JPH0331342A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition having excellent thermal aging resistance and weather resistance and useful for the exteriors of cars, hollow containers, sheet molding materials, etc., by adding a specific nitrogen-containing stabilizer, a phenolic stabilizer, a phosphorous stabilizer and a hindered amine stabilizer in a specified ratio to a polyolefin resin. CONSTITUTION:(A) 100 pts.wt. of a polyolefin is compounded with (B) a phenolic stabilizer and (C) compounds of formulas I, II and III (R1 and R2 are 1-8C alkyl or group of formula IV or V; R<3> and R<4> are H or 1-6C alkyl; R<5> is group of formula VI; R<6> is 1-6C alkyl or branched alkyl; A is group of formula VII, etc.; B is group of formula VIII, etc.; R<7> is 1-18C alkyl, 5-8C cycloalkyl, etc.; R<8> is H or 1-8C alkyl; R<9> is H or 1-4C alkyl; R<10> is H or 1-18C alkyl; a is 1-4; when a is 1, Z is 1-18C alkylene; when a is 2, Z is 1-18C alkylene, etc.) in a weight ratio of 1:0.5-15:0.5-15:0.5-15, respectively, in the total amount of 0.03-3 pts.wt. to provide the objective composition.

Description

[Detailed Description of the Invention] [Background of the Invention] [Industrial Field of Application] The polyolefin resin composition of the present invention, which contains various stabilizers, has excellent heat aging resistance and weather resistance, and is suitable for use in automobile exterior materials, hollow spaces, etc. It is useful as a container, sheet molding material, etc.

<Prior art> Polyolefin resins have excellent physical, chemical, and electrical properties, so they can be made into containers, pipes, sheets, etc. by extrusion molding, injection molding, blow molding, etc.
It is processed into films, fibers, etc. and used in a wide range of fields.

However, polyethylene, polypropylene, and
When used alone, polyolefin resins such as copolymers undergo oxidative deterioration relatively easily due to the effects of heat and light in the presence of oxygen during molding or use, resulting in softening and brittleness. It is also known that along with phenomena such as discoloration, the physical properties deteriorate significantly, making it difficult to withstand various uses. For this reason, improved techniques using various antioxidants or combinations of antioxidants have been developed.

For example, in order to improve the heat aging resistance of polyolefin resins, there is a technique (Japanese Unexamined Patent Publication No. 47-25234) in which hindered phenol-based, sulfur-based, or phosphorus-based antioxidants are added to polyolefin resins, either alone or in combination. (see official bulletin) is known.

On the other hand, in order to improve the weather resistance of polyolefin resins, ultraviolet absorbers such as benzophenone and benzotriazole, or hindered amine light stabilizers (HALS) are used.
) etc. are known to be blended into polyolefin resins (see Japanese Patent Publication No. 47-25234).

However, a drawback is that there is an antagonistic effect between certain antioxidants and light stabilizers.

For example, in order to improve both the heat aging resistance and weather resistance of polyolefin resin, when a sulfur-based antioxidant and HALS are used together, compared to when HALS is used alone,
It is known that a phenomenon occurs in which weather resistance is significantly reduced.

[Summary of the invention]

Summary> As a result of intensive studies aimed at improving the heat aging resistance and weather resistance of polyolefin resins, the present inventors have found that the nitrogen-based stabilizers represented by the following general formula (1) or (II) We have discovered that by using a phenolic stabilizer, a phosphorus stabilizer, or a hindered amine stabilizer in combination with a polyolefin stabilizer, a polyolefin resin composition can be obtained that has an extremely excellent stabilizing effect that was not achieved using conventional techniques. The present invention has now been completed.

That is, the polyolefin resin composition of the present invention contains 100 parts by weight of a polyolefin resin, a phenolic stabilizer, a nitrogen stabilizer represented by the following general formula (1), (II), or (III), a phosphorus stabilizer, and Hindered amine stabilizer 1:0.5-15:0.5-15:0.5-15 (
It is characterized in that it is used in combination at a ratio of 0.03 to 3 parts by weight (weight ratio).

