JPH06128432A - Propylene-based polymer composition - Google Patents

Abstract

PURPOSE:To provide a polymer composition composed of a propylene-based polymer, an olefin-based elastomer, a specified conjugated diene polymer (hydrogenated polymer) and a specified modified olefin-based polymer and excellent in coating properties with a coating material and moldability. CONSTITUTION:A composition composed of 100 pts.wt. mixture of (A) 99 to 10 pts.wt. propylene-based polymer, preferably crystalline propylene-ethylene block (or random) copolymer exhibiting 0.5 to 60g/10min MFR and (B) 1 to 90 pts.wt. olefin-based elastomer preferably exhibiting 40 to 120 Mooney viscosity and >=16 iodine value, (C) 0.01 to 20 pts.wt. conjugated diene polymer containing an OH group at one or both of the terminals, preferably containing one to five OH groups per one molecule in average and exhibiting 500 to 100000 number-average molecular weight or hydrogenated polymer thereof and (D) 0.01 to 20 pts.wt. olefin-based polymer modified by grafting a polar group- containing ethylenic unsaturated compound (preferably a compound containing a COOH or an acid anhydride group, especially acrylic acid, etc.).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a propylene-based polymer composition having excellent coatability. More specifically, the present invention relates to a propylene-based polymer composition having high adhesion to a paint such as a urethane resin-based paint even when it is not surface-treated with a primer or a solvent.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Propylene-based polymers are widely industrially manufactured because they have various properties such as mechanical properties, heat resistance, solvent resistance, oil resistance and chemical resistance. Such a propylene-based polymer is widely used as a raw material for manufacturing industrial parts such as automobiles and electric appliances and daily necessities. However, the propylene-based polymer has no polar group in the molecule and is chemically inactive and excellent in safety, but on the other hand, since it does not have a polar group, the adhesiveness with other resins is low. Is not good, for example, for coating with urethane resin-based paints, electrical treatment methods such as corona discharge, mechanical surface roughening method, flame treatment method, oxygen treatment method or surface treatment method such as ozone treatment method. Therefore, it is necessary to perform a treatment for improving the affinity of the surface of the molded product with other resins by utilizing. When performing these surface treatments, a method of previously cleaning the surface of the molded product with a solvent such as alcohol or aromatic hydrocarbon, a method of cleaning with a solvent vapor such as trichlene, perchlorethylene, pentachloroethylene, or toluene is generally used. Has been taken.

In order to carry out these methods, an apparatus for processing all is required, which is disadvantageous in terms of equipment and requires a considerable amount of time for processing these. In addition to the method of coating after performing the above-mentioned pretreatment, a primer capable of adhering to a propylene-based polymer is undercoated on the molded product, and a coating such as a urethane resin-based coating is applied on this undercoat layer. However, even in this method, since the undercoating step and the overcoating step are required, it takes a long time for the coating step, and since the coating film has a two-layer structure, the cost of the molded product is increased. There is a problem that is high.

As described above, with respect to the coating of a molded product made of a propylene-based polymer, the molded product itself is generally subjected to some treatment. As described above, in the conventionally known propylene-based polymer, a pretreatment was required when coating the molded product, but a propylene-based polymer excellent in coatability that does not require such a pretreatment was prepared. Development is coveted.

As a method for improving the coating property of a propylene-based polymer, for example, in Japanese Patent Laid-Open No. 3-157168, a diene polymer having a hydroxyl group at its molecular end or a hydrogenated product thereof is added to a propylene / ethylene block copolymer. Although a method for coating a molded article composed of a composition added to a polymer and / or a propylene / ethylene random copolymer is disclosed, its coatability is insufficient.

Further, in JP-A-3-157169, a copolymer of a conjugated diene having a hydroxyl group at the molecular end and an aromatic vinyl compound or a hydrogenated product thereof is described as a propylene / ethylene block copolymer and / or a propylene / ethylene block copolymer. Although a coating method for a molded article made of a composition added to an ethylene random copolymer is disclosed, its coatability is insufficient.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems in a propylene resin composition, and has excellent coatability with respect to paints such as urethane resin paints. It is intended to provide a propylene-based polymer composition.

