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 18 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, and the tensile strength was measured, 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 Examples 1 to 9 of Table 1, it is understood that the polymer (A) is once mixed with the component (B) having a polyisocyanate group and the hindered amine component (C) having a reactive functional group, And the composite material formed by the addition reaction of the component (B) having a polyisocyanate group and the hindered amine component (C) having the reactive functional group in the mixing process is broken after 5,000 hours of calender irradiation. The elongation loss rate was 44.12% to 50.23%.

From the experimental data of Examples 10 to 18 of Table 2, it is understood that a part of the polymer (A) is first with the component (B) having a polyisocyanate group and a hindered amine component (C) having a reactive functional group. Mixing, and during the mixing process, the component (B) having a polyisocyanate group and the hindered amine component (C) having the reactive functional group are subjected to an addition reaction, and then the remaining polymer (A) is added. After 5,000 hours of calendering, the elongation loss of the composite was 30.12% to 65.12%.

From the experimental data of Comparative Examples 5 to 12 of Table 3, it is understood that the component (B) having a polyisocyanate group and the hindered amine component (C) having a reactive functional group are mixed and subjected to an addition reaction to form an addition product. Thereafter, the composite material formed by further adding the polymer (A) was subjected to 5,000 hours of calender irradiation, and the elongation at break value was 84.65% to 90.15%.

It can be seen from the above that the composite material obtained by the method for preparing a composite material of the present invention has a low loss rate of elongation at break after illuminating, so that the method for preparing the composite material of the present invention can make the composite material have better photostability. Furthermore, in the method for preparing a composite material of the present invention, the polymer (A) is divided into two additions, so that the loss rate of elongation at break after illuminating is lower, and the composite material has better light stability.

In summary, the polyisocyanate group-containing component (B) and the reactive functional group-containing hindered amine component (C) in the mixture are mixed while the additive composition is mixed with the polymer (A). The addition reaction is carried out to form an addition product, and the addition product is uniformly dispersed in the polymer (A), which in turn effectively protects the polymer (A), so that the formed composite material is light-stable, It is not easy to deteriorate, so the object of the present invention can be achieved.

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 (9)

A method for preparing a composite comprising the steps of: mixing a polymer and an auxiliary composition to form a mixture, wherein the auxiliary composition comprises a component having a polyisocyanate group and a hindered amine group having a reactive functional group And then subjecting the polyisocyanate group-containing component and the hindered amine component having a reactive functional group in the mixture to an addition reaction; the hindered amine component having a reactive functional group includes the formula (2) a hindered amine compound having a reactive functional group, 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 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 a cycloalkyl group to C ₁₀ , 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; each of R ⁷ and R ¹⁸ 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; R ¹⁹ and R ₂₄ are hydrogen, phenyl, C ₁ to C ₂₀ Linear alkyl group, C ₃ to C ₂₀ branched alkyl group, C ₄ to C ₇ cycloalkyl group, or benzyl group; Z ¹ is a C ₂ to C ₂₀ linear alkyl group, C ₂ to C ₂₀ branched alkylene, at least one -CH ₂ - is oxo substituted linear C ₂ to C ₂₀ alkylene group, and at least one -CH ₂ - is replaced with sulfur in the linear extending alkoxy C ₂ to C ₂₀ 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 C ₂ to C ₂₀ branched alkyl group substituted by sulfur, or a C ₂ to C ₂₀ branched alkyl group substituted with at least one hydrogen by a nitro group. The method for producing a composite according to claim 1, wherein a part of the polymer and the auxiliary composition are mixed to form the mixture, and the polyisocyanate group-containing component and the reaction in the mixture are obtained. The hindered amine component of the functional group is subjected to an addition reaction; subsequently, the remaining polymer is added. The method of preparing a composite material according to claim 2, wherein the portion of the polymer is used in an amount smaller than the amount of the remaining polymer. The method for producing a composite according to claim 1, wherein the reaction temperature of the addition reaction ranges from 130 ° C to 300 ° C. The method for producing a composite according to claim 1, wherein the component having a polyisocyanate group comprises a compound having a polyisocyanate group represented by the formula (1); 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, ,or A composite material obtained by the method for producing a composite material according to any one of claims 1 to 5. A method for preparing a composite comprising the steps of: mixing a polymer and an auxiliary composition to form a mixture, wherein the auxiliary composition comprises a component having a polyisocyanate group and a hindered amine group having a reactive functional group And then subjecting the polyisocyanate group-containing component and the hindered amine component having a reactive functional group in the mixture to an addition reaction; the hindered amine component having a reactive functional group includes the formula (5) a hindered amine compound having a reactive functional group; 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 and 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 a cycloalkyl group to C ₁₀ , 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; each of R ⁷ and R ¹⁸ 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; R ¹⁹ and R ₂₄ are hydrogen, phenyl, C ₁ to C ₂₀ Linear alkyl group, C ₃ to C ₂₀ branched alkyl group, C ₄ to C ₇ cycloalkyl group, or benzyl group; Z ³ is a C ₂ to C ₂₀ linear alkyl group, C ₂ to C ₂₀ branched alkylene, at least one -CH ₂ - is oxo substituted linear C ₂ to C ₂₀ alkylene group, and at least one -CH ₂ - is replaced with sulfur in the linear extending alkoxy C ₂ to C ₂₀ 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 C ₂ to C ₂₀ branched alkyl group substituted by sulfur, or a C ₂ to C ₂₀ branched alkyl group substituted with at least one hydrogen by a nitro group. The method for producing a composite according to claim 7, wherein the component having a polyisocyanate group comprises a compound having a polyisocyanate group represented by the formula (1); 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, ,or A composite material obtained by the method for producing a composite material according to any one of claims 7 to 8.