JPH0782425A - Modified polyolefin resin composition - Google Patents

Abstract

PURPOSE:To provide a modified polyolefin resin composition causing no change in hue, excellent in light resistance and appearance, useful for fibers, films, etc., comprising a polyolefin resin, specific modifier, free radical initiator and antioxidant, etc., at specified proportions. CONSTITUTION:This composition can be obtained by incorporating (A) 100 pts.wt. of a polyolefin resin such as PE with (B) 0.01-30 pts.wt. of a glycidyl group-bearing modifier of formula I (R is H or methyl; Ar is 6-23C aromatic hydrocarbon having at least one glycidyl group), e.g. a compound of formula II, (C) 0.01-2 pts.wt. of a free radical initiator such as cumene hydroperoxide, and (D) 0.1-10 ptswt. of at least one kind of stabilizer selected from antioxidant and light stabilizer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which, when a modified polyolefin resin is produced, reduces the coloring of the resin by a stabilizer and is excellent in light deterioration resistance.

[0002]

2. Description of the Related Art Polyolefin resin is widely used as an inexpensive plastic material which is excellent in mechanical properties, chemical properties, physical properties, molding and processing. However, since the polyolefin resin is non-polar, it has a poor affinity for metals, glass, polar polymer materials, etc., and it is difficult to form a composite with these materials. Among them, maleic anhydride is used for the purpose of introducing a functional group into polypropylene to improve chemical properties such as adhesion, paintability, printability, etc., which are conventional defects, and to improve compatibility with other polymers. A method in which an unsaturated compound having an acid or a glycidyl group is graft-polymerized in the presence of an organic radical generator is used (for example, Japanese Patent Publication No. 3-290418). However, in these conventional methods, the polyolefin resin before modification is colorless, whereas the modified polyolefin resin after modification is colored yellow, which is not preferable when the modified polyolefin is used alone as a product. Further, even when it is mixed with another thermoplastic resin to be used as a product, it is not preferable in terms of appearance to color it yellow, especially when mixed with a white thermoplastic resin.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a modified polyolefin resin composition having no hue change before and after grafting a polyolefin resin with an unsaturated glycidyl monomer in the presence of a radical initiator. To provide things.

[0004]

As a result of intensive research to solve the above problems in view of the above circumstances, the present inventors have modified a polyolefin resin in the presence of a radical using a glycidyl compound having an acrylamide group and a glycidyl group. In doing so, they have found that the above problems can be achieved by adding a specific antioxidant and / or light stabilizer as a stabilizer, and have reached the present invention. The present invention will be described in detail below.

That is, in the present invention, (B) the following general formula (I) is added to 100 parts by weight of (A) polyolefin resin.

[0006]

[Chemical 3]

(In the formula, R represents a hydrogen atom or a methyl group, and Ar is a C ₆ -containing at least one glycidyl group.
The C ₂₃ aromatic hydrocarbon group is shown. ) 0.01 to 30 parts by weight of a modifier having a glycidyl group represented by), 0.01 to 2 parts by weight of a radical initiator (C), and at least one selected from the group consisting of (D) an antioxidant and a light stabilizer. A modified polyolefin resin composition containing 0.1 to 10 parts by weight of one type of stabilizer is included.

The polyolefin resin which is the component (A) used in the present invention is selected from the group consisting of polydiene and a mixture of two or more kinds thereof in addition to polyolefin in a narrow sense, and an olefin monomer and a diene monomer. It is used as a broad concept including a copolymer composed of two or more kinds. For example ethylene, propylene, 1
-Butene, 1-pentene, isobutene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-
Cyclohexadiene, 1,4-cyclohexadiene,
Of homopolymers or copolymers selected from the group of monomers such as 1,5-cyclooctadiene, 1,3-cyclooctadiene, α, ω-non-conjugated dienes, and mixtures thereof, that is, homopolymers. Examples include a mixture, a mixture of copolymers, and a mixture of a homopolymer and a copolymer.