4 [R1 and R- in the above formula (1) are the same or different alkyl groups having 1 to 18 carbon atoms, 0
A group represented by 0, in which R
6 is an alkylene group having 1 to 6 carbon atoms or an alkylene group having a branch, B is an O atom or an S atom, and R8 in -N- is an H atom or an alkyl group having 1 to 18 carbon atoms; Further, R9 represents an H atom, an alkyl group having 1 to 4 carbon atoms, or an oxyl group.

In addition, R3 and R4 in the above formulas (I) to (III) represent the same or different H atom or an alkyl group having 1 to 6 carbon atoms.

Furthermore, A in the above formula is 0 atom, S atom, or a group containing carbon atoms, and R7 is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an aryl group, an alkylaryl group, or an aryl group. Represents an alkyl group. R10 in the formula
is an H atom, an alkyl group having 1 to 18 carbon atoms, -R6-C-
Represents a group represented by B-R7 or 1-R-B-C-R7.

Furthermore, R5 in the above formulas (If) and (III) is -R
When a is 1, 2 is an alkyl group having 1 to 18 carbon atoms, and when a is 2, it is a group represented by 6-C-B-, and a is an integer of 1 to 4. 1 to 18 alkylene groups, a group represented by -Ca- or -Ba-, a
is 3 (n in the formula represents an integer of 1 to 4 and represents the group shown in Table H2) Effect> The polyolefin resin composition of the present invention contains a phenolic stabilizer, By blending a nitrogen-based stabilizer, a phosphorous-based stabilizer, and a hindered amine-based stabilizer in a specific amount in a specific combination ratio, the chemical bonds of the polyolefin resin are stabilized by the interaction of these stabilizers, and the polyolefin resin composition is improved. It can prevent oxidative deterioration of the polyolefin resin due to the action of heat and light in the presence of oxygen, and can prevent embrittlement and discoloration of the polyolefin resin composition for a longer period of time than when it is used alone.

[Detailed description of the invention]

(1) Polyolefin resin The polyolefin resin used in the polyolefin resin composition of the present invention includes low density polyethylene, medium density polyethylene, linear low density polyethylene, polypropylene, polybutene-1, ethylene/propylene random or block copolymer, ethylene/propylene random or block copolymer, α-olefins alone or copolymers such as butene-1 random copolymers,
Examples include ethylene/vinyl acetate copolymers, copolymers of α-olefins with other vinyl monomers such as maleic anhydride-modified polypropylene, and mixtures thereof, among which propylene polymers, especially propylene homopolymers It is particularly effective against .

Incidentally, the stabilizer system used in the present invention is also effective for synthetic polymers other than polyolefin resins.

Examples of such synthetic polymers include polyvinyl chloride,
Styrenic resins such as methacrylic resin, polystyrene, high impact polystyrene, ABS resin and AES resin, polyester such as polyethylene terephthalate and polybutylene terephthalate, polyamide, polycarbonate, polyacetal, polyethylene oxide, polyphenylene ether, polysulfone, polyurethane, unsaturated Examples include polyester resin. It can also be applied to natural polymers such as cellulose, rubber, protein, cellulose acetate, etc. or derivatives thereof, and natural organic compounds such as mineral oils, animal and vegetable oils, and waxes.

(11) Stabilizer - Phenolic stabilizer> The phenolic stabilizer used in the polyolefin resin composition of the present invention generally has at least one of the ortho positions of the hydroxyl group substituted with an alkyl group, an aralkyl group, or a cycloalkyl group. A monovalent or polyhydric phenol compound is desirable.

This substituent preferably has about 3 to 10 carbon atoms, and the alkyl group (including that in aralkyl and cycloalkyl groups) may be unsaturated. This phenol compound may have other substituents in addition to the above-mentioned substituents, and may have a structure such as bisphenol in which a phenol nucleus is connected with a linking group such as an alkylene group.

