JPH04239547A - Stabilized polyphenylene ether-based resin composition - Google Patents

Abstract

PURPOSE:To obtain title composition useful for parts of automobile, having excellent impact resistance, thermal stability, environmental crack resistance, comprising a polyphenylene ether resin, a styrenic resin, a specific high impact styrenic and a specific stabilizer in a given ratio. CONSTITUTION:The objective composition comprising (A) 100-90 pts.wt. polyphenylene ether resin, (B) 90-10 pts.wt. high impact styrenic resin which is a partially hydrogenated conjugated diene-based rubber-containing high impact styrenic resin wherein the partially conjugated diene-based rubber is partially hydrogenated by 5-70wt.% based on total double bond of conjugated diene-based rubber, and has <=3wt.% 1.2-vinyl bond after hydrogenation and <=30wt.% 1,4 vinyl bond, (C) 0-80 pts.wt. styrenic resin and (D) 0.01-2 pts.wt. based on 100 pts.wt. total amounts of the components A to C of stabilizer shown by the formula (A is amino, H, alkyl, etc.; B1 and B2 are H or alkyl).

Description

Description: FIELD OF THE INVENTION The present invention relates to a resin composition having excellent impact resistance, thermal stability and environmental cracking resistance. More specifically, when reinforcing polyphenylene resin with impact resistant styrene resin, impact resistant styrene resin containing partially hydrogenated conjugated diene rubber in which a portion of all double bonds of the conjugated diene rubber is hydrogenated is used. The present invention relates to a resin composition with improved impact resistance, molding stability, and hot water resistance, which uses a resin and further contains a heat stabilizer sufficient to stabilize the impact resistant styrenic resin. [Prior Art] Polyphenylene ether resin has heat resistance,
Although this resin has excellent electrical properties, acid resistance, alkali resistance, etc., as well as low specific gravity and low water absorption, it is difficult to melt and mold due to its low fluidity, and its impact strength is low. It also has the disadvantage of being somewhat brittle. In order to improve these drawbacks at the same time, a technique of blending high-impact polystyrene containing a polybutadiene component was developed and disclosed in US Pat. No. 3,383,435. [0003] Separately, a technique for compounding impact-resistant polystyrene using polybutadiene with a specified microstructure is also disclosed in Japanese Patent Publication No. 54-20537. The technology of Tokkosho is characterized in that the contents of 1,4 cis bonds and vinyl groups in the entire microstructure of polybutadiene are 50% by weight or more and 10% by weight or less, respectively. However, with these techniques, the total amount of double bonds does not change regardless of the microstructure, so the degree of physical property change due to oxidative deterioration, etc. due to the chemical instability of double bonds is extremely high. There was no significant difference, and it was extremely difficult to avoid deterioration of physical properties due to melt molding, heat exposure, light exposure, etc. On the other hand, a technology for reinforcing with a hydrogenated styrene-butadiene block copolymer containing almost no double bonds is disclosed, for example, in JP-A-50-71742; Although the rubber particles of the impact-resistant styrenic resin do not contain dispersed particles of styrene polymer, the rubber efficiency is low, and it is necessary to add a large amount of rubber component to improve impact resistance. there were. Moreover, since the affinity between the hydrogenated styrene-butadiene block copolymer and the polyphenylene ether resin is not necessarily sufficient, peeling often occurs in molded products. In addition, as the hydrogenation rate of the 1,4-butadiene component in the butadiene block increases, the glass transition point of the rubber component increases, making it impossible to obtain sufficient low-temperature impact resistance with this technique. . Separately, a technique for improving the impact strength of impact-resistant styrene resin while maintaining its rigidity is disclosed in JP-A-64-90208. It has been shown that impact strength is improved compared to high impact styrenic resins. However, resin compositions containing polyphenylene ether resins are characterized by high heat resistance, and in the area where there are many 1,2-vinyl residues in the technique disclosed in this publication,
