JPH04183748A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent impact resistance, heat resistance, processing properties and chemical resistance by blending a polyphenylene ether resin with specific amounts of a (rubber-reinforced) polystyrene resin, a specific hydrogenated diene copolymer, a polyolefin resin, etc. CONSTITUTION:100 pts.wt. total amounts of (A) 10-99wt.% polyphenylene ether resin and (B) 1-90wt.% polystyrene resin and/or rubber-reinforced polystyrene resin are blended with (C) 0.5-85 pts.wt. hydrogenated diene copolymer obtained by hydrogenating a block copolymer comprising a vinyl aromatic compound polymer block, a random copolymer block of a vinyl aromatic compound and a conjugated diene, etc., having >=90wt.% saturated double bond of the conjugated diene part and 50,000-300,000 calculated as polystyrene of number-average molecular weight and (D) 0-100 pts.wt. polyolefin resin.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyphenylene ether resin composition,
More specifically, the present invention relates to a polyphenylene ether resin composition that has excellent impact resistance, heat resistance, processability, and chemical resistance.

[Prior Art] Polyphenylene ether resin (hereinafter referred to as rP P EJ) is a resin with excellent heat resistance, mechanical strength, electrical properties, etc., but its moldability and impact resistance are insufficient, and improvements are needed. Products containing rubber-reinforced polystyrene resin are generally used. However, PPE
The rubber-reinforced polystyrene used in
~10% by weight (therefore, sufficient impact resistance improvement effect of PPE cannot be obtained.Furthermore, PPE compositions containing rubber-reinforced polystyrene resin do not have sufficient solvent crack resistance and require chemical resistance. There was a problem that it could not be used for the intended purpose.

[Problems to be Solved by the Invention] The present invention has been made against the background of the problems of the prior art described above, and has excellent impact resistance and chemical resistance, as well as heat resistance and
It is an object of the present invention to provide a PPE composition that also has excellent moldability.

[Means for Solving the Problems] The present invention provides (a) 10 to 99% by weight of polyphenylene ether resin (b) 1 to 90% by weight of polystyrene resin and/or rubber reinforced polystyrene resin (a) and (b) above. ) for a total of 100 parts by weight, (C) the following c-1 to c-
A polyphenyl ether resin composition comprising 0.5 to 85 parts by weight of at least one hydrogenated diene copolymer selected from the group No. 6 and 0 to 100 parts by weight of (d) a polyolefin resin.

C-1=vinyl aromatic compound polymer block (A);
Consisting of a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene, and a tapered block (C) in which the vinyl aromatic compound gradually increases among the vinyl aromatic compound and conjugated diene as necessary, these blocks A block copolymer in which (1) the vinyl aromatic compound/conjugated diene ratio is 5 to 40/95 to 60 by weight, (2) the (A) component and optionally (C) The bond content of vinyl aromatic compounds in the components is 3% of the total monomers.
~25% by weight, and the bond content of the vinyl aromatic compound in component (A) is at least 3% by weight, and (B) the vinyl bond content of the conjugated diene moiety in component (B) is 15 to 60%. A hydrogenated diene copolymer obtained by hydrogenating the combined product, in which at least 80% of the double bonds in the conjugated diene portion are saturated, and the number average molecular weight in terms of polystyrene is 50,000 to 300,000.

C-22 In c-1 above, general formula C(A) (B) E n-X, or [(
A) (B)-(C) ] n-X (wherein (A),
(B) and (C) are the same as c-1, n is an integer from 2 to 4, X
A hydrogenated diene-based copolymer obtained by hydrogenating a block copolymer represented by (indicates a coupling agent residue).

c-32 100 parts by weight of the hydrogenated diene copolymer of c-1 and/or c-2 above was added with an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group, an oxazoline group, an imide group and an epoxy group. A modified hydrogenated diene copolymer graft-polymerized with 0.01 to 20 parts by weight of an unsaturated compound having at least one functional group selected from the group.