[0008]

SUMMARY OF THE INVENTION The propylene polymer composition according to the present invention comprises (a) a propylene polymer 99 to 10 parts by weight,
(B) Olefin-based elastomer 1 to 90 parts by weight [however, the total amount of the (a) component and the (b) component is 100 parts by weight], the total amount of the (a) component and the (b) component is 1
(C) 0.01 to 20 parts by weight of a conjugated diene polymer having a hydroxyl group at at least one molecular end, or (d) a graft modification with a polar group-containing ethylenically unsaturated compound, relative to 00 parts by weight. The composition is composed of 0.01 to 20 parts by weight of the obtained olefin polymer.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The propylene polymer composition according to the present invention will be specifically described below. The propylene-based polymer composition according to the present invention comprises (a) a propylene-based polymer, (b) an olefin-based elastomer, (c) a conjugated diene polymer having a hydroxyl group at at least one molecular end, or a hydrogenated product thereof, and (D) An olefin-based polymer graft-modified with a polar group-containing ethylenically unsaturated compound.

First, each component of the propylene polymer composition according to the present invention will be specifically described. [Propylene-based Polymer (a)] The propylene-based polymer (a) used in the present invention is a propylene homopolymer or a copolymer of propylene and another α-olefin. Examples of α-olefins copolymerizable with propylene include ethylene, butene-1, pentene-1,2-methylbutene-1,3-methylbutene-1, hexene-1,3.
-Methylpentene-1, 4, 4-Methylpentene-1, 3,
3-dimethylbutene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-
1, ethylpentene-1, octene-1, methylpentene-1, dimethylhexene-1, trimethylpentene-
1, ethylhexene-1, methylethylpentene-1,
Diethyl butene-1, propyl pentene-1, decene-
1, methylnonene-1, dimethyloctene, trimethylheptene-1, ethyloctene-1, methylethylheptene-1, diethylhexene-1, dodecene-1, and hexadodecene. These α-
The olefin may form a random copolymer with propylene, or may form a block copolymer. In the present invention, the propylene homopolymer has an ethylene content of 2 to
A 40 mol% crystalline propylene / ethylene block copolymer and a crystalline propylene / ethylene random copolymer having an ethylene content of 0.5 to 10 mol% are preferable.

Such a propylene-based polymer (a) is
The melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg is 0.05 to 100 g / 10 minutes,
Further, the MFR is preferably within the range of 0.5 to 60 g / 10 minutes. By using the propylene-based polymer having such MFR, good moldability can be ensured. The density of the propylene-based polymer (a) is
Usually, it is preferably in the range of 0.89 to 0.92 g / cm ³ .

The propylene polymer (a) having such characteristics can be produced by various methods. As a typical production method, a solid titanium catalyst component and an organometallic compound catalyst component are used. It can be produced using the catalyst formed or a catalyst formed from both of these components and an electron donor.

The solid titanium catalyst component used in this method is titanium trichloride or a titanium trichloride composition produced by various methods, and preferably has a specific surface area of 100 m ^2.
/ G or more of a titanium catalyst component supported on a carrier, or magnesium, a halogen, an electron donor, preferably an aromatic carboxylic acid ester or an alkyl group-containing ether and titanium are essential components and have a specific surface area of preferably 100.
It is a titanium catalyst component supported on a carrier of m ² / g or more. In particular, a propylene-based polymer produced by using the latter catalyst component with a carrier is suitable.

Further, as the organometallic compound catalyst component,
Organoaluminum compounds are suitable, and specific examples of the organoaluminum compounds include trialkylaluminum, dialkylaluminum halides, alkylaluminum sesquihalides, alkylaluminum dihalides and the like. The organoaluminum compound can be appropriately selected according to the type of titanium catalyst component used.

As the electron donor, an organic compound having a nitrogen atom, a phosphorus atom, a sulfur atom, a silicon atom, a boron atom or the like can be used, and an ester compound and an ether compound having the above atoms are preferable. Can be given as an example.

Regarding the method for producing a propylene-based polymer using the catalyst component with a carrier as described above, for example, JP-A-50-108385 and JP-A-50-12659.
No. 0, JP-A-51-20297, JP-A-51-281
No. 89, JP-A No. 52-151691, etc., and the techniques described therein can be used in the present invention.