The following general formula (I), which is the component (B) used in the present invention:

[0010]

[Chemical 4]

(In the formula, R represents a hydrogen atom or a methyl group. Ar represents C ₆ -containing at least one glycidyl group.
The C ₂₃ aromatic hydrocarbon group is shown. The denaturing agent having a glycidyl group represented by) is, for example, an aromatic hydrocarbon having at least one phenolic hydroxyl group and N-methylolacrylamide or N-methylolmethacrylamide, or an alkyl ether derivative of N-methylolamide. It can be easily obtained by condensing with a catalyst and then converting the phenolic hydroxyl group into a glycidyl group. Two
When 6-xylenol and N-methylol acrylamide are combined, a compound represented by the following structure (II) is obtained.

[0012]

[Chemical 5]

The method for producing these glycidyl group-containing products has already been disclosed by the present inventors in JP-A-60-130580. The amount of the modifier (B) used is in the range of 0.01 to 30 parts by weight with respect to 100 parts by weight of the polyolefin resin (A). If it is less than 0.01 part by weight, the modification effect aimed at by the present invention is small, and if it exceeds 30 parts by weight, the mechanical properties and fluidity inherent to the polyolefin resin are impaired.

Examples of the radical initiator which is the component (C) used in the present invention include cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, decanoyl peroxide and acetyl peroxide. Peroxide-based, 1,1-bis (t-butylperoxy)
Cyclohexane, 2,2-bis (t-butylperoxy) octane, 2,2-bis (t-butylperoxy)
Butane, 4,4-bis (t-butylperoxy) valerate, 1,1-bis (t-butylperoxy) -3,
Peroxyketal compounds such as 3,5-trimethylcyclohexane and azo compounds such as azobisisobutylnitrile may be used alone or in combination of two or more. The amount of the radical initiator (C) used is in the range of 0.01 to 2 parts by weight with respect to 100 parts by weight of the polyolefin resin (A). If the amount is less than 0.01 parts by weight, the amount of grafting sufficient to exhibit the characteristics of the modified polyolefin resin cannot be achieved, and if the amount exceeds 2 parts by weight, the crosslinking reaction by radicals of the polyolefin resin or the molecular weight reduction due to the main chain cleavage is caused. It is not preferable because the mechanical properties of the resin are deteriorated.

As the stabilizer which is the component (D) used in the present invention, an antioxidant and a light stabilizer are used, and these may be used alone or in combination. Examples of the antioxidant include 2,4-bis- (n-octylthio) -6.
-(4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-
Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ], Octadecyl-3
-(3,5-Di-t-butyl-4-hydroxyphenyl) propionate, 2,2thiobis (4-methyl-6)
-T-butylphenol), 1,3,5-trimethyl-
Phenol-based such as 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, thioether-based or tetrakis (2,4-di-t-butylphenyl) -4,4 Examples thereof include phosphorus-based compounds such as'-biphenylene phosphonite and tris (2,4-di-t-butylphenyl) phosphite, which may be used alone or in combination of two or more.

Examples of the light stabilizer include dimethyl-1- (2-hydroxyethyl) -4-hydroxy-succinate.
2,2,6,6-Tetramethylpiperidine polycondensate, poly [[6- (1,1,3,3-tetramethylbutyl) imino 1,3,5-triazine-2,4-diyl]
[(2,2,6,6-Tetramethyl-4piperidyl) imino] hexamethylene [[2,2,6,6-tetramethyl-4-piperidyl) imino]], 2- (3,5-di-
t-Butyl 4-hydroxybenzyl) -2-n-butyl malonate bis (1,2,2,6,6-bench metal-4
-Piperidyl), such as hindered amines, and these may be used alone or in combination of two or more.

The amount of the stabilizer (D) used is in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the polyolefin resin (A). If it is less than 0.1 parts by weight, it is not sufficient to suppress the hue change of the modified polyolefin resin, and if it exceeds 10 parts by weight, the dispersibility of the stabilizer in the polyolefin resin is deteriorated and the mechanical properties of the resin are deteriorated. Is not preferred.

The method for obtaining the modified polyolefin resin composition of the present invention comprises a glycidyl group-containing modifier (B) represented by the general formula (I) and an olefin monomer or diene monomer of the polyolefin resin (A). A single substance or a mixture is synthesized by a known method, for example, bulk polymerization, emulsion polymerization, solution polymerization, suspension polymerization or extrusion reaction polymerization using a radical initiator (C) in the presence of a stabilizer (D). .