Specific examples of such phenolic antioxidants include:
2.6-di-t-butyl-p-cresol, 2.6. −
Diisobonyl-p-cresol, 2.6. -Bis(2-
p-cresol (phenylisopropyl), 2,6. -di-t-4-nonylphenol, n-octadecyl-β-
(3,5-di-t-4-hydroxy-phenyl)propionate, 2,2'-methylenebis(4-ethyl-
6-t-butylphenol), 2.2'-methylenebis(4-methyl-6-α-methylcyclohexylphenol), 4.4'-methylenebis(2t-butyl-5-methylphenol), 4.4'-methylenebis (2,6-di-t-butylphenol), 4.4'
-butylidenebis(2-t-butyl-5-methylphenol), 4.4'-butylidenebis(2-isopropyl-5-methylphenol), tris(4-t
-butyl-2,6-di-methyl-3-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5,
-di-t-butyl-4-hydroxybenzyl)-2,4
゜6-Dolimethylbenzene, 3.9-(bis1.1-di-methyl-2-(β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl)-2, 4,8,10-tetraoxaspiro(5,5)
Undecane, ethylene glycol-bis-f3,3-bis-(3-t-butyl-4-hydroxyphenyl)butyrate, 1°1.3-)lis-(5-t-butyl-4-
Examples include hydroxy-2-methylphenyl)butane, tetrakis(3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionyloxymethylcomethane), and the like.

Nitrogen Stabilizer> The nitrogen stabilizer used in the polyolefin resin composition of the present invention is represented by the following general formula.

a cycloalkyl group having 5 to 8 carbon atoms, or an aryl group,
Alkylaryl group, arylalkyl group [the above formula (I
), R1 and R2 have the same or different carbon numbers of 1 to
18 alkyl groups, 0
0, in which R6 is an alkylene group having 1 to 6 carbon atoms or a branched alkylene group, and B
is O atom, S atom, -N-, R8 is H atom,
An alkyl group having 1 to 18 carbon atoms, and R9 is an H atom,
Represents an alkyl group having 1 to 4 carbon atoms or an oxyl group.

In addition, R3 and R4 in the above formulas (1) to (III) represent the same or different H atom or an alkyl group having 1 to 6 carbon atoms.

Furthermore, A in the above formula represents 0 atom, an S atom, an alkylene group having 1 to 3 carbon atoms, or a 10 group represented by -N-. R10 in this formula is an H atom, having 1 to 18 carbon atoms.
An alkyl group, -R6-C-B-R7 or a group represented by 1, where R7 represents an alkyl group having 1 to 18 carbon atoms, a group represented by 6-R-B-C-R7.

1 Also, The above formula () () represents a group represented by

] Examples of typical compounds of such nitrogen-based stabilizers are as shown below in the form of an integer of 1 to 4, and 2 is an integer of 1 to 4 carbon atoms.

18 alkyl groups, When a is 2, the number of carbon atoms is 1~ (No.

1) The alkylene group of 18, a group represented by -Ca- or -Ba-, when a is 3, is represented by N, N'-bis[2-(tetradecyloxycarbonyl)ethylcopiperazine (NOo 2) Group (n in the formula represents an integer of 1 to 4. N'-bis[2-(octadecyloxycarbonyl)ethylcopiperazine (NO8 3)

6) N, N’-Bis [2- Circopiperazine (methoxycarbonyl) (No.

4) N,N'-bis[2-(tetradecyloxycarbonyl)ethyl)-2,5-dimethylpiperazine (N
o.