[Olefin Elastomer (b)] The olefin elastomer (b) used in the present invention means ethylene, propylene, butene-1, and penten-1.
And α-olefin copolymers or copolymers of these with non-conjugated dienes.

Examples of non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene, and 5-ethylidene-2-norbornene.

Specific examples of the olefin elastomer include ethylene / propylene copolymer rubber and ethylene / propylene copolymer rubber.
Butene-1 Copolymer Rubber, Ethylene / Propylene / Butene
-1 copolymer rubber, ethylene / propylene / non-conjugated diene copolymer rubber, ethylene / butene-1, non-conjugated diene copolymer rubber, ethylene / propylene / butene-1, non-conjugated diene copolymer rubber An amorphous elastic copolymer may be mentioned.

The Mooney viscosity ML _{1 + 4} (100 ° C .; JIS K 630) of the above-mentioned olefin elastomer
It is desirable that 0) is 10 to 150, preferably 40 to 120. The iodine value (unsaturation) of the olefin elastomer is preferably 16 or less.

[Conjugated diene polymer having a hydroxyl group at at least one of its molecular ends or its hydrogenated product (c)] The conjugated diene polymer having a hydroxyl group at at least one of its molecular ends or its hydrogenated product ( Examples of c) include terminal hydroxyl group polybutadiene, terminal hydroxyl group polyisoprene, terminal hydroxyl group polybutadiene hydrogenated product, and terminal hydroxyl group polyisoprene hydrogenated product.

These polymers have a number average molecular weight (Mn)
Is 300 to 200,000, preferably 500 to 10
30,000, particularly preferably 1,000 to 10,000
Is in the range. Further, these polymers have an average number of hydroxyl groups per molecule of 0.5 to 10, preferably 1 to 5, and a hydroxyl value of 10 to 200, preferably 20 to 100.
KOH mg / g.

The conjugated diene polymer having a hydroxyl group at at least one of the molecular terminals is produced from a conjugated diene as a raw material by a conventionally known method such as a radical polymerization method or an anionic polymerization method. In the case of the radical polymerization method, the conjugated diene polymer is easily obtained by polymerizing a diene-based monomer with hydrogen peroxide as a polymerization initiator. Further, in order to obtain a conjugated diene polymer having a hydroxyl group at the molecular end by an anionic polymerization method, the living polymer may be reacted with, for example, a monoepoxy compound, formaldehyde, acetaldehyde or acetone, halogenoalkylene oxide or polyepoxide.

The living polymer referred to here is
According to a well-known method, a conjugated diene is an anionic polymerization catalyst,
For example, it refers to a polymer produced by polymerizing with an alkali metal or organic alkali metal compound and having a structure in which an alkali metal is bonded to at least one of both ends thereof.

Specific examples of the conjugated diene as a raw material for the above-mentioned conjugated diene polymer include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethyl-1,1, Examples thereof include 3-butadiene and 1-phenyl-1,3-butadiene. These conjugated dienes may be used alone or in combination.

Hydrogenation to the above conjugated diene polymer is
Generally used catalytic hydrotreating means can be adopted. As the hydrogenation catalyst, a nickel catalyst (for example, Raney nickel), a cobalt, platinum palladium, ruthenium, rhodium, etc. single, mixed or alloy type catalyst can be used. These catalysts can be used alone, as a solid or soluble homogeneous complex, or supported on carbon, silica, alumina, diatomaceous earth or the like. Furthermore, the conjugated diene polymer may be hydrogenated using a metal complex obtained by reducing a compound containing nickel, titanium, and cobalt with an organometallic compound (eg, trialkylaluminum, alkyllithium, etc.).

Molecular hydrogen is usually used as the hydrogen used in the above hydrogenation, but a hydrogen-containing gas may be used as long as it does not contain a substance which becomes a catalyst poison. The hydrogen pressure may be either a normal pressure flow or a pressurized system. The temperature of hydrogen is room temperature to 200 ° C., preferably 1
It is 80 ° C or lower.