There is a problem in that when molded at high temperatures or exposed to heat, the physical properties deteriorate significantly. Furthermore, there are problems such as not being able to obtain low-temperature impact strength in the region where the hydrogenation rate is high, and it is difficult to fully satisfy the technical range of impact-resistant styrene resins that are required to improve the physical properties of polyphenylene ether resins. It cannot be used as an indicator of [Problems to be Solved by the Invention] The problem of the present invention is to solve the above-mentioned problems when imparting moldability and impact resistance to polyphenylene ether resins, that is, to solve the problem of physical properties due to melt processing and heat exposure. The object of the present invention is to obtain a polyphenylene ether resin composition that does not cause a decrease in water and has excellent hot water resistance. [Means for Solving the Problems] As a result of research, the present inventors found that when a polyphenylene ether resin is reinforced with an impact-resistant styrene resin containing a conjugated diene rubber,
The greater the amount of double bonds in the conjugated diene rubber component, the more
It is easy to undergo oxidative deterioration, resulting in a large decline in physical properties.Furthermore, when the amount of 1,2-vinyl bonds among double bonds increases, oxidative deterioration is accelerated and the main chain splitting of the styrene resin component is induced, resulting in a decrease in physical properties. It was found that this resulted in a decrease in [0009] If the total amount of double bonds is more than necessary, the thermal stability and rigidity will decrease, and if the total amount is less than necessary, the low-temperature impact strength will decrease. We found that there is a quantity. In addition, when an impact-resistant styrenic resin containing partially hydrogenated conjugated diene rubber is added to a polyphenylene ether resin, the resistance is significantly higher than that of a conventional impact-resistant styrene resin containing a conjugated diene rubber. It has been found that it exhibits impact strength and environmental cracking resistance. Furthermore, when a stabilizer represented by the following general formula is blended, the thermal stability is improved to an extent that cannot be expected from the effect when using a conventional impact-resistant styrene resin containing a conjugated diene rubber. It has been found that there is very little decrease in impact resistance due to thermal history, and that it exhibits excellent molding stability and hot water resistance. ##STR2## where A is an amino group, hydrogen, alkyl group, alkoxy group, cycloalkyl group or aryl group,
B1 and B2 each independently represent hydrogen or an alkyl group. ) In addition, we have discovered that thermal stability is further significantly improved by containing at least one of sterically hindered phenols, organic phosphites, organic sulfur antioxidants, and amines, and based on this discovery, we have developed the present invention. completed. That is, the present invention provides (1) (a) polyphenylene ether resin 10-
90 parts by weight, (b) an impact-resistant styrenic resin containing a partially hydrogenated conjugated diene rubber, wherein the partially hydrogenated conjugated diene rubber contains 5 to 70 of the total double bonds of the conjugated diene rubber.
Impact resistant styrene which is a partially hydrogenated conjugated diene rubber in which % by weight is hydrogenated and the amount of 1,2-vinyl bonds after hydrogenation is 3% by weight or less and the amount of 1,4 bonds is 30% by weight or more (c) 0 to 80 parts by weight of a styrene resin (d) Total amount of the components (a), (b), and (c): 100 parts by weight
Stabilizer represented by the following general formula 0.01 per part by weight
A polyphenylene ether resin composition consisting of ~2 parts by weight:
B1 and B2 each independently represent hydrogen or an alkyl group. ) (2) A stabilized polyphenylene ether resin composition comprising the above composition and at least one of a sterically hindered phenol, an organic phosphite, an organic sulfur antioxidant, and an amine. A composition is provided. [0016] The resin composition of the present invention shows little deterioration in physical properties due to long-term thermal aging at high temperatures, and hardly causes deterioration in physical properties even when immersed in hot water for a long time. In addition, compared to conventional technology, the impact resistance increases with the same amount of rubber, so in order to obtain the same impact resistance strength, a smaller amount of rubber is required. Since the amount of rubber is small, the composition becomes difficult to burn, and even when flame retardant is desired, it has the advantage that the objective can be achieved with a small amount of flame retardant. Furthermore, the resin composition of the present invention has a good balance of physical properties such as rigidity, low-temperature impact resistance, and environmental cracking resistance.