In the extrusion reaction polymerization, the compound (B) represented by the general formula (I), the polyolefin resin (A), the radical initiator (C), and the stabilizer (D) are preliminarily reacted in the absence of a solvent. After sufficiently mixing at a temperature that does not exceed 100 to 100 by using a kneading device such as an extruder, a Banbury mixer, a kneader and a roll used in general synthetic resin fields.
This is a method of completing the polymerization by melt-kneading at a temperature of 300 ° C. In particular, this method is preferably adopted from the viewpoint of operability and economy. Solution polymerization means, in the presence of an inert solvent, a modifier (B) having a glycidyl group represented by the general formula (I), a polyolefin resin (A), a radical initiator (C) and a stabilizer (D). ) Is added, each component is dissolved in a solvent, and the polymerization is completed at a temperature of 50 to 150 ° C. The modifier (B) is polymerized in a state in which the mixed state of the polyolefin resin (A) and the modifier (B) is further homogenized as compared with the above-mentioned extrusion reaction polymerization and the like.

The composition of the present invention may further contain a stabilizer such as an ultraviolet absorber, a hydrolyzed water resistance improver, a plasticizer, a lubricant, a flame retardant, a flame retardant aid, and a charge, depending on the use and purpose. Inhibitor,
Additives such as coloring agents, conductivity-imparting agents, inorganic fillers, fibrous reinforcing agents (glass fibers, carbon fibers, graphite fibers, etc.) can also be added. There are no particular restrictions on the method for preparing the components, and known methods can be used. For example, a dry blend with a Henschel mixer can be mentioned.

[0021]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. In the following description, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

Reference Example: Synthesis of denaturing agent A mixture of 102.6 parts of 4-acrylamidomethyl-2,6-dimethylphenol, 181 parts of epichlorohydrin and 2.27 parts of benzyltriethylammonium chloride was stirred at 100 ° C for 30 minutes. The reaction mixture was cooled to room temperature, 147 parts of 5N sodium hydroxide was added dropwise with stirring for 10 minutes, and then the mixture was stirred at 45 to 50 ° C for 1 hour. The obtained reaction mixture was cooled to room temperature, 120 parts of methyl isobutyl ketone and 500 parts of water were added, and the layers were separated. The organic layer was washed with 300 parts of water three times and dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain N-[(2,
3-Epoxypropoxy) -3,5-dimethylphenylmethyl] acrylamide (hereinafter referred to as a modifier) was obtained. The epoxy equivalent measured by the method of JIS K 7236 was 271, and the melting point was 90 to 92 ° C.

Example 1 An ethylene-propylene copolymer having a melt flow rate of 3.2 g / 10 minutes measured at 230 ° C. under a load of 2.2 kg (EPO2P manufactured by Japan Synthetic Rubber Co., Ltd., hereinafter referred to as EPR). ) For 100 parts, 7 parts of modifier and n
-Butyl 4,4-bis (t-butylperoxy) valerate (Perhexa V40 manufactured by NOF CORPORATION, purity 40
%) 0.23 parts, pentaerythrityl-tetrakis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Nippon Ciba-Geigy Co., Ltd. Irganox 1010) 0.5 part was mixed at room temperature, and a 44 mmφ twin-screw extruder (Japan Steel Co., Ltd. Company T
EX 44SS) was used to knead and extrude pellets at a cylinder temperature of 220 ° C. The pellet was dried under reduced pressure at 50 ° C. for 8 hours.

The dried pellets thus obtained were dissolved in xylene heated to 100 ° C., and the xylene solution was added dropwise to acetone to reprecipitate the modified polyolefin, whereby an unreacted modifier and homopolymer of the modifier were obtained. Etc. were removed. The epoxy equivalent of the modified polyolefin was added to the hot xylene-methanol solution of the modified polyolefin after reprecipitation to open the unopened glycidyl group by ring-opening, and then excess xylene hydrochloride-methanol solution was added with sodium methylate. It was measured by back-dropping with a xylene-methanol solution. Evaluation after coloring is JIS K
The yellowing degree (YI) of the dried pellets was measured according to 7130, and the difference (ΔYI) from the yellowing degree of the dried raw material polyolefin resin (EPR) was determined. As a measuring device, a color difference meter Z-Σ80 manufactured by Nippon Denshoku Industries Co., Ltd. was used. The results are shown in Table 1.
Shown in.