The conjugated diene polymer can be used alone or as a solvent solution. Examples of the solvent include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, and aliphatic carboxylic acids. These solvents can be used alone or in combination.

As another method for producing the conjugated diene polymer (c) used in the present invention, there is a method in which the conjugated diene polymer is oxidized, decomposed and then reduced.
For example, a polyhydroxy conjugated diene polymer can be obtained by subjecting a polymer obtained by cationically polymerizing a conjugated diene to ozonolysis and then subjecting it to reduction treatment with lithium aluminum hydride.

[Olefin Polymer Graft-Modified with Polar Group-Containing Ethylenically Unsaturated Compound (d)] Olefin as a raw material for olefin polymer (d) graft-modified with polar group-containing ethylenically unsaturated compound Polymers include ethylene, propylene, butene-1, hexene-
Homopolymers of α-olefins such as 1,4-methylpentene-1 and copolymers of two or more α-olefins,
Alternatively, it is a copolymer of an α-olefin and an ethylenically unsaturated compound such as vinyl acetate, vinyl chloride, methyl methacrylate and styrene.

Specific examples of the olefin polymer include high-pressure low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene / propylene random copolymer, and ethylene / butene.
-1 random copolymer, propylene homopolymer, propylene / ethylene random copolymer, propylene / ethylene block copolymer, butene-1 homopolymer, propylene / butene-1 random copolymer, poly-4-methyl Examples include pentene-1, ethylene / vinyl acetate copolymer, and ethylene / ethyl methacrylate copolymer.

The graft modification in the present invention means that the polar group-containing ethylenically unsaturated compound is prepared by heating the above-mentioned olefin polymer and polar group-containing ethylenically unsaturated compound in the presence of a radical initiator. Is grafted to an olefin polymer.

The polar group-containing ethylenically unsaturated compound used in the present invention is a compound having at least one polar group and at least one ethylenically unsaturated group in the molecule. Specific examples of the polar group-containing ethylenically unsaturated compound include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid and norbornene dicarboxylic acid. acid;
Unsaturated dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxy-3-phenoxy-propyl acrylate, 3-chloro -2-Hydroxypropyl acrylate, glycerin monoacrylate, pentaerythritol monoacrylate, trimethylolpropane monoacrylate, tetramethylolethane monoacrylate, butanediol monoacrylate, polyethylene glycol monoacrylate, 2-
(6-hydroxyhexanoyloxy) ethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxy-3-phenoxy-propyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, glycerin mono Methacrylate, pentaerythritol monomethacrylate, trimethylolpropane monomethacrylate, tetramethylolethane monomethacrylate, butanediol monomethacrylate, polyethylene glycol monomethacrylate, 2-
Hydroxyl group-containing unsaturated compounds such as (6-hydroxyhexanoyloxy) ethyl methacrylate; glycidyl acrylate, glycidyl methacrylate, mono- and diglycidyl esters of itaconic acid, mono- and diglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl of citraconic acid Esters, mono- and diglycidyl esters of endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic Acid ^™ ),
Endo-cis-bicyclo [2.2.1] hept-5-ene-2-methyl-2,3-dicarboxylic acid (methyl nadic acid
^TM ) mono- and diglycidyl esters, mono- and diglycidyl esters of allyl succinic acid, glycidyl esters of p-styrenecarboxylic acid, and other epoxy group-containing unsaturated compounds; aminoethyl acrylate, aminopropyl acrylate, ethylaminoethyl acrylate , Propylaminoethyl acrylate, phenylaminoethyl acrylate, cyclohexylaminoethyl acrylate, -2- (dimethylamino) ethyl acrylate, -3- (dimethylamino) propyl acrylate, -2- (dimethylamino) acrylate -1-Methylethyl, acrylic acid-2- (dimethylamino) -2-methylpropyl, acrylic acid-3- (diethylamino) -3-hydroxypropyl, acrylic acid-2- (diethylamino) -1-methylethyl, acryloyl Oxyethyl Acid Phosphate Monomethanolamino half-sol, aminoethyl methacrylate, aminopropyl methacrylate, ethylaminoethyl methacrylate, propylaminoethyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, methacrylic acid-2- (dimethylamino) Ethyl, methacrylic acid-3- (dimethylamino) propyl, methacrylic acid-2- (dimethylamino) -1-methylethyl, methacrylic acid-2- (dimethylamino) -2-methylpropyl, methacrylic acid-3- (diethylamino) ) -3-Hydroxypropyl, methacrylic acid-2- (diethylamino) -1-methylethyl, methacryloyloxyethyl acid phosphate monomethanolamino half sol, N-vinyldiethylamine, N-acetylvinylamine, allylami N, methacrylamine, N-methylacrylamine, p
Examples include amino group-containing unsaturated compounds such as aminostyrene.