It has the advantage of being able to obtain areas that cannot be reached with conventional techniques. The polyphenylene ether resin as component (a) used in the present invention has the general formula:
, R5 and R6 are monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen, and hydrogen;
R6 is not hydrogen at the same time. ) can be used as a repeating unit, and a homopolymer or a copolymer in which the structural unit has the above general formula can be used. A typical example of a homopolymer of polyphenylene ether resin is poly(2,6-dimethyl-1
,4-phenylene)ether, poly(2-methyl-6-
Ethyl-1,4-phenylene)ether, poly(2,6
-diethyl-1,4-phenylene)ether, poly(2
-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1)
,4-phenylene)ether, poly(2-ethyl-6-
Isopropyl-1,4-phenylene) ether, poly(
2-Methyl-6-chloro-1,4-phenylene)ether, poly(2-methyl-6-hydroxyethyl-1,4)
Examples include homopolymers such as -phenylene) ether and poly(2-methyl-6-chloroethyl-1,4-phenylene) ether. The polyphenylene ether copolymer has 2,
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol or copolymer of o-cresol or 2,3,6-trimethylphenol and o-
It includes polyphenylene ether copolymers mainly having a polyphenylene ether structure, such as copolymers with cresol. In the present invention, the content of polyphenylene ether resin is 10 to 90, preferably 20 to 80.
Parts by weight range. If the content is less than 10 parts by weight, the improvement effect of the polyphenylene ether resin will not be sufficiently exhibited, which is undesirable. If the content exceeds 90 parts by weight, the amount of polyphenylene ether resin will not be sufficient to improve moldability or impact resistance. This is not preferable because it becomes impossible to add impact styrene resin. The partially hydrogenated conjugated diene rubber contained in the impact-resistant styrene resin used as component (b) of the present invention is prepared by partially hydrogenating a conjugated diene rubber obtained by a known method. obtained by. Conjugated diene rubbers obtained by known methods include all rubbers normally used in the production of impact-resistant styrene resins. Examples include polybutadiene (low-cis polybutadiene and high-cis polybutadiene), styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, natural rubber, and the most preferred among them is polybutadiene. In the present invention, the partially hydrogenated conjugated diene rubber has 5 to 70, preferably 10 to 6, of the total double bonds.
0% by weight is hydrogenated, and the amount of 1,2-vinyl bonds is 3
It is not more than 2% by weight, preferably not more than 2% by weight. The amount of 1,4 bonds is desirably 30% by weight or more. If the hydrogenation rate of all double bonds is less than 5% by weight, the effect of partial hydrogenation will not be sufficiently exhibited. For example, even if a conjugated diene rubber containing 8% by weight of 1,2-vinyl before hydrogenation is hydrogenated with less than 5% by weight of 1,2-vinyl,
The amount of 2-vinyl cannot be reduced to less than 3% by weight, and even if less than 5% by weight of the total double bond amount is hydrogenated, impact resistance and environmental cracking resistance can hardly be improved. If the hydrogenation rate exceeds 70% by weight, it is not preferable because impact resistance, especially low-temperature impact resistance, cannot be obtained sufficiently. 1 contained in partially hydrogenated conjugated diene rubber
, 2-vinyl bonds in excess of 3% by weight, the rubber component is oxidized and the main chain of the styrene resin is likely to be split, so that the thermal stability cannot be sufficiently improved, which is not preferable. Furthermore, if the amount of 1,4 bonds is less than 30% by weight, the effect of improving impact resistance becomes poor, which is not preferable. The partially hydrogenated conjugated diene rubber used in the present invention can be obtained by partially hydrogenating the above-mentioned conjugated diene rubber. As the hydrogenation method, any conventionally known method may be used, for example, F. L. Ramp et a
l, J. Amer. Chem. Soc. ,83,4
672 (1961). A method of hydrogenation using a triisobutylborane catalyst described by Hung Yu Ch.
en, J. Polym. Sci. Polym. Lett
er Ed. , 15, 271 (1977). A method of hydrogenation using toluenesulfonyl hydrazide as described above, a method of hydrogenation using an organocobalt-organoaluminum catalyst or an organonickel-organoaluminum catalyst described in Japanese Patent Publication No. 42-8704, etc. I can do it. A particularly preferred method of hydrogenation in the practice of the present invention is disclosed in JP-A-52-41, which uses a catalyst capable of selectively hydrogenating 1,2-vinyl bonds prior to 1,4 bonds.