Example 2 Pentaerythrityl-tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] (Nippon Ciba Geigy KK Irganox 1
010) is a mixture of tris (2,4-di-t-butylphenyl) phosphite and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Nippon Ciba Geigy Co., Ltd.). A modified polyolefin resin composition was obtained in the same manner as in Example 1 except that Irganox B 900) was used, and the epoxy equivalent and yellowing degree were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 3 EPR was changed to polypropylene (Noblene AH561 manufactured by Sumitomo Chemical Co., Ltd., hereinafter referred to as PP), and pentaerythrityl-tetrakis [3- (3,5-di-t-] was used.
Butyl-4-hydroxyphenyl) propionate]
(Irganox 101 manufactured by Nippon Ciba Geigy Co., Ltd.
0) is a mixture of tris (2,4-di-t-butylphenyl) phosphite and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Nippon Ciba-Geigy Co., Ltd. Irga Knox B
A modified polyolefin resin composition was obtained in the same manner as in Example 1 except that the epoxy equivalent and the yellowing degree were measured. The results are shown in Table 1.

Comparative Example 1 Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010 manufactured by Ciba-Geigy Japan Ltd.) 0 used in Example 1 above. A modified polyolefin resin composition was obtained in the same manner as in Example 1 except that 0.5 part was not used, and the epoxy equivalent and yellowing degree were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 Tris (2,4-di-t) used in Example 3 above.
-Butylphenyl) phosphite and octadecyl-3
Modification in the same manner as in Example 1 except that 0.5 part of a mixture with-(3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX B 900 manufactured by Ciba-Geigy Co., Ltd.) was not used. A polyolefin resin composition was obtained, and the epoxy equivalent and yellowing degree were measured by the same method as in Example 1. The results are shown in Table 1.

Example 4 In a reactor, 1000 parts of chlorobenzene, 230 parts
Ethylene-propylene copolymer having a melt flow rate of 3.2 g / 10 minutes measured by applying a load of 2.2 kg at ℃ (EPO2P manufactured by Japan Synthetic Rubber Co., Ltd., hereinafter EPR)
100 parts, a modifier 7 parts, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Nippon Ciba-Geigy KK Irganox 1010). 5 parts and 0.025 parts of 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane (Perhexa 3M, NOF Corporation) were added, and the mixture was stirred at 130 ° C. for 4 hours. The chlorobenzene solution was dropped into acetone to reprecipitate the modified polyolefin, thereby removing the unreacted modifier and the homopolymer of the modifier. The bead-like solid obtained was dried under reduced pressure at 50 ° C. for 8 hours. After the epoxy equivalent of the modified polyolefin resin composition is reprecipitated, a hot xylene-methanol solution of the modified polyolefin after reprecipitation is added with a xylene hydrochloride-methanol solution to open the unopened glycidyl group, and then an excess xylene hydrochloride-methanol solution is added. Was measured by back-dropping with a sodium methyla-toxylene-methanol solution. Evaluation after coloring is JIS K
The yellowing degree (YI) of the beaded solid was measured according to 7130, and the difference (ΔYI) from the yellowing degree of the dried raw material polyolefin resin (EPR) was determined. As a measuring device, a color difference meter Z-Σ80 manufactured by Nippon Denshoku Industries Co., Ltd. was used. The results are shown in Table 2.
Shown in.

Example 5 Pentaerythrityl-tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] (Nippon Ciba Geigy KK Irganox 1
010) to tris (2,4-di-t-butylphenyl)
Phosphite and octadecyl-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate (Irganox B900 manufactured by Ciba-Geigy Co., Ltd., Japan) was used, except that a modified polyolefin resin composition was obtained in the same manner as in Example 4 and was the same as Example 4. The epoxy equivalent and yellowing degree were measured by the method. The results are shown in Table 2.