C-4 = consisting of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer or a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene (A)
)-(B) a block copolymer, or if necessary, a tapered block (C) in which the vinyl aromatic compound of the vinyl aromatic compound and conjugated diene gradually increases (
A)-(B)-(C) block copolymer or (A)-(B) consisting of a vinyl aromatic polymer block (A)
-(A) a block copolymer, wherein the weight ratio of vinyl aromatic compound/conjugated diene is from 5 to 60/95;
40, ■ The bond content of the vinyl aromatic compound in component (A) and optional component (C) is 3% of the total monomers.
~50% by weight, and the bond content of the vinyl aromatic compound in component (A) is at least 3% by weight, and ■ the vinyl bond content of the conjugated diene moiety in component (B) exceeds 60%. A hydrogenated diene copolymer which is hydrogenated so that at least 80% of the double bonds in the conjugated diene portion are saturated and has a number average molecular weight of 50,000 to 600,000.

C-52 In c-4 above, general formula C(A) (B)]n-X, [(A)
(B) (C)]n-X, or C(A)-(B
) -(A) ]n -X (wherein (A), (B), (
C) is the same as c-4, n is an integer of 2 to 4, and X represents a coupling agent residue) A hydrogenated diene copolymer obtained by hydrogenating a block copolymer represented by:

C-6 = 100 parts by weight of the hydrogenated diene copolymer of the above c-4 and/or the above c-5, an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group, an oxazoline group,
A modified hydrogenated diene copolymer graft-polymerized with 0.01 to 20 parts by weight of an unsaturated compound having at least one functional group selected from the group of imide groups and epoxy groups.

It provides:

The present invention will be explained in detail below.

[1] Description of polyphenylene ether resin as component (a) of the present invention (hereinafter referred to as "a")
component") is represented by the following general formula (I) (wherein R,...
R2, R3 and R4 are the same or different alkyl groups,
It is a polymer consisting of repeating structural units represented by aryl groups, halogen atoms, hydrogen atoms, etc., where n represents the degree of polymerization. Specific examples include poly(2,6-dimethylphenylene) nylene-1,4-ether), poly(2゜6-diethylphenylene-1,4-ether), poly(2,6-diprophenylene-1,4-ether), poly(2-methyl-6
-ethylphenylene-1,4-ether), poly(2-
chloro-6-methylphenylene-1,4-ether),
Poly(2-methyl-6-itubropylphenylene-1.
4-ether), poly(2,6-di-n-propylphenylene-1,4-ether), poly(2-chloro-6-
polyphenylene-1,4-ether), poly(2-chloro-6-nitylphenylene-1,4-ether), poly(2-methylphenylene-1,4-ether), poly(2-chlorophenylene) -1,4-ether), poly(
2-phenylphenylene-1,4-ether), poly(
2-methyl-6-phenylphenylene-1゜4-ether), poly(2-bromo-6-phenylphenylene-1
, 4-ether), poly(2゜4'-methylphenylphenylene-1,4-ether), poly(2,3,6-drimethylphenylene-1,4-ether), and copolymers thereof. Examples include styrenic compound graft copolymers and styrenic compound graft copolymers thereof. Particularly preferred are polymers obtained from 2,6-dimethylphenol and copolymers obtained from 2,6-dimethylphenol and 2.3.6-dimethylphenol.

The amount of component (a) used in the present invention is 10 to 99% by weight, preferably 15 to 90% by weight, more preferably 15% by weight.
~70% by weight, particularly preferably 15-60% by weight. If the amount used exceeds 99% by weight, moldability and impact resistance will be poor, and if it is less than 10% by weight, heat resistance will be poor.

[2] Description of component (b) of the present invention Component (b) of the present invention is a styrenic resin consisting of a polystyrene resin and/or a rubber-reinforced polystyrene resin (
Hereinafter, it will be referred to as "component (b)." ).

The polystyrene resin is a polymer made of an aromatic vinyl compound or a copolymer of another vinyl monomer copolymerizable with the aromatic vinyl compound. The aromatic vinyl compounds used here include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromustyrene, dibromostyrene, p-tert-butylstyrene, ethylstyrene, Examples include vinylnaphthalene, which may be used alone or in combination of two or more. A preferred aromatic vinyl compound is styrene.

Other copolymerizable vinyl monomers include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-
Acrylic acid alkyl esters such as ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, pendyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethyl hexyl methacrylate,
Methacrylic acid alkyl esters such as cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, maleimide, N-methylmaleimide, N
-Ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-
Examples include maleimide compounds such as phenylmaleimide and N-(p-bromophenyl)maleimide.