JP-A-59-1 using the method shown in Japanese Patent Application No. 890 or using a catalyst capable of hydrogenation under mild conditions of low temperature and low pressure.
This is the method disclosed in No. 33203 and Japanese Unexamined Patent Publication No. 60-220147. In the present invention, the content of the impact-resistant styrene resin containing partially hydrogenated conjugated diene rubber is 90 to 10
, preferably in the range of 80 to 20 parts by weight. If the content exceeds 90 parts by weight, the required amount of polyphenylene ether resin cannot be added, and if the content is less than 10 parts by weight, the partially hydrogenated conjugated diene rubber cannot be sufficiently contained, resulting in poor impact resistance. Also, the environmental cracking resistance cannot be sufficiently improved, which is not preferable. The method for producing the impact-resistant styrenic resin containing the partially hydrogenated conjugated diene rubber as component (b) in the present invention may be any known method and is not limited to this method. Japanese Patent Application Laid-open No. 64-902 filed by the same applicant
A preferred example is the method described in Japanese Patent No. 08. The styrenic resins used as component (c) of the present invention include: (1) A resin made of a polymer of a styrene compound; (2) A resin made of a copolymer of a styrene compound and a compound copolymerizable with the styrene compound; (2) mentioned above; and a rubbery polymer ■ Said ■
and resins made of rubbery polymers. The styrenic compound used as component (c) of the present invention has the general formula: ##STR5## where R7 represents hydrogen, lower alkyl or halogen, R8 represents vinyl, , halogen, and lower alkyl, and k is an integer of 0 to 5). Specific examples of these include styrene, α-methylstyrene, 2,
Examples include 4-dimethylstyrene, monochlorostyrene, dichlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Compounds that can be copolymerized with styrene compounds include methacrylic esters such as methyl methacrylate and ethyl methacrylate; acrylic esters such as butyl acrylate and 2-ethylhexyl acrylate; and acrylonitrile and methacrylonitrile. Unsaturated nitrile compounds; examples include acid anhydrides such as maleic anhydride. Examples of the rubbery polymer include conjugated diene rubber and ethylene-propylene copolymer rubber. As examples of the resins listed in ■ to ■ above, ■ resins made of styrene compound polymers include:
Polystyrene, styrene-α-methylstyrene copolymer, etc. Resins made of copolymers of styrene compounds and compounds copolymerizable with styrene compounds include styrene-acrylonitrile copolymers and styrene-methyl methacrylate copolymers. Coalescence, styrene-maleic anhydride copolymer, etc. ■ Examples of resins made of a polymer of a styrene compound and a rubbery polymer include rubber-modified polystyrene. As resins made of polymers and rubbery polymers,
Examples include rubber-modified styrene-acrylonitrile copolymer, rubber-modified styrene-maleic anhydride copolymer, and the like. When the styrene resin contains a rubbery polymer, the amount of 1,2-vinyl bonds and 1,4
It is necessary that the bonding amount is 3% by weight or less and 30% by weight or more, respectively. In the present invention, the styrene resin is used to adjust the heat distortion temperature and moldability, and if the purpose is achieved by the impact resistant styrene resin containing partially hydrogenated conjugated diene rubber, it may not be added. Good, but up to 80 parts by weight can be added if necessary. If it exceeds 80 parts by weight, it is not preferable because the required amount of impact-resistant styrene resin containing polyphenylene ether resin and partially hydrogenated conjugated diene rubber cannot be added. The stabilizer used in the present invention has the general formula 0
[0038] (A is an amino group, hydrogen, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, B1,
B2 each independently represents hydrogen or an alkyl group. )
It is a compound represented by A typical example is melamine (2
, 4,6-triamino-sym-triazine), guanamine (2,4-diamino-sym-triazine), 2,
4-diamino-6-phenyl-sym-triazine, 2
, 4-diamino-6-methyl-sym-triazine, 2
, 4-diamino-6-butyl-sym-triazine, 2
, 4-diamino-6-butoxy-sym-triazine,
Examples include 2,4-diamino-6-cyclohexyl-sym-triazine. Among these, a particularly preferred stabilizer is melamine. In order to improve the dispersibility of the stabilizer, it is preferable to use a commonly known dispersant, such as a metal salt of a higher fatty acid or a higher fatty acid ester, to fully exhibit the effect of the stabilizer. The amount of the stabilizer used in the present invention may be the amount in which this type of stabilizer is normally used,
0.01 to 2 parts by weight, preferably 0.03 to 1 part by weight, based on 100 parts by weight of the total amount of components (a), (b), and (c).
