JPH02187437A - Polymer material composition having improved light resistance - Google Patents

Abstract

PURPOSE:To provide a polymer material composition having improved light resistance and suitable for agricultural materials, automotive coatings, etc., by compounding a specific light stabilizer with a polymer material in a specified ratio. CONSTITUTION:A benzophenone compound of formula III (R2 is 2-4C alkylene, etc.; R3 and R4 are H, halogen, etc.; X and Y are H, halogen, etc.) is compounded with a polymer material in an amount of 0.001-5 pts.wt., preferably 0.01-3 pts.wt., per 100 pts.wt. of the polymer material to contrive the improvement of the light resistance of the resin. The compound of formula III is prepared, for example, by addition-reacting a compound of formula I (R1 is 1-8C alkyl, alkoxy, etc.; n is 0-3) to 2-(2-hydroxy-3-alkenyl-4-alkoxybenzophenone compound in the presence of a catalyst such as platinic chloride at 30-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymer material composition with improved light resistance, and more particularly, the present invention relates to a polymer material composition with improved light resistance over a long period of time by adding a specific 2-hydroxybenzophenone compound. Relating to molecular material compositions.

It is known that polymer materials such as polyethylene, polypropylene, styrene resins, and polyvinyl chloride deteriorate due to the action of light, causing discoloration or a decrease in mechanical strength, and thus cannot withstand long-term use.

Therefore, in order to prevent the deterioration of polymeric materials, various light stabilizers have been conventionally used. As these light stabilizers, hindered amine light stabilizers, benzophenone-based or benzotriazole-based ultraviolet absorbers are mainly used, and 2-hydroxybenzophenone-based ultraviolet absorbers in particular have a large stabilizing effect. , widely used.

However, conventionally used benzophenone compounds have poor heat resistance, and may volatilize during processing of polymeric materials or when used at high temperatures, or
It has the disadvantage of being easily extracted by organic solvents, and is unsatisfactory in practical terms.

For this reason, attempts have been made to improve the volatility of light stabilizers by increasing their molecular weight; for example, it has been proposed to use polymers made by polymerizing compounds having vinyl groups and acrylic ester bonds. The volatility has been improved to some extent. However, such polymers have poor dispersibility in polymer materials such as synthetic resins, and almost no movement occurs in the resin, so they have the disadvantage that they are difficult to fully demonstrate their effects. It couldn't be practical.

In addition, dimeric compounds in which two molecules of 2-hydroxyphenylbenzophenone compounds are bonded with aldehydes such as formaldehyde and octylaldehyde have also been proposed as low-volatility ultraviolet absorbers; However, it has the disadvantage that it cannot satisfactorily demonstrate its effectiveness under harsh conditions such as during high-temperature processing.

In view of the above-mentioned current situation, the present inventors have conducted intensive studies to obtain a new type of high molecular weight light stabilizer, and have found that a compound represented by the following general formula (I) has excellent heat resistance, The present invention was achieved by discovering that long-term weather resistance can be imparted to polymeric materials such as synthetic resins even under severe processing conditions.

That is, in the present invention, 0.001 to 0.001 of the siloxane compound represented by the following formula (I) is added to 100 parts by weight of the polymeric material.
The object of the present invention is to provide a polymeric material composition with improved light resistance, which is obtained by adding 5 parts by weight.

[Wherein, R represents a group represented by the following formula (n), R8 represents an alkyl group, an alkoxy group, or a phenyl group having 1 to 8 carbon atoms, and n represents 0 to 3.

(X and Y each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkylene group, R1 is an alkylene group having 2 to 4 carbon atoms, and oxyalkylene group R" is a carbon atom number. 2 to 4 alkylene groups, R" represents a hydrogen atom or a methyl group. R3 and R4 each represent a hydrogen atom, a halogen atom, a hydroxyl group, or a carbon atom number of 1 to 1.
8 shows an alkyl group or an alkoxy group. )] Hereinafter, the present invention having the above-mentioned summary will be described in detail.

In the above formula, examples of the alkyl group represented by R include methyl, ethyl, propyl, isopropyl, butyl,
Examples include nibutyl, isobutyl, amyl, octyl, etc., and examples of the alkoxy group include alkoxy groups derived from the above-mentioned alkyl groups. Examples of the alkylene group represented by R2 include Eva, ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-
Examples include butylene, 1,4-butylene, 2-methyl-1,3-propylene, and the like. Examples of the alkyl group represented by R1 and R4 include methyl, ethyl, propyl, butyl, nibutyl, isobutyl, amyl, hexyl, octyl, decyl, lauryl, palmityl, myristyl, stearyl, and benzyl. Examples of the alkoxy group include an alkoxy group derived from the alkyl group described above. Examples of the alkyl group or alkoxy group represented by X and Y include the alkyl group or alkoxy group represented by R1 and R4 described above. Examples of halogen atoms include chlorine atoms, bromine atoms,
Examples include fluorine atoms.