The above unsaturated compounds can be used alone or in combination of two or more. Among these,
Unsaturated compounds containing a carboxyl group or an acid anhydride group are preferable, and (meth) acrylic acid, maleic acid, and maleic anhydride are particularly preferable.

As the radical initiator, compounds such as organic peroxides and azo compounds are used. Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane,
1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane,
Peroxyketals such as n-butyl-4,4-bis (t-butylperoxy) valalate and 2,2-bis (t-butylperoxy) butane; di-t-butylperoxide, dicumylperoxide , T-butylcumyl peroxide, α, α'-bis (t-butylperoxy-m-
Isopropyl) benzene, (2,5-dimethyl-2,5-
Bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-
Dialkyl peroxides such as 3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4 -
Diacyl peroxides such as dichlorobenzoyl peroxide and m-trioyl peroxide; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t- Butylperoxylaurylate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, Peroxyesters such as t-butyl peroxyisopropyl carbonate, cumyl peroxyoctate; t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-
2,5-dihydroperoxide, 1,1,3,3-
Hydroperoxides such as tetramethylbutyl hydroperoxide may be mentioned.

Among these, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, di-t-butylperoxide, dicumyl peroxide, (2,5-dimethyl-2) , 5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m- Trioil peroxide and t-butylperoxy-2-ethylhexanoate are preferred.

As the azo compound, specifically,
Examples thereof include azoisobutyronitrile. Such radical initiators can be used alone or in combination.

In the present invention, the polar group-containing ethylenically unsaturated compound is used in an amount of 0.01 to 50 parts by weight, preferably 0.1 to 40 parts by weight, based on 100 parts by weight of the olefin polymer.

The radical initiator is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the olefin polymer. The graft modification in the present invention can be performed by a known method. For example, a method of melt-kneading an olefin polymer and a polar group-containing ethylenically unsaturated compound in the presence of a radical initiator, a polar group-containing ethylenically unsaturated compound and radical initiation in an organic solvent solution of the olefin polymer. Of adding an agent and heating, a method of adding a polar group-containing ethylenically unsaturated compound and a radical initiator to an aqueous dispersion of an olefin polymer, and heating it, an olefin polymer and an ethylenically unsaturated group of a polar group Examples include a method in which the compound and a compound are heated at a temperature not higher than the melting point of the propylene-based polymer in the presence of a radical initiator.

The graft amount of the polar group-containing unsaturated compound in the olefin polymer graft-modified with the polar group-containing unsaturated compound produced by the above-mentioned method is 0. 0 based on the weight of the olefin polymer. 01-50% by weight,
It is preferably 0.05 to 10% by weight.

[Production of Propylene-Based Polymer Composition] Suitable examples of the propylene-based polymer composition in the present invention include the above-mentioned (a) propylene-based polymer 99 to 10 parts by weight, preferably 95 to 20 parts by weight. And particularly preferably 85 to 15
Parts by weight, (b) olefin elastomer 1 to 90 parts by weight, preferably 5 to 80 parts by weight, particularly preferably 15 to
85 parts by weight, the total amount of [(a) component and (b) component is 10]
0 parts by weight], (c) Conjugated diene polymer having a hydroxyl group at least at the molecular end or its hydrogenated product 0.01 to 2
0 parts by weight, preferably 1 to 10 parts by weight, particularly preferably 2 to 7 parts by weight, (d) 0.01 to olefin polymer graft-modified with a polar group-containing ethylenically unsaturated compound
It is produced by melt-kneading 20 parts by weight, preferably 1 to 15 parts by weight, particularly preferably 2 to 10 parts by weight.