．． 5 parts by weight are used, particularly preferably 0.05 to 1 part by weight. The sterically hindered phenol used in the present invention is normally used as an antioxidant or processing stabilizer, and is not particularly limited. For example, octadecyl-3-(3,5-di-t -butyl-4-dihydroxyphenyl)propionate, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-
hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydroxynamamide), 2-t-butyl-6
-(3'-t-butyl-5'-methyl 2'-hydroxybenzyl)-4-methylphenylacrylate. 2,2'-oxamide bis[ethyl-
3-(3,5-di-t-butyl-4-hydroxyphenyl)propinate], 1,3,5-trimethyl-2,4
, 6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ], tris-(3,5-di-t-
Butyl-4-hydroxybenzyl)-isocyanurate, pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]. 2,4-bis-(n-octylthio)-6
-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 1,1,3-tris(2
-Methyl-4-4hydroxy-5-t-butylphenyl)butane, 1,6-hexanediol-bis[3-(3
, 5-di-t-butyl-4-hydroxyphenyl)propionate], 4,4'-butylidenebis(3-methyl-6-tert-butylphenol). and 3,9-bis[1,1-dimethyl 2-
{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)ethyl}-2,4,8,
10-tetraoxapyro[5,5]undecane, 2-[
1-(2-hydroxy-3,5-di-t-propylphenyl)ethyl]-4,6-di-t-propylphenyl acrylate, 3,9-bis[2-[3-(3-t-butyl) -4-hydroxy-5-methylpropyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8
, 10-tetraoxaspiro[5,5]undecane, and the like. [0044] The amount used is the above-mentioned components (a), (b), (
It is 0.001 to 1 part by weight, preferably 0.01 to 0.7 part by weight, particularly 0.001 to 1 part by weight, based on 100 parts by weight of the total amount of c).
．． 05 to 0.5 parts by weight is preferred. The organic phosphites used in the present invention are not particularly limited, but specific examples include triphenyl phosphite, diphenyldecyl phosphite, didecyl phenyl phosphite, tridecyl phosphite, and trioctyl phosphite. phyto, tridodecyl phosphite, triotadecyl phosphite, trinonylphenyl phosphite, tridodecyl trithiophosphite. Distearyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, 4,4'-isopropylidene diphenol alkyl phosphite, 3,9-dioctadecyloxy-2,4 , 8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-dinonylphenyloxy-2,4,8,10-tetraoxa-3,9
-diphosphaspiro[5,5]undecane, 3,9-bis(2,4-di-t-butylphenyloxy)-2,4
, 8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane and the like. [0046] The amount used is the above components (a), (b), (
It is 0.01 to 2 parts by weight, preferably 0.03 to 1.5 parts by weight, particularly 0.01 to 2 parts by weight, based on 100 parts by weight of the total amount of c).
05 to 1 part by weight is preferred. As the organic sulfur antioxidant used in the present invention, those commonly used as antioxidants are used. For example, dilauryl-3,3'-thio-di-propionate, dimyristyl-3,3'-thio-di-propionate, distearyl-3,3'-thio-di-propionate, ditridecyl-3,3 '-thio-di-propionate, pentaerythritol-tetrakis-(β-lauryl-thiopropionate), 2-mercaptobenzimidazole, 4,4'-thio-bis-(3
-methyl-6-t-butylphenol) and the like. [0048] The amount used is the above components (a), (b), (
It is 0.01 to 2 parts by weight, preferably 0.02 to 1.5 parts by weight, particularly 0.0 parts by weight, based on 100 parts by weight of the total amount of c).
