JPH0236248A - Polypropylene based resin composition - Google Patents

Abstract

PURPOSE:To obtain a polypropylene based resin composition having excellent impact resistance and coating properties and suitable for automobile part and various kind of molding materials by blending polypropylene with a thermoplastic polyurethane and/or specific thermoplastic resin and modified polyolefin. CONSTITUTION:The aimed resin composition obtained by blending 100 pts.wt. total of (A) polypropylene based resin and (B) thermoplastic polyurethane and/or (C) 5-95 pts.wt. thermoplastic resin selected from a group consisting of polyamide resin, polyester resin, aromatic polyether resin, polyacetal resin, etc., with (D) 1-30 pts.wt. modified polyolefin obtained by reacting a polyolefin modified with an unsaturated acid (anhydride) with low-molecular diol, low-molecular diamine or low-molecular compound containing hydroxyl group and amino group and/or further polyurethane having NCO end.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polypropylene resin composition.

[Prior Art] A composition of polyolefin and thermoplastic polyurethane is described in JP-A-62-2954154.

[Problem to be solved by the invention] However, the conventional products have problems when used for various molded products.
It was inappropriate in terms of strength.

[Means for solving the problem] In view of the above-mentioned points, the present inventors have developed a composition mainly composed of polyolefin and thermoplastic polyurethane elastomer, or a polypropylene resin and heat As a result of intensive studies to obtain a composition mainly composed of a plastic resin, the present invention was achieved. That is, the present invention provides a
) A polypropylene resin composition prepared by blending b) a thermoplastic polyurethane and C) a modified polyolefin into a polypropylene resin, and a) a polypropylene resin containing d.
) A thermoplastic resin selected from the group consisting of polyamide resin, polyester resin, aromatic polyether resin, polyacetal resin, polycarbonate resin, ABS resin, and if necessary, thermoplastic polyurethane and C) modified polyolefin as a compatibilizer. A polypropylene resin composition, a method for producing a polypropylene resin molded product characterized by injection molding, extrusion molding or compression molding of this composition, and a low molecular weight polyolefin modified with an unsaturated acid or an unsaturated acid anhydride. diol,
A low-molecular diamine, or a product obtained by reacting a low-molecular compound containing a hydroxyl group and an amine group, and/or further N
This is a compatibilizer for polypropylene resins made of a modified polyolefin reacted with CO-terminated polyurethane.

The polypropylene resin used in the present invention includes polypropylene homopolymers and α- Olefin-propylene random copolymer α-olefin-propylene bronocopolymer (α-olefin has 2 to 18 carbon atoms), and propylene-containing ff120
% by weight or more, MI is preferably 0.5-100,
More preferably, the propylene content is 50% by weight or more, MI2
-70 and is crystalline.

Examples of the modified polyolefin used in the present invention include (a) obtained by modifying a polyolefin with a hydroxyl group-containing unsaturated compound and/or an amino-based unsaturated compound.

The amount of unsaturated compound or unsaturated compound mixture used for modification is usually 1.5 to 30%, preferably 3 to 30%.
It is 10% by weight. If it is less than 1.5% by weight, no compatibilizing effect on polyurethane will be exhibited, and if it exceeds 30% by weight, the compatibility with polypropylene resin will decrease.

The polyolefins used for this modification include high-density polyethylene, medium-density polyethylene, low-density polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, a copolymer of ethylene and α-olefin, and a copolymer of propylene and α-olefin. Polyolefin thermoplastic elastomers such as polymers or their oligomers, ethylene-propylene rubber, EPDM, EVA, butyl rubber, butane rubber, low-crystalline ethylene-propylene copolymers, or propylene-butene copolymers, or , their oligomers, polyolefin elastomers such as polyolefin thermoplastic elastomers mainly composed of blends of polypropylene and ethylene-propylene rubber, ethylene-vinyl ester copolymers, ethylene-acrylic ester copolymers and their oligomers, etc. and blends of these various polyolefins and oligomers. Preferred are polypropylene, a copolymer of propylene and α-olefin, EPDM or low density polyethylene, and oligomers thereof. The molecular weight used is usually 1,000 to 500,000, preferably 3,000 to 200,000.

There is no particular limit to the amount of double bonds in the polyolefin used for modification, but if the number of carbon atoms is 100 at the terminal and/or within the molecule
It is preferable that the number is 0.5 or more per 0, and it is particularly preferable that the number is more than 1.5. Furthermore, it is preferable to have more than 1.5 molecules only at the ends.

Among the unsaturated compounds used for modification in the present invention, the unsaturated compound containing a hydroxyl group contains one hydrocarbon group having 2 to 3 carbon atoms and one or more hydroxyl groups each having an ethylenically unsaturated bond in one molecule. Examples include compounds that.