Example 6 EPR was changed to polypropylene (Noblene AH561, manufactured by Sumitomo Chemical Co., Ltd., hereinafter referred to as PP), and pentaerythrityl-tetrakis [3- (3,5-di-t-] was used.
Butyl-4-hydroxyphenyl) propionate]
(Irganox 101 manufactured by Nippon Ciba Geigy Co., Ltd.
0) is a mixture of tris (2,4-di-t-butylphenyl) phosphite and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Nippon Ciba-Geigy Co., Ltd. Irga Knox B
A modified polyolefin resin composition was obtained in the same manner as in Example 4 except that the epoxy equivalent and the yellowing degree were measured in the same manner as in Example 4. The results are shown in Table 2.

Comparative Example 3 Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Ciba-Geigy Japan Ltd.) 0 used in Example 4 above. A modified polyolefin resin composition was obtained in the same manner as in Example 4 except that 0.5 part was not used, and the epoxy equivalent and yellowing degree were measured in the same manner as in Example 4. The results are shown in Table 2.

Comparative Example 4 Tris (2,4-di-t) used in Example 6 above.
-Butylphenyl) phosphite and octadecyl-3
Modification in the same manner as in Example 4 except that 0.5 part of the mixture with-(3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX B900 manufactured by Ciba-Geigy Co., Ltd.) was not used. A polyolefin resin composition was obtained, and the epoxy equivalent and yellowing degree were measured by the same method as in Example 6. The results are shown in Table 2.

Evaluation of Modified Polyolefin Resin From the epoxy equivalents of the modified polyolefin resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 4, the grafting amount (wt%) of the modifier to the polyolefin resin was calculated,
The grafting efficiency of the modifying agent was calculated by taking the ratio of the grafting amount of the modifying agent and the blending amount (wt%) of the modifying agent based on the following formula. The results are shown in Tables 1 and 2. Grafting efficiency (%) = (amount of grafted modifier / amount of modifier added) × 100

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

As is clear from the results of Tables 1 and 2, the modified polyolefin resin composition of the present invention has a high modification efficiency as in the case of no addition, and the polyolefin used as a raw material by adding a stabilizer. When compared with the original hue of the system resin, the hue change is extremely small. Taking advantage of such characteristics, the modified polyolefin-based resin composition of the present invention can be widely used for molded articles as well as fibers and films.

Claims (8)

[Claims] 1. To 100 parts by weight of (A) a polyolefin resin, (B) the following general formula (I): (In the formula, R represents a hydrogen atom or a methyl group, and Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyl group.) A modifier having a glycidyl group represented by 0. 01 to 30 parts by weight, (C) radical initiator 0.01 to 2 parts by weight, and (D) at least one stabilizer selected from the group consisting of an antioxidant and a light stabilizer.
A modified polyolefin-based resin composition containing 1 to 10 parts by weight. 2. The polyolefin resin of component (A) comprises
Ethylene, propylene, 1-butene, 1-pentene, isobutene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4
-Cyclohexadiene, 1,5-cyclooctadiene,
The resin composition according to claim 1, which comprises a homopolymer or a copolymer selected from monomers consisting of 1,3-cyclooctadiene and α, ω-nonconjugated dienes, and a mixture thereof. 3. The glycidyl group-containing modifier of component (B) is represented by the following formula (II): The resin composition according to claim 1, which is represented by: 4. The resin composition according to claim 1, wherein the antioxidant is at least one selected from the group consisting of phenol compounds, thioether compounds and phosphorus compounds. 5. The resin composition according to claim 1, wherein the light stabilizer is a hindered amine compound. 6. (A) a polyolefin resin, (B) a modifier having a glycidyl group represented by the general formula (I),
The resin composition according to any one of claims 1 to 5, which is obtained by reacting a radical initiator (C) and a stabilizer (D) under the condition that the radical initiator (C) decomposes. 7. (A) a polyolefin resin, (B) a modifier having a glycidyl group represented by the general formula (I),
100 to 30 (C) radical initiator and (D) stabilizer
The resin composition according to claim 1, which is obtained by melt-kneading at a temperature of 0 ° C. 8. (A) a polyolefin resin, (B) a modifier having a glycidyl group represented by the general formula (I),
The resin composition according to claim 1, which is obtained by dissolving (C) a radical initiator and (D) a stabilizer in a solvent and reacting them.