7) CH3CH3 N, N'-bis[2-(tetradecyloxycarbonyl)-1-methylethylcopiperazine N,N'-bis(2-()lysozylcarboxy)ethylcopiperazine (NOo 5) N, N ' -Bis[2-(tetradecyloxycarbonyl)methyl]piperazine (No, 8) (No, 10) Tetrakis(3-morpholinopropionyloxymethyl)methane (No, 11) N,N' -Bis(2-( 2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)ethylcopiperazine (No, '9) Tetrakis(3-(4-[2(tetradecyloxycarbonyl)ethyl]piperazinyl)propionyloxymethylcomethane (No. 12) Tetrakis(3-piperidinopropionyloxymethyl)methane N,N'-dioctadezylbiverazine (No.
13) Tetrakis(3-pyrrolidylpropionyloxymethyl)methane phosphorus stabilizer> The phosphorus stabilizer used in the polyolefin resin composition of the present invention is an organic stabilizer represented by the following general formula (■) or (V). Preferably, it is a phosphorus compound.

(In the formula, R and R12 are monovalent alcohol residues, -valent phenol residues, or monovalent thiol residues that may have substituents, and may be the same or different. b is an integer from 1 to 12.X
When l is b-1, it is a halogen atom, a group defined for R11 above, an aryloxy group having a substituent, or an aryl group or an alkaryl group which may have a substituent, and b When ≧2, Xl is a hydrocarbon group having 1 to 30 carbon atoms that may contain an ether bond, a polyhydric alcohol residue, or a polyhydric phenol residue. ) (in the formula, R13 is an alkyl group which may have a substituent,
Even if it is a cycloalkyl group, aryl group, alkaryl group or aralkyl group, and the two R13s are the same,
It doesn't matter if they are different.

Yl has 1 to 20 carbon atoms and may contain an ether bond
is a tetravalent hydrocarbon group. ) In the above general formula (IV), for example, R and RI2 in the formula are an alkoxy group, a cycloalkylsushi group, an aryloxy group, an alkaryloxy group, an aralkyloxy group, an alkylthio group, and RII
and R12 are directly or alkylene group, sulfur atom,
They may be bonded through oxygen atoms or the like to form a cyclic structure.

Specific examples of such phosphorus stabilizers include distearyl pentaerythritol diphosphite, tris(2
, 4-di-t-butylphenyl) phosphite, tris(2-1-butyl-4-methylphenyl) phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis( 2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite, 4,4'- Butylidene-bis(2-t-butyl-5
-methylphenyl)-di-tridecyl phosphite, 2
．． 2'-ethylidene-bis(4,6-di-t-butylphenyl)fluorophosphite, trilauryl-
Trithio-phosphite, etc. can be mentioned.

Hindered Amine Stabilizer> Among those used as light stabilizers, the hindered amine stabilizer used in the polyolefin resin composition of the present invention is preferably a piperidine derivative represented by the following general formula (v). In the formula, substituent R14 is
hydrogen or an alkyl group which may have a substituent,
represents an acyl group or a benzyl group, R15 is an aliphatic group,
It refers to acyl groups derived from aromatic or heterocyclic carboxylic acids (including polyhydric carboxylic acids), and monovalent or polyvalent groups obtained by removing hydroxyl groups from oxyacids such as phosphorous acid. Further, R14 and R15 may be constituent components of the polymer main chain.

c RlB is a hydrogen atom, an alkyl group, an aryl group, a group derived from a heterocycle, or a constituent component of the polymer main chain, and these groups may have a substituent).

As a specific example, 2. 2. 6.6-Tetramethyl-
4-piperidylbenzoate, bis(2,2゜6.6-
Tetramethyl-4-piperidyl) sebacate, 2-(3
,5-di-t-butyl-4-hydroxybenzyl)-2
-n-butyl-malonate bis(1,2,2,6,6-bentamethyl-4-piperidyl), 1-(2-D-
(3,5-di-t-butyl-4-hydroxyphenyl)
propionyloxy)ethyl)-4-(3-(3,5-
di-t-butyl-4-hydroxyphenyl)propionyloxy)-2,2,6,6-titramethylbiperidine, dimethyl succinate 1-(2-hydroxyethyl)-4-hydroxy-2,2, 6,6-titramethylpiveridine polycondensate, tris(1゜2.2,6.6-bentamethyl-4-biveridylnophosphite, poly((
6-(1,1,3,3-tetramethylbutylimino)-
1,3,5-triazine-2,4-diyl)((2,2
,6,6tetramethyl-4-piperidyl)imino]hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], poly[[6-morpholino-2
,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene((2,2
,6,6-tetramethyl-4=piperidyl)imino))
, 1,8.1'-tris[4,6-pis1N-nonyl-N-(2,2,6°6-tetramethyl-4-piperidyl)amino)1.3.5-)lyazine-2- Examples include yl-aminoco-4-methyloctane.