Specifically, for example, hydroxyethyl acrylate, hydroquine ethyl methacrylate, glycerol methacrylate, glycerol acrylate, hydroquine propyl acrylate, hydroxypropyl methacrylate,
Examples include polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glycol acrylate, polypropylene glycol methacrylate, caprolactone-modified 2-hydroxyethyl acrylate, caprolactone-modified 2-hydroxyethyl methacrylate, N-(4-hydroquinphenyl)maleimide, etc. These compounds can be used as -m or in combination of two or more. Preferred is glycerol acrylate,
They are hydroxyethyl methacrylate and N-'(4-hydroquinphenyl)maleimide.

Examples of the amino group-containing unsaturated compound include vinyl monomers containing at least one type of amine group or substituted amine group as shown in general formula (+).

(In the formula RI: hydrogen, methyl group or ethyl group R2:
Hydrogen, alkyl group with 1 to 1 carbon atoms, 2 to 18 carbon atoms
an alkanoyl group, a phenyl group, an alkylphenyl group, and a cycloalkyl group having G to 12 carbon atoms. ) Specifically, aminoethyl acrylate, propylaminoethyl acrylate, dimethylamineethyl methacrylate,
Alkyl ester derivatives of acrylic acid or methacrylic acid such as aminopropyl methacrylate, phenylaminoethyl methacrylate and cyclohequinylaminoethyl methacrylate; allylamine derivatives such as allylamine, methalylamine and N-methylamine; Examples include vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, aminostyrenes such as P-aminostyrene, acrylamide derivatives such as acrylamide and methacrylamide, and mixtures of two or more thereof. Preferred are aminostyrene and allylamine.

Examples of unsaturated acids include acrylic acid, methacrylic acid,
Examples include crotonic acid, cinnamic acid, itaconic acid, maleic acid, and mixtures of two or more thereof. Preferred is maleic acid.

Examples of unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, chloroitaconic anhydride, chloromaleic anhydride,
Examples include anthraconic anhydride, and these unsaturated acid anhydrides can be used alone or in combination of two or more. Preferred is maleic anhydride.

The above-mentioned unsaturated compounds used for modifying the polyolefin may be used in combination. Preferred are unsaturated compounds containing hydroxyl groups and/or unsaturated compounds containing amino groups.

The modified polyolefin (a) can be produced by reacting the above functional group-containing unsaturated compound with a polyolefin in the presence of an organic peroxide.

As the organic peroxide, those generally used as initiators in radical polymerization can be used, and there are no particular restrictions on the type of peroxide used, but those with a half-life of +00°C or more are preferred. Ketone peroxides such as 1-bis-1-butylperoxy-3,3,5-)limethylcyclohexane, dialkyl peroxides such as dicumyl peroxide, and diacyl peroxides such as benzoyl peroxide. , peroxy esters such as 2,5-dimethyl-dibenzoylperoquine hexane, and hydroperoxides such as 2,5-dimethylhexane-2,5-hydroperoxide.

As a method for producing the modified polyolefin (a), any known method such as a solution method or a melt method can be used. In the solution method, it can be obtained by dissolving the polyolefin and the unsaturated compound or the unsaturated compound mixture in an organic solvent and heating the solution. The organic solvent used is a hydrocarbon having 6 to 12 carbon atoms, or a hydrocarbon having 6 to 12 carbon atoms.
halogenated hydrocarbons and the like can be used. Further, the reaction temperature is a temperature at which the polyolefin used is dissolved, and is generally preferably 110 to +60''C.

In the melt method, it can be obtained by mixing a polyolefin and the unsaturated compound or the unsaturated compound mixture with an organic peroxide, melt-mixing, and reacting. This can be carried out using an extruder, Brabender kneader, Banbury mixer, blast mill, etc., and the kneading temperature is between the melting point of the polyolefin used and 300"C.
The following temperature ranges are preferred.

Modified polyolefin is obtained by reacting a polyolefin modified with an unsaturated acid or an unsaturated acid anhydride with a low-molecular diol, a low-molecular diamine, or a low-molecular compound having a hydroxyl group and an amine group (b), and further NCO terminal (C) can be produced by the following method.

Examples of the unsaturated acid or unsaturated acid anhydride used for producing the modified polyolefin (b) include the following.

Examples of unsaturated acids include acrylic acid, methacrylic acid,
Examples include crotonic acid, cinnamic acid, itaconic acid, maleic acid, and mixtures of two or more thereof. Preferred is maleic acid.

Examples of unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, chloroitaconic anhydride, chloromaleic anhydride,
Examples include citraconic anhydride, and these unsaturated acid anhydrides can be used alone or in combination of two or more. Preferred is maleic anhydride.

The method for producing the polyolefin modified with an unsaturated acid or an unsaturated acid anhydride can be the same as that for the modified polyolefin (a). The poison of unsaturated acids and unsaturated acid anhydrides used for modification is usually 1.5 to 30% by weight based on the polyolefin, preferably 3 to 10 mm.
%.

As the low-molecular diol and low-molecular diamine used in the production of the modified polyolefin (b), those used in the polyurethane production method described below can be used. For example, diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, bishydroxyethoxybenzene, ethylenediamine,! , 4-butylenediamine,
Diamines such as cyclohexane diamine, tolylene diamine, and isophorone diamine. Examples of low molecular weight compounds having both a hydroxyl group and an amino group include alkanolamines such as monoethanolamine and jetanolamine. Among these, preferred low molecular weight compounds are those having both a hydroxyl group and an amine group.