5 to 1 part by weight is preferred. The amines used in the present invention are alkanolamines (2
), (3), and (4), and amines represented by formula (5), either singly or as a mixture. (1) N(R9)3 (Each R9 is independently hydrogen or a lower alkanol having 1 to 4 carbon atoms, and at least two R9's are alkanols.) (2) R10NH-(R11O)aH(R10 is an alkyl group, R11 is an alkyl group having 2 to 4 carbon atoms, and a is an integer of 1 to 50.) (3) [Chemical formula 7] (R12 is an alkyl group, R13 and R14 are carbon (R15 is an alkyl group, R16 is an alkyl group having 1 carbon number, and m and n are integers of 1 to 50.)
-4 alkyl group, R17, R18, R19 have 2 carbon atoms
-4 alkyl group, p, q, r are integers of 1-50. )(5) A compound containing an N-CH2-CH2-N skeleton in the amine molecule and is represented by the following (i) or (ii) (i) [Chemical formula 9] (ii) H2N (CH2 ・CH2
NH)t CH2 CH2 NH2 (t = integer of 0 to 2) Typical examples are diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, dibutanolamine, tributanolamine, dodecylethanolamine, 10 [0056] [Chemical 11] [Chemical 12] [Chemical 12] N,N' diphenylethylenediamine, triethyltetramine and the like can be mentioned. These are used in an amount of 0.005 to 5, preferably 0.1 to 3 parts by weight per 100 parts by weight of the total amount of components (a), (b) and (c). The compositions of the invention may contain other additives, such as plasticizers,
UV absorbers, flame retardants, coloring agents, mold release agents, fibrous reinforcing agents such as glass fiber and carbon fiber, various whiskers such as potassium titanate whiskers, and glass beads.
Fillers such as calcium carbonate, talc, clay, wollastonite, etc. can be added. [0059] As the flame retardant, aromatic phosphate ester,
Red phosphorus, aromatic halogen compounds, antimony trioxide, etc. are particularly effective. Any method may be used to mix the components constituting the present invention, and for example, an extruder, heated roll, Banbury mixer, kneader, etc. can be used. [Examples] Examples are shown below, but the present invention is not limited to the following examples. Hereinafter, % and parts are respectively % by weight.
and parts by weight. The impact-resistant styrene resin used in the following Examples and Comparative Examples was prepared by the manufacturing method described below. Further, the impact-resistant styrenic resin used in the Examples and Comparative Examples, and the conjugated diene rubber and partially hydrogenated conjugated diene rubber used in preparing the same, are as shown in Table 2. Further, the substance names in Tables 3 to 5 are as follows. <Stabilizer>*0-1; Melamine *0-2; Benzoguanamine <sterically hindered phenol>*1-1; Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate *1- 2
; Pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] *1-3; 2-t-butyl-6-(3'-t-butyl-
5'-Methyl-2'-hydroxybenzyl)-4-methylphenylacrylate *1-4; Tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate *1-5; 2,
4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-
triazine. <Organic phosphites>*2-1; Tris(2,4-di-t-butylphenyl) phosphite *2-2; Trinonylphenyl phosphite *2-3;
3,9-Dioctadecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane <Organic sulfur antioxidant>*3-1;Di-stearyl-3,3'-thio-di-propionate*3-2;di-lauryl-3,3-thio-di-propionate*3-3; pentaerythritol-tetrakis-(β-
lauryl-thio-propionate) <Amines>*4-1; Triethanolamine *4-2; Triisopropanolamine *4-3; Nippon Oil & Fats Corporation, Nissan Nymeen L-202 0063] [Chemical formula 13 *4-4; Nippon Oil & Fats Co., Ltd., Nissan Nymeen L-207 [Chemical formula 14] [Production Example 1] Used in production examples of partially hydrogenated conjugated diene rubber Partially hydrogenated conjugated diene rubber is typically
It was manufactured by the method described below. Using a jacketed autoclave with an internal volume of 10 liters and a stirrer as a reactor, a butadiene/n-hexane mixture (butadiene concentration 20%) was reacted with n-butyllithium/n-butyllithium at 20 liters/hr.