The rubber-reinforced polystyrene resin is a resin obtained by polymerizing the above-mentioned aromatic vinyl compound or it and other vinyl monomers in the presence of rubber.

Rubbers used in such polymers include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, diene rubber such as polyisoprene, ethylene-α-olefin copolymer, ethylene-
α-olefin-polyene copolymer, non-diene rubber such as polyacrylic acid ester, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, ethylene-propylene elastomer, styrene-grafted ethylene-propylene Examples include elastomers, ethylene-based ionomer resins, and hydrogenated styrene-isoprene block copolymers.

Such styrene-butadiene block copolymers include XY type, XYX type, xyx tapered type, radial teleblock type, and the like.

These rubbers can be used alone or in combination of two or more.

Examples of methods for producing rubbery styrenic polymers include graft polymerization, solution polymerization, bulk polymerization, and suspension polymerization.

The amount of component (b) used is 1 to 90% by weight, preferably 10% by weight.
~85% by weight, more preferably 30-85% by weight, particularly preferably 40-85% by weight. If the amount of component (b) used is less than 10% by weight, moldability will be poor;
If it exceeds 0% by weight, heat resistance will be poor.

[3] Description of hydrogenated diene polymers c-1 to 'c-6 which are component (C) of the present invention 3-1) Description of monomer components c-1 to c-6 c-1 ~c
The aromatic vinyl compounds used in -6 include styrene, t-butylstyrene, α-methylstyrene, P-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, vinylpyridine, N,N-diethyl-P- Examples include aminoethylstyrene, especially styrene, α
- Methylstyrene is preferred.

In addition, examples of conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,
3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-
Examples include octadiene, 3-butyl-1,3-octadiene, chloroprene, etc., but in order to obtain a hydrogenated diene copolymer that can be used industrially and has excellent physical properties, 1゜3-butadiene, isoprene, 1,3-pentadiene is preferred, and 1,3-butadiene is more preferred.

3-2) Description of hydrogenated diene polymer of c-1
-1 is a vinyl aromatic compound polymer block (A);
A random copolymer block (B) of a vinyl aromatic compound and a conjugated diene, and if necessary, a tapered block (C) in which the vinyl aromatic compound gradually increases among the vinyl aromatic compound and conjugated diene are combined in a block manner. First, the weight ratio of vinyl aromatic compound/conjugated diene in all monomers is 5 to 40/
95-60, preferably 7-40/93-60.

If the content of the vinyl aromatic compound is less than 5% by weight, the modification effect when blending the finally obtained hydrogenated diene copolymer with other resins is insufficient, for example, when blended with PPE. , the desired impact resistance cannot be obtained.

On the other hand, when the content of the vinyl aromatic compound exceeds 40% by weight, it becomes resinous, and when blended with other resins,
Impact resistance improvement effect, especially low-temperature impact resistance, is insufficient.

In addition, the bond content of the vinyl aromatic compound in the vinyl aromatic compound polymer block (A) and the taper block (C) which is optionally constituted is 3 to 25% by weight of the total monomers, preferably 5 to 20% by weight of the total monomers. % by weight, and the combined content of vinyl aromatic compounds in component (A) is at least 3% by weight, preferably from 5 to 15% by weight. (A) component and (C
) If the bond content of the vinyl aromatic compound of the component is less than 3% by weight of the total monomers, when the obtained hydrogenated diene copolymer is pelletized, blocking will not occur and P
When blended with PE, the molded appearance will be inferior,
On the other hand, when the bond content of the vinyl aromatic compound in the components (A) and (C) exceeds 25% by weight, it becomes resinous,
The desired impact resistance cannot be obtained, and especially low-temperature impact resistance is greatly reduced.

Furthermore, the vinyl bond content of the conjugated diene moiety in the block (B) consisting of a random copolymer of a vinyl aromatic compound and a conjugated diene is 15 to 60%, preferably 20 to 55%.
%. In order to produce products with a vinyl bond content of less than 15%, severe polymerization conditions are required, which not only poses an industrial disadvantage in terms of production, but also provides insufficient impact resistance improvement effects when blended with PPE. If it is 60% or less, even better impact resistance can be obtained.

Further, in the hydrogenated diene copolymer of the present invention, at least 80% of the double bonds in the conjugated diene moiety, preferably 93 to
It is necessary that 100% is hydrogenated and saturated; if it is less than 90%, the heat resistance, weather resistance, and ozone resistance will be poor.