The modified polyolefin (b) can be obtained by reacting at least one selected from these groups with the polyolefin modified with the unsaturated acid or unsaturated acid anhydride. As for the manufacturing method, the above-mentioned solution method and melting method can be similarly used. Do not use organic peroxide.

Alternatively, the above-mentioned diol, diamine, or compound having both a hydroxyl group and an amine group may be reacted in advance with the above-mentioned unsaturated acid or unsaturated acid anhydride, and then a melt method or a solution method can be used using an organic peroxide. A modified polyolefin can also be obtained in the same manner.

The modified polyolefin (C) is the aforementioned polyolefin modified with an unsaturated acid or an unsaturated acid anhydride, and a diol,
It can be obtained by reacting a diamine or a compound having a hydroxyl group and an amine group with an NCO-terminated polyurethane. A melt method can be used for this reaction. As this polyurethane, the same polyurethane as described below can be used. Preferably molecular fil 3000-50000 (7) also note, NG
The one containing 10.3-1.5% of Off is used. Further, m of the polyurethane used for modifying the modified polyolefin (C) is usually 5 to 80% by weight, preferably 15 to 6% by weight.
I am a heavy worker.

In the polypropylene resin composition of the present invention, the plasticizing polyurethane includes a child diisocyanate (a), a polymeric diol (b), and a low-molecular active hydrogen-containing compound (
Polyurethanes from c) can be used.

As the organic diisocyanate (a) used in the production of such polyurethane, those conventionally used in the production of polyurethane can be used.

Such diisocyanates include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group), aliphatic diisocyanates having 2 to 18 carbon atoms, and 4-1 carbon atoms.
5 alicyclic diisocyanates, aromatic aliphatic diisocyanates having 4 to 15 carbon atoms, and modified products of these diiso/anates (urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, uretdione groups,
(modified products containing uretdione groups, innurate groups, oxazolidone groups, etc.). Specific examples of such diisocyanates include those described in JP-A-53-42294, such as 1.3- and 1.4-phenylene diisocyanate, 2.4- and/or 2.6-) lylene diisocyanate) (TDI), diphenylmethane-
2,4-and/or 4,4-diisonane) (M
DI), naphthylene-1,5-diisocyanate 9m-
and aromatic diisocyanates such as p-isocyanatophenylsulfonyl isocyanate, ethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, 2.2.4-trimethylhexane diisocyanate, lysine diisocyanate, 2.
6-dicyanatomethylcabroate, bis(2-
Ethyl isocyanate) fumarate, bis(2-iso/
aliphatic diisocyanates such as 2-isocyanatoethyl-2,6-di-anetohexanoate, isophorone diiso/anate, zinc clohexylmethane diisocyanate (hydrogenated MD■)
, /Chloheki/Diiso/Anate, Methylene Chloheki/Diiso/Anate (Hydrogenated TDI), Bis(2-
alicyclic diisocyanates such as 4-7-lylohexene-1.2 dicarboxylate (iso/anetoethyl), cycloaliphatic diisocyanates such as quinoliene diisocyanate, diethylbenzene diisocyanate, modified MDI
(Urethane-modified MDI, carbodiimide-modified MDI,)
Modified diiso/anates such as urethane-modified TD), urethane-modified TD, and mixtures of two or more of these may be mentioned. Among these, aromatic diisocyanates and alicyclic diisocyanates are preferred.

Examples of polymeric diols used in the production of polyurethane include polyether diols, polyester diols, polybutadiene diols, and mixtures of two or more of these.

Examples of polyether diols include low molecular weight glycols [described later (described as raw materials for polyester diols), such as ethylene glycol, propylene glycol, 1.
Alkylene oxides such as 4-butanediol (alkylene oxides having 2 to 4 carbon atoms: ethylene oxide,
Propylene oxide, 1.2-12.3-11. butylene oxide) adducts and alkylene oxides,
Those obtained by ring-opening polymerization or ring-opening copolymerization (block and/or random) of cyclic ethers (such as tetrahydrofuran), such as polyethylene glycol, polypropylene glycol, polyethylene-polypropylene (block and/or random) glycol,
Polytetramethylene ether glycol, polytetramethylene-ethylene (pro, poly and/or random)
Mention may be made of glycol, polytetramethylene-propylene (block and/or random) glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol and mixtures of two or more thereof.