An n-hexane solution (concentration 5%) was introduced at a rate of 70 ml/hr, and conjugation polymerization of butadiene was carried out at a polymerization temperature of 110°C. The obtained active polymer was deactivated with methanol, 8 liters of the polymer solution was transferred to another 10 liter reactor equipped with a stirrer and jacket, and at a temperature of 60°C, di-p- 250 ml of tolylbis(1-cyclopentadienyl) titanium/cyclohexane solution (concentration 1.2 mmol/l) and 50 ml of n-butyllithium solution (concentration 6 mmol/l) were mixed at 0°C at 2.0 Kg/cm.
Add the mixture under hydrogen pressure of 2, hydrogen partial pressure 3.0
The reaction was carried out at Kg/cm2 for 60 minutes. The obtained partially hydrogenated polymer solution contained 0.5% of 2,6-di-tert-butylhydroxytoluene per polymer as an antioxidant.
part was added and the solvent was removed. The analytical values of polybutadiene before partial hydrogenation and partially hydrogenated polybutadiene obtained by sampling after methanol deactivation were as shown in Table 1. Production Example 2 Production of Impact-Resistant Styrenic Resin The impact-resistant styrenic resin used in the Examples was produced by a bulk polymerization method. Representative examples are described below. 10 parts of the partially hydrogenated polybutadiene in Table 1 were mixed with 90 parts of styrene and 8 parts of ethylbenzene.
Furthermore, 0.05 part of benzoyl peroxide and 0.10 part of α-methylstyrene dimer were added to the styrene, and the mixture was heated at 80°C for 4 hours and at 110°C for 4 hours.
Polymerization was carried out at 150° C. for 4 hours with stirring. Furthermore, 23
Heat treatment was performed at around 0°C for 30 minutes, and then unreacted styrene and ethylbenzene were removed in vacuum to obtain impact-resistant styrenic resin No. 1 shown in Table 2. I got 1. The content of partially hydrogenated polybutadiene in the resulting impact-resistant styrenic resin was 11%, and the average particle diameter of the partially hydrogenated polybutadiene containing dispersed particles of polystyrene was 2.7 μm. there were. The impact-resistant resins used in Examples and Comparative Examples below were similarly produced by the bulk polymerization method. The results are shown in Table 2. [Example 1] Intrinsic viscosity 0.50 (30°C in chloroform)
45 parts by weight of poly 2,6-di-methyl-1,4 phenylene ether (hereinafter abbreviated as PPE), Table 2
No. High impact polystyrene (hereinafter referred to as HIPS) shown in 1
0.1 part by weight of melamine is mixed with 55 parts by weight (abbreviated as ),
The mixture was melt-kneaded and pelletized using a PCM-30 twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd.) with a cylinder temperature of 320°C. The obtained pellets were heated to a cylinder temperature of 290℃.
IS-80C injection molding machine (Toshiba Machine Co., Ltd.) set at ℃
The specimen was molded into a 1/8-inch thick Izod impact strength test piece using the following methods. This test piece was left in a hot air circulation constant temperature bath set at 125° C. for 500 hours to conduct an aging test. The Izod impact strength before and after the aging test was measured based on ASTM D-256. In addition, as a hot water resistance test, the same test piece was placed in hot water at 90°C for 1000 hours.