Furthermore, the hydrogenated diene copolymer of the present invention has a polystyrene equivalent number average molecular weight of 50,000 to 300,000, preferably 7 to 25
If it is outside this range, a sufficient modifying effect cannot be obtained in a composition blended with other resins. For example, if the number average molecular weight is less than 50,000, the impact resistance of the resulting composition will decrease, while if it exceeds 300,000, it will result in deterioration in moldability and surface appearance.

In addition, the hydrogenated diene copolymer of the present invention has a surface gloss of 230% in terms of processability and surface gloss of a blend composition with other resins.
℃, the melt flow rate measured under a load of 5 kg is preferably 0.1 g/10 minutes or more, more preferably 1 to 1
00g/10 minutes.

The hydrogenated diene copolymer of the present invention can be prepared by combining block (A), random copolymer block (B), and optionally block (C) in an organic solvent using an organic alkali metal compound as an initiator. After anionic polymerization to obtain a block copolymer, this block copolymer is further hydrogenated.

Any method may be used to form the block copolymer, but generally the block (A) or random copolymer block (B) is first polymerized using a polymerization initiator such as an alkali metal compound in an organic solvent, and then The random copolymer block (B) or block (A) is polymerized. There is no limitation as to which of the block (A) or the random copolymer block (B) is polymerized first. Further, the boundary between the block (A) and the random copolymer block (B) does not necessarily need to be clearly distinguished.

In addition, when copolymerizing the block (C) as necessary, the taper block (
C) is polymerized.

In this case, the tapered block (C) is first polymerized, then the random copolymer block (B), the block (
Examples include a method of polymerizing A).

The amount of vinyl bonds in the conjugated diene can be adjusted to a desired vinyl bond content by appropriately selecting the amount and type of microstructure modifier such as tetrahydrofuran used during polymerization.

Furthermore, the number average molecular weight and melt flow rate are controlled by the amount of a polymerization initiator, such as n-butyllithium.

c-1 of the present invention is obtained by dissolving the block copolymer obtained in this way in an inert solvent, and heating at 20 to 150°C for 1 to 10 minutes.
Hydrogenation is carried out under pressurized hydrogen of 100 kg/cIiY in the presence of a hydrogenation catalyst.

3-3) Description of hydrogenated diene copolymer of c-2 C-2 of the present invention has the general formula C(A)-(B)]n-X in which c-1 is coupled with a coupling agent. , or C(A) -(B) -(C) ) n-X (wherein (A), (B), and (C) are the same as c-1, and n is 2 to
This is a hydrogenated diene copolymer obtained by hydrogenating a block copolymer represented by the following formula (integer 4, X indicates a coupling agent residue).

When c-2 is used, a material with an even better balance of physical properties between impact resistance and moldability can be obtained.

Coupling agents used in the production of block copolymers include, for example, diethyl adipate, divinylbenzene,
Tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1,4-chloromethylbenzene, bis(trichlorosilyl)ethane, epoxidized linseed oil, Tolylene diisocyanate, 1. ．． Examples include 2,4-pencent triisocyanate.

3-4) Description of the hydrogenated diene copolymer of c-3
1 and/or C') hydrogenated diene copolymer 100
0.01 to 20 parts by weight of an unsaturated compound having at least one functional group selected from the group of acid anhydride groups, carboxyl groups, hydroxyl groups, amino groups, oxazoline groups, imide groups, and epoxy groups. Modified hydrogenated diene copolymer graft-polymerized in parts.

When c-3 is used, a molded product with even better chemical resistance and appearance can be obtained.

3-5) Description of the hydrogenated diene copolymer of c-4 The c-4 of the present invention comprises a vinyl aromatic compound polymer block (A), a conjugated diene polymer or a vinyl aromatic compound and a conjugated diene. A (A)-(B) block copolymer consisting of a random copolymer block (B) of ) consisting of (A)-(B)-(C) block copolymer, or (A)-( consisting of vinyl aromatic polymer block (A))
B) - (A) Consisting of a block copolymer, first, ■
The weight ratio of hinyl aromatic compound/conjugated diene in all monomers is 5 to 60/95 to 40, preferably 7 to 40.
/93 to 60 is required.