Other additives> The polyolefin resin composition of the present invention may contain other additives, such as ultraviolet absorbers, light stabilizers, metal deactivators, metal soaps, nucleating agents, lubricants, antistatic agents, and flame retardants. , pigments and fillers.

In particular UV absorbers, such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2 (2'hydroxy-5'
-methylphenyl)benzotriazole, 2(2'-hydroxy-3'-t-butyl-5'-methylphenyl)
-5-chloro-benzotriazole, 2(2-hydroxyl-3'5'-di-t-butylphenyl)-5-chloro-benzotriazole, 2(2'-hydroxy-3', 5'-di-amyl The light resistance can be further improved by adding phenyl)benzotriazole, [2,2'-thiobis(4-t-octylphenolate)]butylamine Ni salt, or the like.

(111) Produced quantity ratio of composition> In the polyolefin resin composition of the present invention, a phenolic stabilizer, general formula (1), (II) or (III)
The total amount of the nitrogen stabilizer, phosphorus stabilizer, and hindered amine light stabilizer (HALS) represented by is 0.03 to 3 parts per 100 fflf parts of the polyolefin resin.
It is important that the amount is by weight, preferably from 0.05 to 1 part by weight. In addition, the general formula for phenolic stabilizers (
The combined Mf ratio of the nitrogen stabilizer, phosphorus stabilizer, and HALS (1), (II), or (III) is 0.5 to 15, preferably 0.1 to 1 of the phenolic stabilizer.
It is 5-6.

Compounding> The polyolefin resin composition of the present invention can be produced by blending and kneading the above-mentioned components using a common kneading machine such as a roll or an extruder, and the obtained product can be used in various molding materials. can be trusted.

The following Examples and Comparative Examples are provided to further specifically explain the present invention.

[Experiment example]

<Example 1> The intrinsic viscosity measured in tetralin at 135°C is 1.9,
Each additive shown in Table 1 was blended with 100frR parts of polypropylene powder with 98% isotactic content.
Mix thoroughly with a mixer.

And cylinder temperature 260℃, L/D angle 20゜20m
The mixture was melt-kneaded and granulated using an m-diameter extruder.

The pellet thus obtained was heated to a thickness of 0.5++ at 230°C.
It was compression molded into a +m sheet and used as a test piece.

Heat aging resistance was measured by heating a test piece in a circulating air oven at 150° C. and measuring the time required for the test piece to brown and become brittle due to oxidative deterioration.

Weather resistance was measured using an Atlas 65/XW-WR xenon weather meter at a black panel temperature of 80.
The time required for the test piece to become brittle and crack when the test piece was irradiated with light at ℃ and bent at 180 degrees was determined as n1.

The results were as shown in Table 1.

The abbreviations in the table are as follows.