An immersion test was conducted, the Izod impact strength before and after immersion was measured, and the retention rate (%) was determined. The above results are shown in Table 3. [Example 2] The same procedure as in Example 1 was carried out except that melamine was changed to 0.3 parts by weight. The results are shown in Table 3. [Example 3] In addition to Example 1, octadecyl-3-(3,5-di-t-butyl-4-
The same procedure as in Example 1 was carried out except that 0.1 part by weight of hydroxyphenyl) propionate was added. The results are shown in Table 3. [Example 4] The same procedure as Example 1 was repeated except that 0.3 parts by weight of tris(2,4-di-t-butylphenyl) phosphite was added as an organic phosphite to Example 1. I did the same. The results are shown in Table 3. [Example 5] Completely the same as Example 1 except that 0.2 parts by weight of di-stearyl-3,3'-thio-di-propionate was further added as an organic sulfur antioxidant. I went to The results are shown in Table 3. Example 6 The same procedure as in Example 1 was carried out except that 0.5 parts by weight of triethanolamine was further added as an amine. The results are shown in Table 3. Comparative Example 1 The same procedure as in Example 1 was carried out except that 0.1 part by weight of melamine was not added. The results are shown in Table 3. [Comparative Example 2] The impact-resistant polystyrene used in Comparative Example 1 was No. 2 in Table 2. Comparative Example 1 was carried out in exactly the same manner as in Comparative Example 1 except that the impact-resistant polystyrene shown in No. 2 was used. The results are shown in Table 3. [Comparative Example 3] The impact-resistant polystyrene used in Example 1 was replaced with No. 1 in Table 2. The same procedure as in Example 1 was conducted except that the impact-resistant polystyrene shown in Example 2 was used. The results are shown in Table 3. Comparative Example 4 The impact-resistant polystyrene used in Example 6 was No. 2 in Table 2. Example 6 was carried out in exactly the same manner as in Example 6, except that the high-impact polystyrene shown in Example 2 was used. The results are shown in Table 3. [Examples 7 to 17] Exactly the same as Example 1 except that the substances and amounts shown in Table 4 among sterically hindered phenol, organic phosphite, organic sulfur antioxidant, and amines were added. I went to The results are shown in Table 4. [Example 18] The HIPS of Example 1 was used as No. 1 in Table 2. 3, and changed the amount of melamine added to 0.
The same procedure was carried out except that the amount was changed to 3 parts by weight. Table 5 shows the results.
Shown below. [Examples 19 to 22] Examples 19 to 22 except that the substances and amounts shown in Table 5 among sterically hindered phenols, organic phosphite esters, organic sulfur antioxidants, and amines were added to Example 18. It was carried out in exactly the same manner as in 18. The results are shown in Table 5. Comparative Example 5 The same procedure as in Example 18 was repeated except that melamine was not added. The results are shown in Table 5. [Comparative Example 6] The HIPS of Example 18 was compared to No. 2 in Table 2. The procedure was carried out in exactly the same manner except that HIPS was changed to No. 4 HIPS. The results are shown in Table 5. [Example 23] The HIPS of Example 18 was used as No. 2 in Table 2. 5
Implemented except for changing to HIPS and adding 0.2 parts by weight of pentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] as a sterically hindered phenol. It was carried out in exactly the same manner as in Example 18. The results are shown in Table 5. Example 24 The same procedure as in Example 23 was repeated except that 0.5 parts by weight of benzoguanamine was added in place of the melamine used in Example 23. The results are shown in Table 5. [Table 1] [Table 2] [Table 2] [Table 3] [0090] [Table 4] [Table 5] [Effects of the Invention] The resin composition of the present invention It is a useful molding material with improved impact resistance and thermal stability during high-temperature molding, improved retention of physical properties of high-temperature molded products over long periods of high temperatures, and excellent hot water resistance. Therefore, molded products of the composition of the present invention are suitable for automobile parts, water supply and drainage equipment, etc., and flame-retardant products are suitable for home appliance parts, power distribution parts, etc., and their excellent durability extends the product life. It is of great help.

Claims (1)

[Claims] 1. An impact-resistant styrenic resin comprising (a) 10 to 90 parts by weight of a polyphenylene ether resin, and (b) a partially hydrogenated conjugated diene rubber, wherein the partially hydrogenated conjugated diene rubber is a conjugated 5 of all double bonds in diene rubber
Impact resistant partially hydrogenated conjugated diene rubber with ~70% hydrogenation and 1,2-vinyl bonds after hydrogenation of 3% by weight or less and 1,4 bonds of 30% by weight or more 90 to 10 parts by weight of styrene resin, (c) 0 to 10 parts by weight of styrene resin
80 parts by weight (d) Total amount of components (a), (b), and (c) 100
Stabilizer represented by the following general formula 0.01 per part by weight
-2 parts by weight of a polyphenylene ether resin composition. [Formula 1] (wherein A is an amino group, hydrogen, alkyl group, alkoxy group, cycloalkyl group or aryl group, B1, B2
each independently represents hydrogen or an alkyl group. ) [
2. The polyphenylene ether resin composition according to claim 1, which contains at least one of a sterically hindered phenol, an organic phosphite, an organic sulfur antioxidant, and an amine.