If the content of the vinyl aromatic compound is less than 5% by weight, the modification effect when blending the finally obtained hydrogenated diene copolymer with other resins is insufficient, for example, when blended with PPE. , the desired impact resistance cannot be obtained.

On the other hand, if it exceeds 60% by weight, it becomes resin-like, and the desired impact resistance cannot be obtained, and in particular, the low-temperature impact resistance is greatly reduced.

In addition, the bond content of the vinyl aromatic compound in the vinyl aromatic compound polymer block (A) and the taper block (C) which is optionally constituted is 3 to 50% by weight, preferably 5 to 40% by weight of the total monomers. % by weight, more preferably 5~
25% by weight, and the combined content of vinyl aromatic compounds in component (A) is at least 3% by weight, preferably from 3 to 20% by weight.

If the bond content of the vinyl aromatic compound of component (A) or component (A) and component (C) is less than 3% by weight of the total weight, blocking may occur when the resulting hydrogenated diene copolymer is pelletized. In addition, when blended with PPE, the molded appearance becomes inferior. On the other hand, if the bond content of the vinyl aromatic compound of component (A) or components (A) and (C) exceeds 50% by weight, the resin The effect of improving impact resistance is insufficient, especially low-temperature impact resistance.

Furthermore, the amount of vinyl bond gold t in the conjugated diene moiety in the conjugated diene polymer or the random copolymer block (B) of a vinyl aromatic compound and a conjugated diene exceeds 60%,
Preferably it is 70% or more, more preferably 80% or more. When the vinyl bond content is 60% by weight or more, even better moldability can be obtained.

In addition, the vinyl bond here refers to a monomer unit in which a conjugated diene compound is polymerized at a double bond at a 1,2- or 3,4-bond position.

Furthermore, the hydrogenated diene copolymer of the present invention has a block (
at least 80% of the double bonds of the conjugated diene moiety of B);
Preferably 90% or more, more preferably 95-100
% must be hydrogenated and saturated, 80%
If it is less than %, heat resistance, weather resistance, and ozone resistance will be poor.

Furthermore, the hydrogenated diene copolymer of the present invention has a polystyrene equivalent number average molecular weight of 50,000 to 600,000, preferably 8 to 50,000.
If it is outside this range, a sufficient modifying effect cannot be obtained in a composition blended with other resins. For example, if the number average molecular weight is less than 50,000, the impact resistance of the resulting composition will decrease, while if it exceeds 600,000, fluidity and processability will decrease, leading to a deterioration in surface appearance.

Note that the hydrogenated diene copolymer of the present invention is heated at 230°C,
The melt flow rate measured under a load of 12.5 kg is preferably 0.1 g/10 minutes or more, more preferably 0.1 g/10 minutes or more.
If it is 5 g/10 minutes or more, and if it is less than 0°1 g/10 minutes, it will be difficult to pelletize.

3-6) Description of hydrogenated diene copolymer of c-5 The c-5 of the present invention has the general formula [(A)-(B)
]n-X, [(A) (B)-(C)]n-X, or [(A
)-(B)-(A) ] n-X (wherein (A), (B)
, (C) is the same as c-4, n is an integer of 2 to 4, and X represents a coupling agent residue) A hydrogenated diene copolymer obtained by hydrogenating a block copolymer represented by the following.

When c-5 is used, a product with a higher level of physical property balance between impact resistance and moldability can be obtained.

Incidentally, the coupling agent is the one exemplified in c-2 above.

3-7) Description of hydrogenated diene copolymer of c-6 The c-6 of the present invention is produced by adding 100 parts by weight of the hydrogenated diene copolymer of the above c-4 and/or the above c-5 to an acid. Unsaturated compound having at least one functional group selected from the group of anhydride group, carboxyl group, hydroquine group, amino group, oxazoline group, imide group and epoxy group 0.01 to 20
A modified hydrogenated diene copolymer graft-polymerized in parts by weight.

When c-6 is used, a molded product with even better chemical resistance and appearance can be obtained.

3-8) Manufacturing method of c-1 to c-6 The manufacturing method of c-l to c-3 is described in Japanese Patent Application No. 1-124
429. The manufacturing method of c-4 to c-6 is
This is shown in Japanese Patent Application No. 1-236846.