The compound represented by the above general formula (I) can be easily produced by, for example, the method described above.

2-Hydroxy-3-alkenyl-4 used for producing the compound represented by the above-mentioned Monka (I) of the present invention
-As the alkoxybenzophenone compound, for example,
The following compounds can be mentioned.

(2-Hydroxy-3-alkenyl-4-alkoxybenzophenone compound is mixed with toluene, hexane, octane, isopropanol, tetrahydrofuran, dioxane, etc. as necessary in the presence of chloroplatinic acid or a siloxane-based catalyst. Addition reaction is carried out in a solvent inert to the reaction or in the absence of a solvent t ■ Hydrolysis is carried out after reacting with R+ hydroxy-3-alkenyl-4-alkoxybenzophenone compound CHt The reaction is carried out in the range from room temperature to about 200°C. The temperature is preferably selected from 30°C to 100°C.

Next, a specific synthesis example of the compound represented by the above-mentioned Monna (III) used in the present invention will be given, but the present invention is not limited by the following synthesis example.

Synthesis example-1 Nasuyu J and Kanagi A pale yellow solid was obtained at ~97°C.

As a result of infrared spectroscopy, there is an absorption at 1625 cm-'.
In addition, as a result of NMR analysis, 0.12 ppm 5t-CH
t 12 H, 3,39 ppm -0-CHt-48,
There was a peak at 12.53 ppmφ-O2H, confirming that it was the target product.

Synthesis example-1 2-hydroxy-4-allyloxybenzophenone 17
．． 8 g of xylene was dissolved in 17 g of xylene, 4.7 g of tetramethyldisiloxane and 110 cm of a siloxane-based platinum catalyst manufactured by Dow Corning were added, and the mixture was stirred at 95 to 100°C for 7 hours.

After confirming the completion of the reaction by high performance liquid chromatography, the solvent was removed under reduced pressure. The obtained crude product was crystallized from methanol to give a melting point of 932-hydroxy-3-
Besides using 11.0 g of allyl-4octyloxybenzophenone and 2.1 g of tetramethyldisiloxane,
A viscous pale yellow liquid was obtained in the same manner as in Example 1.

As a result of infrared spectroscopy, there is an absorption at 1620 cm-'.
Also, as a result of NMR analysis, 0.07 ppn+ 5t-C
Hs 12 H, 2,73 ppm φ-CL-4H
,4,0ppm -0-CHz-4H,12,62p
There was a peak at pm φ-OH2H, confirming that it was the target product.

The following compound was synthesized by the same operation as in the above synthesis example.

The present invention uses the above-mentioned specific 2-hydroxybenzophenone compound as a light stabilizer for polymeric materials, and the amount added is not particularly limited.
The amount is usually 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight.

Examples of polymeric materials whose stability is to be improved in the present invention include high-density, low-density, or linear low-density polyethylene, polypropylene, polybutene-1, poly-3
- α-olefin polymers such as methylpentene or polyolefins such as ethylene-vinyl acetate copolymers and ethylene-propylene copolymers, and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene,
Chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer , halogen-containing resins such as vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexylmaleimide copolymer, vinyl chloride-cyclohexylmaleimide copolymer, petroleum resin , copolymerization of coumaron resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and/or α-methylstyrene with other monomers (e.g., maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) coalescence (for example, As resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.), polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, linear polyesters such as polyethylene terephthalate and polytetramethylene terephthalate, polyphenylene oxide, polycaprolactam and thermoplastic synthetic resins such as polyamides such as polyhexamethylene aziboamide, polycarbonates, polyacetals, polyphenylene sulfides, polyurethanes, cellulose resins, and blends thereof, phenolic resins, urea resins, melamine resins, epoxy resins, Examples include thermosetting resins such as saturated polyester resins. Furthermore, elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber may be used.

In the composition of the present invention, other general-purpose additives such as antioxidants and stabilizers can be used together with the compound represented by the above-mentioned formula (I).

Particularly preferable examples of these additives include phenol-based, sulfur-based, phosphite-based antioxidants, and hindered amine-based light stabilizers.