Sulfur-based antioxidant> DMTDP: Similistyl thiodipropionate Phenol-based antioxidant> F-1= Tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethylcomethane) (Product name: Irganox 1010) F-2= Tris(4-t-butyl-2,6-di-methyl 3-hydroxybenzyl) isocyanurate (Product name: Cy
anox 1790)F-3=3.9-(bis1.1-di-methyl-2-(β(3-t
-Butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl] -2゜4.8.10-tetraoxaspiro(5,5)undecane (Product name: )IARK AO-80) Phosphorous oxidation inhibitor Agent> P-1: Distearylbentaerythritol diphosphite (trade name: %eston 018) P-2= Tris(2,4-di-t-butylphenyl)phosphite (trade name: Irgaphos 168) hindered amine type Light stabilizer (HALS) > H-1 = Bis(2,2,6,6,-tetramethyl-4-piperidinyl) sebacate (trade name: 5anol LS770) H-2: Poly((6-(1,1 ,3,3,-tetramethylbutylimino)-1,3,54 riazine-2゜4-diyl)(
(2,2,6,6,-tetramethyl-4-piperidyl)
Imino] Hexamethylene ((2,2,6,6,~tetramethyl-4-piperidyl)imino) (Product name: 5anol LS944) Nitrogen stabilizer> (No, 1) N, N'-bis[2- (Tetradecyloxycarbonyl)ethylcopiperazine (No.

2) N,N'-bis[2-(octadecyloxycarbonyl)ethylcopiperazine (No.

3) N,N'-bis[2-(methoxycarbonyl)ethylcopiperazine (NOl (NOl 7) CH3CH3 N,N'-bis[2-(tetradecyloxycarbonyl)-1-methylethylcopiperazine N,N '-Bis[2-(tridecylcarboxy)ethylcopiperazine (No.

(NOo 8) N,N'-bis[2-(tetradecyloxycarbonyl)methylcopiperazine (NO2N,N'-bis[2-(tetradecyloxycarbonyl)ethyl)-2,5-dimethylpiperazine N,
N'-bis(2-(2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)ethyl)biperazine (No.

9) Tetrakis(3-piperidinopropionyloxymethyl)methane (No.

10) Tetrakis(3-morpholinopropionyloxymethyl)methane (NO3 11) Tetrakis[3- (4- [2 (tetradecyloxycarbonyl)ethyl] Piperazinyl) Propionyloxymethyl] Methane (No.

12) (No.

13) Tetrakis(3-pyrrolidylpropionyloxymethyl) methane

Claims (1)

[Claims] 1. 100 parts by weight of polyolefin resin, a phenolic stabilizer, a nitrogen stabilizer represented by the following general formula (I), (II) or (III), a phosphorus stabilizer, and a hindered amine stabilizer. agent 1:0.5-15:0.5-15:0.5-1
A polyolefin resin composition characterized in that it is used in combination in a ratio of 0.03 to 3 parts by weight at a ratio of 5 (weight ratio). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [R^1 and R^2 in the above formula (I) are the same or different carbon numbers 1 to 18 an alkyl group, -R^6-C-B-R^7 or -R^6-B-C-R
It is a group represented by ^7, and R^6 in this formula has 1 carbon number.
-6 alkylene group or alkylene group with branching, B is O atom, S atom, ▲ Numerical formula, chemical formula, table, etc. is a group represented by ▼, R^7 is alkyl having 1 to 18 carbon atoms group, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group, or a group represented by ▲a numerical formula, a chemical formula, a table, etc.▼, in which R^8 is an H atom , an alkyl group having 1 to 18 carbon atoms,
Further, R^9 represents an H atom, an alkyl group having 1 to 4 carbon atoms, or an oxyl group. In addition, R^3 and R^4 in the above formulas (I) to (III)
represent the same or different H atoms and alkyl groups having 1 to 6 carbon atoms. Furthermore, A in the above formula represents an O atom, an S atom, an alkylene group having 1 to 3 carbon atoms, or a group represented by -N-. In the formula, R^1^0 is an H atom, an alkyl group having 1 to 18 carbon atoms, R^6-C-B-R^7 or -R^6-B-C-
Represents a group represented by R^7. In addition, R^5 in the above formulas (II and (III)) is -R^6
-C-B-, a is an integer of 1 to 4, Z is an alkyl group having 1 to 18 carbon atoms when a is 1, and 1 to 18 carbon atoms when a is 2; 18 alkylene group, -C
When a is 3, the group represented by a- or -Ba- is represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n in the formula represents an integer of 1 to 4)
When a is 4, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Represents a group represented by. ]