3-9) Amount of component (c) to be used and reason for limiting the numerical value. (C) component is at least one selected from the group of c-1 to c-6 above.
This is a type of hydrogenated diene-based copolymer, and by using component (C), compared to conventional impact resistance improvers such as rubber, there is less sacrifice in reducing chemical resistance (and impact resistance is improved). It has the excellent effect of improving

The amount of component (C) used is 0.5 to 85 parts by weight, preferably 0.5 to 70 parts by weight, more preferably 1 to 70 parts by weight, based on 100 parts by weight of the total amount of components (a) and (b). 60 parts by weight, particularly preferably 1 to 50 parts by weight. If the amount of component (c) used is less than 0.5 parts by weight, the desired impact resistance cannot be obtained, and if it exceeds 85 parts by weight, the heat resistance decreases, which is not preferable.

[4] Description of polyolefin resin as component (d) The polyolefin resin as component (d) of the present invention (hereinafter referred to as "(d)")
) is preferably a polypropylene resin and/or a polyethylene resin. Examples of the polypropylene resin include propylene homopolymers, copolymers of propylene with ethylene and α-olefins, and mixtures of these with homopolymers or copolymers of α-olefins other than propylene.

The α-olefin used here has a carbon number of 6 to
12 are used, and 1-^, xeno, 1-octene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene and the like are particularly preferred. The abundance ratio of α-olefin in the copolymer is preferably 0.5% by weight or less.

Further, as the polyethylene resin, any one of high density, medium density, or low density can be used, and polyethylene resin modified with other monomers, halogen compounds, etc. can also be used. A particularly preferred component (d) is a polypropylene resin.

When component (d) is blended into a composition consisting of components (a), (b) and (c) described above, a composition with much better chemical resistance can be obtained. (d) The usage amount of component (a) and (
The amount is 0 to 100 parts by weight, preferably 0.5 to 75 parts by weight, more preferably 1 to 50 parts by weight, particularly preferably 1 to 25 parts by weight, based on 100 parts by weight of the total amount of components b). If the amount of component (C) used exceeds 100 parts by weight, impact resistance and heat resistance will be poor.

The polyphenylene ether resin composition of the present invention can be produced using an extruder, kneader, Banbury mixer, roll, etc.
It can be obtained by melt-kneading. When producing the polyphenylene ether resin composition of the present invention, each component may be mixed all at once, or a split mixing method in which two or more arbitrary components are premixed in part or in full, and then the remaining components are added and mixed. But that's fine.

When using the polyphenylene ether resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass beads, glass flakes, wastrite, calcium carbonate, talc, barium sulfate, mica, potassium titanate,
Fillers such as aramid fibers, molybdenum disulfide, and fluororesins can be added singly or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more.

These fillers are used in an amount of 5 to 150 parts by weight based on 100 parts by weight of the polyphenylene ether resin composition.

Moreover, various other compounding agents can be added to the composition of the present invention.

Examples of these compounding agents include 2,6-di-t-butyl-4-methylphenol, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, and 2,2-methylene-bis-(4- ethyl-6-t-butylphenol), 4,4'-thiobis-(6-t-butyl-3
-methylphenol), dilaurylthiodipropionate, tris(di-nonylphenyl)phosphite, wax, and other antioxidants: pt-butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone, 2 - (2'-hydroxy-4'-n-
UV absorbers such as (octoxyphenyl) benzotriazole; paraffin wax, stearic acid, hydrogenated oil,
Lubricants such as stearamide, methylene bis stearamide, n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride; antimony oxide, ammonium hydroxide, zinc borate, tricresyl phosphate, tris(dichloro Flame retardants such as propyl) phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, and tetrabromobisphenol A; antistatic agents such as stearamidopropyldimethyl-β-hydroxyethylammonium nitrate; titanium oxide, carbon black, etc. colorants; pigments, etc.

The polyphenylene ether resin composition of the present invention can be molded into various molded products by contrast molding, sheet molding, vacuum molding, irregular molding, foam molding, blow molding, stamp sample molding, and the like.

The obtained molded product can be used for automobile exteriors, interior parts, various electric/electronic parts, housings, etc. by taking advantage of its excellent properties.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the examples, parts and percentages are based on weight unless otherwise specified.

The molecular weight and styrene bond content in the examples were measured by the method described in the patent application.