Polyester diols include condensed polyester diols obtained by reacting low-molecular diols and/or polyether diols with molecules of 11,000 or less with dicarboxylic acids, and polylactone diols obtained by ring-opening polymerization of lactones. The low molecular weight diols include ethylene glycol diethylene glycol, propylene glycol, dipropylene glycol, 1.4-,
1.3-butanediol, neopentyl glycol,!
, 6-hexanediol, l,8-octamethylene diol, alkylnoalkanolamine; low molecular weight diols containing a cyclic group [e.g., those described in Japanese Patent Publication No. 1474/1974: bis(hydroquinomethyl)cyclohexane, m
- and p-quinrylene glycol, bis(hydroxyethylbenzene, 1,4-bis(2-hydroxyethquine)benzene, 4,4'-bis(2-hydroxyethquine)diphenylpropane (ethylene oxide of bisphenol A) Examples of polyether diols having a molecular ffi of 1000 or less include polyethylene glycol, polytetramethylene ether glycol, polypropylene glycol, and triethylene. Glycols; and mixtures of two or more of these.Main dicarboxylic acids include aliphatic dicarboxylic acids (cono-oxylic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.) , aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.)
and mixtures of two or more of these; examples of the lactone include ε-caprolactone.

Polyester diols can be prepared by conventional methods such as low molecular weight diols and/or polyether diols with a molecular i of 1000 or less, dicarboxylic acids or their ester-forming derivatives [e.g. React (condensate) esters (such as dimethyl terephthalate), halides, etc., or their anhydrides and alkylene oxides (such as ethylene oxide and/or propylene oxide), or react with initiators (low molecular diols and/or propylene oxides). or the molecule ff1lO
This structure can be prepared by adding a lactone to a polyether diol (polyether diol having a QO or less).

Specific examples of these polyester diols include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene propylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, polydiethylene anobate, and polyester diol. (Polytetramethylene ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate,
Examples include polybutylene sebacate, polycaprolactone nol: and mixtures of two or more thereof.

The average molecular nobility (by hydroxyl value measurement) of these polymeric diols is usually 500 to 5000, preferably 700 to 40.
It is 00.

Examples of the polybutadiene diol include hydroxyl-terminated polybutadiene oligomers (hydroxyl-terminated liquid polymers of polybutadiene). Specific examples of polybutadiene polyols include PolyBd manufactured by RCO of the United States and Nippon Soda El NO 15 SO-PBC NO U-SUKA. Po1y Bd includes butadiene homopolymer types and copolymer types (styrene-butane-ene copolymer, acrylonitrile-butane-ene copolymer, etc.). Its chemical structure is as follows.

Homopolymer type HO-[CCH2-CH=CH-C)12)e,
2 (CIl-CH2), 2 (CH2-CI=C
HC)l:CH2Cl+2)9.6-Co. OH(2) n: 55 (for R-45M) 50 (for R-45HT) Copolymer type 110 ((CH2-CH=CH-CH2)1(C1l-
CL)b]. O1l, (3)X: C6
1(s (C5-15) a=o, 75 b=0.25. n=54X:
CN (CN-15) a=0 85 b=o, +s n=78-87
Molecular weight is usually 500-5000, preferably 00-3
It is 000. The number of functional groups is usually 2 to 3.

Further, the chemical structure of Nl5SO-PBG-Nries is as follows.

Specifically, G~1000, G~2000, G-300
There is 0.

Its molecular weight is usually 500 to 5000, preferably 100
It is 0-3000.

In the present invention, in addition to the above-mentioned polymeric diols, the following compounds can be used as other active hydrogen-containing compounds.

For example, the glycols mentioned as raw materials for the polyester nols and their alkylene oxide low molar adducts (molecular weight less than 500), aliphatic diamines (ethylene diamine, etc.), alicyclic diamines (inophorone diamine, etc.)
, aromatic diamines (such as 4,4-cyaminonophenylmethane), araliphatic diamines (such as kiln diamine),
Examples include alkanolamines (such as ethanolamine), hydrazine, dihydranods (such as adipic acid dihydranods), and mixtures of two or more thereof.

Preferred among these are low molecular weight glycols, and particularly preferred are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and mixtures of two or more thereof.

Moreover, trifunctional or higher-functional low-molecular-weight polyols can also be used in combination. Examples of this low-molecular polyol include glycerin,
Examples include trimethylolpropane and pentaerythritol.

In the present invention, the content of polymeric diols in the polyol is 50% by weight or more, preferably 65% by weight or more.

The amount of low molecular weight diol is usually 50% by weight or less, preferably 5 to 30% by weight in the polyol component. ■ of trifunctional or higher-functional low-molecular-weight polyols is usually 3 in the polyol component.
It is less than 1% by weight, preferably less than 1% by weight. The amount of low molecular weight diamino is usually 20% of the total active hydrogen-containing compounds.
It is not more than 0% by weight, preferably not more than 0% by weight.

Such thermoplastic polyurethane can be synthesized by bulk polymerization method or solution polymerization method, and usually has a molecular weight of 3000 to +0000.
00 is used, and preferably has a molecular weight of 10,000 to 10,000.
It is 5oooooo.

The thermoplastic polyurethane used in the present invention is usually in the range of 5 to 95% by weight, preferably 5 to 95% by weight, based on 100 parts by weight of the polypropylene resin and thermoplastic polyurethane.
The amount is 50% by weight, particularly preferably in the range of 10 to 40% by weight.

When it is less than the above range, the effect of improving impact resistance and paintability is small, and when it exceeds the above range, the rigidity of the resulting polypropylene resin composition decreases, making it difficult to use.