As the above-mentioned phenolic antioxidant, for example, 2.6-
di-tert-butyl-p-cresol, 2,6-diphenyl-
4-octadecyloxyphenol, stearyl (3,5
-di-tert-butyl-4-hydroxyphenyl)-propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis((3,5-di-tert-butyl-4-hydroxyphenyl) propionate) L 1,6-hexamethylenebis((3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 1,6-hexamethylenebis((3,5-di-tert-butyl-4-hydroxyphenyl)
propionic acid amide], 4°4°-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(
4-Methyl-6=tert-butylphenol L2,2°-methylenebis(4-ethyl-6-tert-butylphenol)
, bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid coglycol ester, 4.4'-butylidene bis(6-tert-butyl-m-cresol), 2.2'- Ethylidene bis(4,6-ditert-butylphenol), 2,2'-ethylidene bis(
4-Sec-butyl-6-tert-butylphenol), 1
．． 1.3-) Lis(2-methyl-4-hydroxy-5-
tert-butylphenyl)butane, bis(2-tert-butyl-
4-methyl-6-(2-hydroxy-3-tert-butyl-
5-Methylbenzyl)phenyl]terephthalate, 1,
3.5-)Lis(2,6-dimethyl-3-hydroxy-
4-tert-butylbenzyl) isocyanurate, 1,3.
5-) Lis(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1.3.5-Tris(3,
5-ditert-butyl-4-hydroxybenzyl)-2,4
, 6-trimethylbenzene, 1,3.5-)lith[(3
゜5-Ditert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[
Methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate comethane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methyl benzyl)phenol, 3,9-
Bis[1゜1-dimethyl-2-((3-tert-butyl-4
-hydroxy-5-methylphenyl)propionyloxy)ethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, triethylene glycol bis[
(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] and the like.

Examples of the sulfur-based antioxidants include dialkyl thiodipropionates such as dilauryl thiodipropionate, simiristyl, and distearyl, and β-alkyl thiodipropionates of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Examples include mercaptopropionate esters.

In addition, examples of the phosphite-based antioxidants include:
Trisnonylphenyl phosphite, tris(2,4-
di-tert-butylphenyl) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5
-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di(decyl) monophenyl phosphite, di(tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite , di(nonylphenyl)pentaerythritol diphosphite, bis(2,4-ditert-butylphenyl)pentaerythritol diphosphite, bis(2,6-ditert-butyl-4-methylphenyl)pentaerythritol diphosphite phyto, tetra(tridecyl)isopropylidenediphenol diphosphite, tetra(tridecyl)-
4,4”-n-butylidene bis(2-tert-butyl-5-
methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2゜4-di-tert-butylphenyl)biphenylene Examples include range phosphonite, 9.10-cybide-rho-9-oxer-10-phosphaphenanthrene-10-oxide, and the like.

Examples of the hindered amine light stabilizers include 2.2,6.6-tetramethyl-4-piperidylbenzoate, N-(2,2,6°6-tetramethyl-4
-piperidyl)dodecylsuccinimide, 1-((3,
5-ditert-butyl-4-hydroxyphenyl)propionyloxyethyl)-2,2,6,6-tetramethyl-
4-piperidyl-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis(2,2°6.6
-tetramethyl-4-piperidyl) sebacate, bis(
1,2,2,6,6-bentamethyl-4-piperidyl)
Sebacate, bis(1,2゜2.6.6-bentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, N,
N''-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, tetra(2,2゜6
．． 6-tetramethyl-4-piperidyl)butane tetracarboxylate, tetra(1,2,2゜6.6-bentamethyl-4-piperidyl)butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4 -piperidyl) di(tridecyl)butanetetracarboxylate, bis(1゜2.2.6.6-bentamethyl-4-piperidyl)di(tridecyl)butanetetracarboxylate, 3.9-bis[1,1- Dimethyl-2-(tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy)butylcarbonyloxy)ethyl]-2.4,8.10-tetraoxaspiro(5,5
) undecane, 3,9-bis[1,1-dimethyl-2-
(tris(1,2゜2.6.6-bentamethyl-4-piperidyloxycarbonyloxy)butylcarbonyloxy)ethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 1,5, 8.12-tetrakis[4,6-bis(N-(2,2,6,6-tetramethyl-4-piperidyl)butylamino)-1,3,5-)
riazin-2-yl)-1,5゜8.12-tetraazadodecane, 1-(2-hydroxyethyl)-2,2,6
, 6-tetramethyl-4-piperiditul/dimethyl succinate, 2-tertiary octylamino-4,6-dichloro-8-triazine/N,N'-bis(2,2,6,
6-tetramethyl-4-piperidyl)hexamethylenediamine condensate, N,N'-bis(2,2,6゜6-tetramethyl-4-piperidyl)hexamethylenediamine/
Examples include dibromoethane condensates.

In addition, if necessary, the composition of the present invention may contain heavy metal deactivators, nucleating agents, metal soaps, organotin compounds, plasticizers, epoxy compounds, blowing agents, antistatic agents, flame retardants, lubricants, processing aids, etc. Agents, etc. can be included.