The 1,2-vinyl bond content of polybutadiene in the examples was calculated by the Morello method using infrared analysis.

The physical properties of the polyphenylene ether resin composition of the present invention were evaluated by the following method.

[Forming method] A polyphenylene ether resin composition having the compounding ratio shown in Table 1 was kneaded and extruded using a twin-screw extruder with a barrel temperature of 280 to 300°C to form pellets. After drying the obtained pellets, test pieces for measuring physical properties were molded using an injection molding machine with a molding temperature of 280°C.

[Physical property evaluation method] Impact resistance: According to ASTM D-256, thickness 1/
4″ notch with 23 mounting options.

Heat resistance: Thickness 1 according to ASTM D-648
/4'' and a load of 18.5 kg/cd.

A 1% strain was applied to a solvent-resistant knee test piece (1/8" UL bar), and after immersing it in kerosene and leaving it for 48 hours, the state of fracture and crack occurrence was observed, and the test was divided into four stages as shown below. evaluated.

◎: No breakage or cracking occurred.

○: A small rack has occurred.

△: A large rack has occurred.

×: Fracture Flexural modulus: Thickness 1 according to ASTM D-790
/8' test piece.

Processability (MFR): Using a sufficiently dry pellet, 28
It was measured at 0° C. and a load of 10 kg (unit: 2710 minutes).

Description of components (a), (b), (C), and (d) used in the examples (a) component polyphenylene ether A-12,6-xylenol, cupric bromide and di-n- Polyphenylene ether (A-1) [η] obtained by carrying out a polymerization reaction using butylamine in a toluene solution at 30°C while blowing oxygen (chloroform, 30°C
) is 0.40.

(b) Components B-1, B-2 B-1: Rubber-reinforced polystyrene resin Riflex HF-76 (manufactured by Mitsubishi Polytic ■) B-2; Polystyrene resin Topolex 500-51 (manufactured by Mitsui Toatsu ■) ) Component (C) Hydrogenated diene copolymers H-1 to H-(c)
The components are hydrogenated diene copolymers H-1 to H-16 shown in Table 1, where (A) is a styrene polymer block and (B) is a random copolymer block of styrene and butadiene. , (C) is a tapered block in which styrene gradually increases among styrene and butadiene.

H-3 and H-12 in the table are examples of hydrogenated diene copolymers using a coupling agent (butyltrichlorosilicon) during polymerization of the block copolymer.

H-7 and H-14 in the table are examples of modified hydrogenated diene copolymers in which 1 part maleic anhydride was grafted onto 100 parts by weight of the hydrogenated diene copolymer.

H-1 to H-8 and H-15 in the table are Japanese Patent Application No. 1-124
429, and H-9 to H-14 and H-16 are manufactured by the method shown in Japanese Patent Application No. 1-2368.
It was manufactured by the method shown in No. 46.

(d) Component D-1; Polypropylene MX3A (manufactured by Mitsubishi Yuka ■) D-2; Polypropylene MH8 (manufactured by Mitsubishi Yuka ■) D-3; Polyethylene Staphrene E791 (Japan Petrochemical Corporation) Examples 1 to 22 (The formulation and evaluation results are shown in Table 2) The polyphenylene ether resin composition of the present invention has excellent impact resistance, heat resistance, chemical resistance, moldability, and flexural modulus, and meets the objectives of the present invention. A resin composition has been obtained.

Comparative Examples 1 to 7 (The formulation and evaluation results are shown in Table 2) Comparative Example 1 is an example in which the amount of component (a) used exceeds the range of the present invention, and the impact resistance and moldability are poor. Inferior.

Comparative Example 2 is an example in which the amount of component (a) used is less than the range of the present invention, and the impact resistance, heat resistance, and chemical resistance are poor.

Comparative Example 3 is an example in which the amount of component (c) used is less than the range of the present invention, and the impact resistance and processability are poor.

Comparative Example 4 is an example in which the amount of component (d) used exceeds the range of the present invention, and the impact resistance, heat resistance, and flexural modulus are inferior.

Comparative Example 5 is an example in which the amount of component (C) used exceeds the range of the present invention, and the heat resistance, chemical resistance, and flexural modulus are inferior.