The amount of modified polyolefin used in the present invention is usually 1 to 30 parts by weight, preferably 3 to 0 parts by weight, per 100 parts by weight of polypropylene resin and thermoplastic polyurethane.
1g1E. If it is less than the above range, the compatibility between the polypropylene resin and thermoplastic polyurethane will be poor, and if it exceeds the above range, moldability will be poor and it will be difficult to use.

In addition, modified polyoffins (a, b, c) are
It can be used as a compatibilizer between other thermoplastic resins and polypropylene resins. Examples of such thermoplastic resins include thermoplastic resins such as polyamide resins, polyester resins, aromatic polyether resins, polyacetal resins, polycarbonate resins, and ABS resins. A resin composition in which the compatibility between a thermoplastic resin and a polypropylene resin is improved by using the modified polyolefin of the present invention, that is, a) polypropylene resin and d
) A polypropylene resin composition prepared by blending a thermoplastic resin selected from the group consisting of polyamide resin, polyester resin, aromatic polyether resin, polyacetal resin, polycarbonate resin, and ABS resin, and optionally thermoplastic polyurethane and C) modified polyolefin. You can get things.

Preferred thermoplastic resins are polyester and/or A
BS resin and/or polyacetal resin.

As the polyamide resin in the present invention, any known polyamide resin can be used without particular limitation. Examples include nylon 6, nylon 6.6, nylon 6.10, nylon 1
1. Aliphatic polyamides such as nylon 12 and nylon/6.12, polyhexamethylene diamine terephthalamide,
Examples include aromatic polyamides such as polyhexamethylene diamine isophthalamide and quinceline polyamide.

These can also be used as a mixture or coelectrocondensation product of two or more types. Preferred polyamide is nylon 6
and nylon 6.6.

The polyamide resin in the present invention may be produced by any known method and is not particularly limited. A well-known example is "Engineering Plastinok" edited by the Society of Polymer Science and Technology (1932).
However, it is obtained by ring-opening (co)polymerization, (co)polycondensation, etc. of lactams with three or more membered rings, polymerizable ω-amino acids, dibasic acids, diamines, etc. be able to.

Examples include ε-caprolactam, aminocaproic acid,
(Co)polymerization of 11-aminoundecanoic acid, etc., diamines such as hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, methaquinyl diamine, and terephthalic acid, isophthalic acid, adipic acid, sepanonic acid, dodecane Examples include (co)M condensation on dicarboxylic acid such as dibasic acid and geltaric acid.

In the aromatic polyether resin in the present invention, the repeating unit has the general formula may be different.

n represents 1 or more 'X Fl).

Examples include poly(2-methylphenylene-1°4-ether), poly(2-ethylphenylene-1,4-ether), poly(2-propylphenylene-1,4-ether), poly(2- phenylphenylene-1,4-ether), poly(2-chlorophenylene-1,4-ether), poly(2-bromophenylene-1,4-ether)
, poly(2,6-dimethylphenylene-1.4-ether), poly(2,6-dimethylphenylene-1゜4-
ether), poly(2,6-cyphenylphenylene-1
, 4-ether), poly(2,6-1 chlorophenylene-1,4-ether), poly(2,6-dibromphenylene-L 4-ether) poly(2-methyl, 6-ethylphenylene- 1゜4-ether], poly(2-methyl, 6-brobylphenylene-1,4-ether),
Poly(-2-methyl, 6-chlorophenylene-L 4
-ether), poly(2-ethyl, 6-chlorophenylene-1,4-ether), poly(2,3,5,6-tetramethylphenylene-1.4-ether), 2, e-y
methylphenylene-1,4-ether and 2. 3.
6-) Dimethylphenylene-1°4-ether copolymer, 2,6-nomethylphenylene-1,4-ether and 3-methyl-〇-t-butylphenylene-1. 4-
Examples include ether compounds. Among these, preferred is poly(2,6-dimethylphenylene-1,
4-ether), poly(2,6-cyphenylphenylene-1,4-ether), 2,6-cyphenylphenylene-1,4-ether and 2. 3. 6-) dimethylphenylene-1,4-ether copolymer, 2, 6-dimethylphenylene-1. It is a copolymer of 4-ether and 3-methyl-et-butylphenylene-1°4-ether.

In addition, the aromatic polyether resin in the present invention includes:
Also included are known derivatives or modified products of these, such as those obtained by graft polymerization with a styrene compound, and those obtained by copolymerization with a polyhydric hydroxyl group-containing compound. Examples of the styrene compound used in this case include styrene, α-methylstyrene, trimethylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene. Further, examples of the polyvalent hydroquine base compound include hydroquinone, resolunon, bisphenol A1, bisphenol S1, tetrabromobisphenol A1, novolak resin, and the like.

The aromatic polyether resin in the present invention may be produced by a known method, and an example of the method can be found in the Society of Polymer Science, ed.
Engineering Plasticox” (June 1, 1988)
5 daily), Special Publication No. 47-47862, Special Publication No. 49-5
No. 628, JP 52-88596, JP 52-1
No. 42799 and other publications.