The polymeric material stabilized by the present invention is particularly useful in fields that require a high degree of light resistance, such as agricultural materials and automotive paints. Binders for materials, paints and lacquers,
It can be used for adhesives, putty, base materials in photographic materials, etc.

〔Example〕

Next, the present invention will be specifically explained using examples.

Example 1 A pellet was produced by extrusion processing at 250°C using the following formulation. Then injection molded at 250°C,
A test piece with a thickness of 1 mm was prepared. Regarding this test piece,
A light resistance test was conducted using a high-pressure mercury lamp. Also, 8
A similar test was conducted on the test piece after immersing it in hot water at 0°C for 48 hours.

The results are shown in Table 1 below.

Blend> Polypropylene (Profax 6501) 10
0 parts by weight Calcium stearate 0.
1 Sample Compound (See Table-1) 0.25 Table-1 Note 2 In Table-1 above, Comparative Compound 1 and Comparative Compound 2 are as follows. (The same applies to Tables 2 to 6 below) Comparative compound 1 2-hydroxy-4-n-octoxybenzophenone Comparative compound 2 1.4-bis(4-benzoyl-3-hydroxyphenoxy)butane Example 2 This implementation In this example, we looked at changes in the stabilizing effect of high-temperature processing by repeating extrusion processing.

A compound was prepared by mixing the resin and additives in a mixer for 5 minutes and then extruding at 250°C according to the following formulation. After repeating extrusion 10 times, 250°
A test piece was prepared by injection molding. Using the obtained test piece, a light resistance test was conducted using a high-pressure mercury lamp. Also,
Compounds extruded once and extruded five times were similarly tested. The results are shown in Table-2.

<Formulation> Ethylene-propylene copolymer resin 100 parts by weight Calcium stearate 0. 2 Dilauryl thiodipropionate 0.2 Sample compound (see Table-2) 0.2 Table-2 Polyethylene 100 parts by weight Calcium stearate 1.5 Sample compound (see Table-3) Table-3 0,1 Example 3 Using the following formulation, the mixture was kneaded and then pressed to a thickness of 0.
Test specimens were prepared for five gardens. Using this test piece, the light resistance was measured in a weatherometer, and the time until embrittlement was measured.

The results are shown in Table 3.

Blend> Example 4 The following blend was extruded at 260°C to create pellets, and then injection molded at 260°C to create a test piece with a thickness of 1 ml. Using this test piece, 8
A weather resistance test was conducted using a 3°C sunshine weatherometer (no rain), and the color difference after 400 hours of irradiation was measured.

The results are shown in Table 4 below.

Table 4 Calcium stearate 0.4 Titanium dioxide sample compound (see Table 4) 0.5 0.5 Example 5 The following formulation was kneaded on a roll at 70°C for 5 minutes, and 12
A test piece with a thickness of 0.5 mm was prepared by pressing at 0°C for 5 minutes. Using this test piece, the residual elongation rate after irradiation for 50 hours and 100 hours was measured using a fade meter.

The results are shown in Table-5.

Blend> Polyurethane resin 100 parts by weight (Asahi Denka tJ-100) Barium stearate zinc stearate sample compound (see Table-5) Table-5 0, 65 0, 35 0° thickness 0.1+nn film was prepared did. A test piece was cut from this film and subjected to a weather resistance test using a weatherometer.

The results are shown in Table-6.

Blend> Vinyl chloride resin (degree of polymerization 1,000) 100 parts by weight Dioctyl phthalate 47 Epoxidized soybean oil 3 Zinc stearate
0. 8 ether sorbitan monopalmitate sample compound (see Table 6) 0゜Example 6 Using the following formulation, the mixture was kneaded using a kneading roll. It is clear that when a specific benzophenone compound is used, the stabilizing effect is significantly greater than when the previously known monomeric or dimeric compounds are used.

Claims (1)

[Claims] The following general formula (I) is applied to 100 parts by weight of the polymeric material.
A polymer material composition with improved light resistance, which contains 0.001 to 5 parts by weight of a benzophenone compound represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R represents a group represented by the following formula (II), and R_1
represents an alkyl group, an alkoxy group, or a phenyl group having 1 to 8 carbon atoms, and n represents 0 to 3. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (X and Y each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group, and R_2 represents a group having 2 to 18 carbon atoms. 4 alkylene group,
Oxyalkylene group formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼, R' represents an alkylene group with 2 to 4 carbon atoms, and R'' is a hydrogen atom or methyl represents a group. R_3 and R_4 each represent a hydrogen atom, a halogen atom, a hydroxyl group, and a carbon atom number of 1.
~18 alkyl group or alkoxy group. )〕