Comparative Example 6 is an example in which an A-B-A type hydrogenated diene copolymer whose structure is outside the scope of the present invention is used as c-1 of the component (C), and it has good impact resistance and chemical resistance. Poor properties and moldability.

Comparative Example 7 is an example in which a block copolymer before hydrogenation is used as the component (C), but it is inferior in impact resistance, chemical resistance, and moldability.

Blank space below [Effects of the invention] In the past, attempts have been made to blend rubber or hydrogenated diene copolymers to improve the impact resistance of polyphenylene ether and (rubber-reinforced) polystyrene resins. However, even if impact resistance is obtained, chemical resistance is reduced.

The present invention provides a polyphenylene ether resin composition that has an excellent physical property balance of moldability and impact resistance and has excellent chemical resistance by blending a specific hydrogenated diene copolymer defined in the present invention. The industrial value is extremely large.

Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] (1) (a) 10 to 99% by weight of polyphenylene ether resin (b) 1 to 90% by weight of polystyrene resin and/or rubber-reinforced polystyrene resin With respect to the total of 100 parts by weight of the above (a) and (b), (c) Contains 0.5 to 85 parts by weight of at least one hydrogenated diene copolymer selected from the group c-1 to c-6 below and (d) 0 to 100 parts by weight of a polyolefin resin. A polyphenylene ether resin composition. c-1: vinyl aromatic compound polymer block (A),
Consisting of a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene, and a tapered block (C) in which the vinyl aromatic compound gradually increases among the vinyl aromatic compound and conjugated diene as necessary, these blocks [1] A vinyl aromatic compound/conjugated compound having a weight ratio of 5 to 40/95 to 60, [2] Component (A) and optionally (C)
The bond content of the vinyl aromatic compound in the component is 3 to 25% by weight of the total monomers, and the bond content of the vinyl aromatic compound in the component (A) is at least 3% by weight; [3] Conjugation in the component (B) A block copolymer having a vinyl bond content of 15 to 60% in the diene portion is hydrogenated, and at least 90% of the double bonds in the conjugated diene portion are saturated, and the number average molecular weight in terms of polystyrene is 50,000 to 300,000. A hydrogenated diene copolymer. c-2: In c-1 above, the general formula [(A)-(B)] n-X, or [(A)-(B)-(C)] n-X (in the formula, (A), (B) and (C) are the same as c-1, n is an integer of 2 to 4, and X represents a coupling agent residue). Polymer. c-3: 100 parts by weight of the hydrogenated diene copolymer of c-1 and/or c-2 above is added to an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group, an oxazoline group, an imide group and an epoxy group. A modified hydrogenated diene copolymer graft-polymerized with 0.01 to 20 parts by weight of an unsaturated compound having at least one functional group selected from the group. c-4: consisting of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer or a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene (A)
)-(B) a block copolymer, or if necessary, a tapered block (C) in which the vinyl aromatic compound of the vinyl aromatic compound and conjugated diene gradually increases (
A)-(B)-(C) block copolymer or (A)-(B) consisting of a vinyl aromatic polymer block (A)
-(A) a block copolymer, wherein the weight ratio of [1] vinyl aromatic compound/conjugated diene is 5 to 60/95;
~40) [2] (A) component and optionally configured (C)
The bond content of the vinyl aromatic compound in the component is 3 to 50% by weight of the total monomers, and the bond content of the vinyl aromatic compound in the component (A) is at least 3% by weight; [3] Conjugation in the component (B) Hydrogenated block copolymers with a vinyl bond content of more than 60% in the diene part, at least 80% of the double bonds in the conjugated diene part are saturated, and a number average molecular weight of 50,000 to 600,000. Diene copolymer. c-5: In c-4 above, the general formula [(A)-(B)] n-X) [(A)-(B)-(C)] n-X, or [(A)-(B )-(A)]n-X (wherein (A), (B), and (C) are the same as c-4, n is an integer of 2 to 4, and X represents a coupling agent residue) A hydrogenated diene copolymer obtained by hydrogenating the block copolymer shown above. c-6: 100 parts by weight of the hydrogenated diene copolymer of c-4 and/or c-5 above, an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group, an oxazoline group,
A modified hydrogenated diene copolymer graft-polymerized with 0.01 to 20 parts by weight of an unsaturated compound having at least one functional group selected from the group of imide groups and epoxy groups.