As the polycarbonate resin in the present invention, known ones can be used. Examples of known types and manufacturing methods are detailed in "Engineering Plastics, Kusu" edited by the Shima Molecular Society (published June 15, 1986) and "Polycarbonate Resin" published by Nikkan Kogyo Shimbun (1964 (TE)). are 2,2-bis(4-oxi/phenyl)alkanes, bis(4-oxi/phenyl)ethers, bis(4-oxi/phenyl)
Examples include polymers or copolymers of bisphenols such as -oxy/phenyl) sulfone, sulfide, and sulfoxide. Further, halogen-substituted bisphenols are also used depending on the purpose.

As the A B S resin used in the present invention, rubber (
Examples include resins obtained by polymerizing one or more compounds (b) selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated carboxylic acid alkyl ester compounds in the presence of a).

The composition ratio of rubber (a) and compound (b) in ABS resin is not particularly limited, but is usually 3 to 70% by weight of rubber (a).
and compound (b) 97 to 30% by weight.

Further, the composition of compound (b) can be arbitrarily selected from the above group, and 2
There is no limit to the composition ratio when using more than one compound, but
Usually, it is a mixture consisting of 40 to 80% by weight of an aromatic vinyl compound and t;o to 20% by weight of a vinyl cyanide compound and/or an unsaturated carboxylic acid alkyl ester compound. Note that the t-stand diameter of the rubber-reinforced thermoplastic resin is usually 0.05 to 5 μ, preferably 0.1 to 0.5 μ.

Various rubbers can be used as the rubber (a) constituting the rubber-reinforced thermoplastic resin, examples include conjugated diene rubbers such as polybutadiene, butadiene-styrene copolymer, butadiene-(meth)acrylonitrile copolymer, Ethylene-propylene rubbers such as ethylene-propylene copolymers, ethylene-propylene-nonconjugated and conjugated diene copolymers, (meth)acrylic esters such as polybutyl (meth)acrylate, butyl (meth)acrylate-styrene copolymers, etc. rubber, chlorinated polyethylene, ethylene-
Examples include vinyl acetate copolymers.

Among the compounds (b), various aromatic vinyl compounds can be used, such as styrene, α-methylstyrene, dimethylstyrene, vinyltoluene, t-butylstyrene, chlorotoluene, and the like.

As the vinyl cyanide compound, common compounds can be used, such as acrylonitrile, methacrylonitrile, and the like.

Usual unsaturated carboxylic acid alkyl ester compounds can be used, examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroquine ethyl (meth)acrylate,
Examples include hydroquine propyl (meth)acrylate.

A normal method can be used to manufacture ABS resin.
Examples include emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, and combinations thereof.

The polyester resin used in the present invention includes a polycondensate produced by polycondensation of a nocarboxylic acid component consisting of a dicarboxylic acid and/or its ester-forming derivative such as methyl ester, and a nool component, and a cyclic ether such as polycaprolactone. Examples include polymers.

1. The dicarboxylic acid component includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid; aliphatic nocarboxylic acids having 2 to 30 carbon atoms such as ambic acid, sepanonic acid, dodecane dibasic acid, and geltaric acid; Examples include alicyclic nocarboxylic acids such as /chlorhexane dicarboxylic acid and/or ester-forming derivatives thereof, and mixtures of two or more thereof. Preferred are terephthalic acid, isophthalic acid and/or ester-forming derivatives thereof.

The diol component is ethylene glycol, ■.

3-propanodiol, 1,4-butanediol, 1G
- Aliphatic diols such as hexanediol, alicyclic diols, bisphenol A1, ethylene oquinodo and/or propylene oquinodo adducts of bisphenol A, polytetramethylene glycol, polypropylene glycol, polyethylene glycol, and mixtures of two or more thereof. can be mentioned. Preferred are ethylene glycol and 1,4-butanediol. Preferred polyesters used in the present invention are polyethylene terephthalate and polybutylene terephthalate, including phenol/
The intrinsic viscosity at 30°C in a tetrachloroethane (6/4) mixed solvent is 0.4 or more. Particularly preferred are those having a viscosity of 0.5 or more.

Polyester resin can be manufactured using normal methods.
There are no particular limitations. For example, it is described in "Engineering Plastics" (published June 15, 1986), edited by the Society of Polymer Science and Technology.

Various known polyacetals can be used as the polyacetal resin used in the present invention. It may contain at least 50% of CH20 groups as repeating units, and includes homopolymers, copolymers, and terpolymers.

Preferably it has a crystallinity of 60 to 90%, particularly preferably 70 to 80%. Polyacetal may be produced by any known method and is not particularly limited. Examples include the method described in "Engineering Plastics" edited by the Society of Polymer Science and Technology (June 15, 1986), US Pat. No. 3,027,352, etc.

In the present invention, a) polypropylene resin, d) thermoplastic resin selected from the group consisting of polyamide resin, polyester resin, aromatic polyether resin, polyacetal resin, polycarbonate resin, ABS resin, and optionally b
) thermoplastic polyurethane/, and C) a polypropylene resin composition blended with modified polyolefin, a) and d) or d) and b) d per 1 part by weight.
) or d) and b) are usually 5 to 95 parts by weight, preferably 15 to 85 parts by weight, and a) and d) or d) and b)
C) is usually 1 to 30 parts by weight, preferably 3 to IO parts by weight per 100 parts by weight of C). If it is less than the above range, the compatibility between the polypropylene resin and the thermoplastic resin will be poor, and if it exceeds the above range, the moldability will be poor.

In producing the composition of the present invention, each composition is mixed using the various mixers described above. At this time, various stabilizers against oxygen, light, and other additives may be added, and the composition of the present invention is molded into a molded article by injection molding, extrusion molding, or compression molding.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. In the following description, parts and % mean 1 part by weight and 1% by weight, respectively.

Example 1 5 parts of maleic anhydride, molecular weight +5000, density 0.89
, terminal Z1 double bond ff11. [i@(carbon number 1000
100 parts of the polypropylene oligomer (1) was dissolved in quinolene and reacted in the presence of dicumyl chloride to obtain a maleic anhydride-modified polypropylene having a maleic anhydride content of 4.5%. Further, this anhydrous maleic a-modified polypropylene and monoethanolamine were reacted in a quincin, and the solvent was distilled off to obtain a modified polyolefin A (compatibilizer of the present invention). The acid value was 0.1 or less.

Example 2 25 parts of modified polyolefin A obtained in Example 1 and molecule fi
7000, residual NCO content ff1o, 82% thermoplastic polyurethane was heated at 180° using a twin-screw extruder.
C to obtain a polyurethane-modified polyolefin (modified polyolefin B2, compatibilizer of the present invention).

Example 3 Low-grade polyethylene (trade name Upe Polyethylene J101
9, Ube Industries, Ltd.) 100 parts, 10 parts of 2-hydroquinoethyl methacrylate, and 0.5 parts of tsucumil peroquinide
After rough mixing in a Hen/L mixer, the mixture was kneaded for 10 minutes at 140''C using a Banbury mixer to obtain modified polyolefin C (compatibilizer of the present invention).

Example 4 5 parts of N-hydroquinophenylmaleimide, molecular weight +0
000. Density 0.89, terminal double bond amount 2.0 (
100 parts of a polypropylene oligomer with a carbon number of 100 O atari) was melted at 200°C and reacted in the presence of di-t-butyl peroxide to produce a modified polyolefin D containing N-hydroquinphenylmaleimide with a fi of 4.2% (the present invention). (solubilizing agent) was obtained.

Examples 5 to 8 Polypropylene (trade name Ube Bolipro J609H1 manufactured by Ube Industries Gi, hereinafter abbreviated as PP) and thermoplastic polyurethane (trade name Peresene 2103-70A).

manufactured by M.D. Kasei A (1), hereinafter abbreviated as PU) and the modified polyolefins prepared in Examples 1 to 3 were kneaded using a twin-screw extruder at the compounding ratio shown in Table 1 to produce the resin of the present invention. A composition was obtained. The kneading temperature was 170-210'C. This composition was pelletized, and the resulting pellets were injection molded to obtain an Izod impact strength (J Is-711).
0) and flexural modulus (JIS-7203) were measured. In addition, as for paintability, the paint residual rate (%
) was determined by the following method. After contacting the test piece with trichloroethane vapor for 45 seconds, apply an alkyd paint (manufactured by Kansai Paint ■) to a film thickness of 20 μm, dry at 120"C for 40 minutes, and then 11
111 Carve 100 horizontal 1 square base marks, repeat the operation of rapidly separating the paint film at a 45 degree angle with cellophane dry tape twice, and calculate the percentage of base marks in the remaining paint film (%)
I asked for The results are shown in Table 1.

Comparative Examples 1 to 3 In Examples 1 to 4, when no modified polyolefin was added and when only polypropylene was used. The results are shown in Table 1.

Examples 9 to 11 PP and polyamide resin (trade name Leona 1300S1
(manufactured by Asahi Kasei Gil, hereinafter abbreviated as PA), PU and the modified polyolefins prepared in Examples 1 to 4 were kneaded using a twin-screw extruder at the compounding ratio shown in Table 2 to obtain the resin composition of the present invention. . After pelletizing, the pellets were injection molded and the Izod impact strength and appearance of the molded products were evaluated. The results are shown in Table 2.

Comparative Examples 4 to 6 Comparative Examples 9 to 11 were carried out in the same manner as in Examples 9 to 11 except that the modified polyolefin was not added. The results are shown in Table 2.

Examples 12-14 PP and polyacetal resin (trade name Duracon M25,
Polyplastics) made of chrysanthemum, hereinafter abbreviated as POM), PU
The modified polyolefins prepared in Examples 1 to 4 were kneaded using a twin-screw extruder at the blending ratios shown in Table 3 to obtain resin compositions of the present invention. After pelletizing, the pellets were injection molded and the Izod impact strength and appearance of the molded products were evaluated. The results are shown in Table 3.

Comparative Examples 7 to 9 Comparative Examples 12 to 14 were carried out in the same manner as in Examples 12 to 14 except that the modified polyolefin was not added. The results are shown in Table 3.

Examples 15-17 PP and polybutylene terephthalate (trade name 1401-
XOe, manufactured by Toshif) 1, hereinafter abbreviated as PBT), PU, and the modified polyolefins prepared in Examples 1 to 4 were kneaded using a twin-screw extruder at the compounding ratio shown in Table 4 to produce the resin of the present invention. A composition was obtained. After pelletizing, the pellets were injection molded and the Izod impact strength and appearance of the molded products were evaluated. The results are shown in Table 4.

Comparative Examples 10 to 12 Comparative Examples 15 to 17 were carried out in the same manner as in Examples 15 to 17 except that the modified polyolefin was not added. The results are shown in Table 4.

Examples 18-20 PP and ABS resin (product name TOYOLAC 500, Higashi 01
! 1 (hereinafter abbreviated as ABS), PU, and the modified polyolefins prepared in Examples 1 to 4 were kneaded using a twin-screw extruder at the compounding ratio shown in Table 5 to obtain a resin composition of the present invention. After pelletizing, the pellets were injection molded and the Izod impact strength and appearance of the molded products were evaluated. The results are shown in Table 5.

Comparative Examples 13 to 15 Comparative Examples 18 to 20 were carried out in the same manner as in Examples 18 to 20 except that the modified polyolefin was not added. The results are shown in Table 5. The results are shown in Table 5.

Examples 21 to 23 PP and polycarbonate resin (trade name: Taflon A250
PU (manufactured by Idemitsu Petrochemical AJ, hereinafter abbreviated as PC) and the modified polyolefin fins prepared in Examples 1 to 4 were kneaded using a twin-screw extruder at the compounding ratio shown in Table 5 to obtain the resin of the present invention. q compositions were obtained. After being made into pellets, injection molding is performed to achieve Izotsu impact strength and the outside of the molded product! Peek was rated. The results are shown in Table 6.

Comparative Examples 16 to 18 Comparative Examples 21 to 23 were carried out in the same manner as in Examples 21 to 23 except that the modified polyolefin was not added.

Table 6 shows the results. Shown below.

[Effects of the Invention] The polypropylene resin composition of the present invention, which is obtained by blending a thermoplastic polyurethane and a modified polyolefin with the polypropylene resin of the present invention, is a combination of a polypropylene resin and a thermoplastic polyurethane, or a combination of a thermoplastic polyurethane and a modified polyolefin. This is a composition with strength suitable for use in various molded products, which was not possible with just a combination of two components. Because it has excellent impact resistance and paintability, it can be used as an industrial material, automobile parts such as bumpers, and various plate molding materials.

Further, in the present invention, a) polypropylene resin and d) polyamide resin, polyester resin, aromatic polyether resin,
A polypropylene resin composition prepared by blending a thermoplastic resin selected from the group consisting of polyacetal resin, polycarbonate resin, and ABS resin, and optionally thermoplastic polyurethane and (C) modified polyolefin, is based on the compatibility of the polypropylene resin and the above-mentioned thermoplastic resin. can be improved by using specific modified polyolefins, and can be used as various molding materials.

Claims (1)

[Claims] 1. A polypropylene resin composition comprising a) a polypropylene resin, b) a thermoplastic polyurethane, and c) a modified polyolefin. 2. a) polypropylene resin and d) polyamide resin,
A polypropylene resin composition containing a thermoplastic resin selected from the group consisting of polyester resin, aromatic polyether resin, polyacetal resin, polycarbonate resin, and ABS resin, and optionally d) thermoplastic polyurethane, and c) modified polyolefin. . 3. Claim 1 or 2, wherein the modified polyolefin is modified with an unsaturated compound containing an amino group and/or a hydroxyl group.
Compositions as described. 4. Modified polyolefin is obtained by reacting a polyolefin modified with an unsaturated acid or an unsaturated acid anhydride with a low-molecular diol, a low-molecular diamine, or a low-molecular compound having a hydroxyl group and an amino group, and/or further NCO The composition according to claim 1 or 2, wherein the polyurethane at the end is reacted. 5, b) and/or d) is 5 to 95 parts by weight, and c) is 1 to 30 parts by weight per 100 parts by weight of a) and b) and/or d).
The composition according to any one of claims 1 to 4, which is in parts by weight. 6, 5 to 50 parts by weight of b) and/or d) and 1 to 30 parts by weight of c) per 100 parts by weight of a) and b) and/or d)
The composition according to any one of claims 1 to 4, which is in parts by weight. 7. Injection molding the composition according to any one of claims 1 to 3,
A method for producing polypropylene resin molded products, characterized by extrusion molding or compression molding. 8. A polyolefin modified with an unsaturated acid or an unsaturated acid anhydride reacted with a low-molecular diol, a low-molecular diamine, or a low-molecular compound having a hydroxyl group and an amino group, and/or an NCO-terminated polyurethane A compatibilizer for polypropylene resins made of modified polyolefin reacted with