In order to produce the propylene-based polymer composition of the present invention, a mixing method which is usually used in the field of propylene-based polymers is applied so that the above components are in the range of the above composition ratio. And mix so that it becomes uniform. At this time, all the composition components may be mixed at the same time, or a part of the composition components may be mixed in advance to produce a so-called masterbatch, and the masterbatch and the remaining composition components may be mixed.

When producing the propylene polymer composition of the present invention, an organotin compound and / or a tertiary amine compound may be further added. In the present invention, the organotin compound and the tertiary amine compound play a role of a catalyst in the reaction between the hydroxyl group of the polyol and the isocyanate, which is the urethane bond formation reaction.

The organotin compound used in the present invention has the formula R ₁ --SnX ₁ Y ₁ Y ₂ (wherein R ₁ is an alkyl group having 4 to 10 carbon atoms, and X ₁ is 4 carbon atoms). 10 is an alkyl group, a chlorine atom or a hydroxyl group, Y ₁ and Y ₂ are chlorine atoms,
OCOR ₂ or hydroxyl group, which may be the same or different. However, R ₂ is an alkyl group,
An aryl group and an allylalkyl group. ).

Specific examples of such an organic tin compound include
Specifically, n-C_FourH₉Sn (OH)₂Cl, n-C_FourH₉S
n (OH) Cl₂, N-C_FourH₉SnCl₃, C₈H₁₇Sn
(OH)₂Cl, C₈H₁₇Sn (OH) Cl₂, C₈H₁₇S
nCl₃, N-C_FourH₉Sn (OH)₂OCOC₇H₁₅, N-
 C_FourH₉Sn (OH)₂OCOC₁₁H_{twenty three}, N-C₈H₁₇S
n (OH)₂OCOC₇H₁₅, N-C₈H₁₇Sn (OH) ₂
OCOC₁₁H_{twenty three}, N-C_FourH₉Sn (OCOC₇H₁₅)₃,
(N-C_FourH₉)₂Sn (OCOC₁₁H_{twenty three})₂, (N- C₈
H₁₇)₂Sn (OCOC₁₁H_{twenty three})₂, (N- C_FourH₉)₂S
n (OCOCH = CHCOOCH₃)₂, (N- C_FourH₉)
₂Sn (OCOCH = CHCOOCH₂Ph)₂Used by etc.
To be

Of these, n-C ₄ H ₉ SnCl ₃ , (n-
_{C 4 H 9) 2 Sn (} OCOC 11 H 23) 2, (n- C 8 H 17) 2
Sn (OCOC ₁₁ H ₂₃ ) ₂ is preferred. The compounding amount of such an organic tin compound is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight.

Specific examples of the tertiary amino compound used in the present invention include dimethylpropylamine, diethylpropylamine, tris (dimethylaminomethyl) phenol, tetraguanidine, N, N-dibutylethanolamine, N- Examples thereof include methyl-N, N-diethanolamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, and tetramethylbutanediamine.

The amount of such a tertiary amino compound compounded is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight. Further, the physical properties of the propylene-based polymer composition of the present invention, in the range that does not impair the coatability, other thermoplastic resins, softeners, fillers, pigments, stabilizers, plasticizers, flame retardants, lubricants, An antistatic agent and an electrical property improving agent can be added as required.

Specific examples of the above-mentioned other thermoplastic resins that can be used in the present invention include high-density polyethylene,
Medium-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, poly-butene-1, propylene-butene-1 copolymer, styrene-butadiene (.styrene) block copolymer and its hydrogenated product, styrene Examples thereof include isoprene (.styrene) block copolymers and hydrogenated products thereof.

Mineral oil-based softening agents can be mentioned as softening agents that can be used in the present invention. The mineral oil-based softening agent weakens the intermolecular acting force of the olefin-based elastomer, facilitates processing, and helps disperse carbon black, white carbon, etc. to be blended as a filler,
Alternatively, it is a high boiling point petroleum fraction used for the purpose of lowering the hardness of the vulcanized rubber and increasing the flexibility and elasticity, and is classified into paraffin type, naphthene type, aromatic type and the like.

Specific examples of the filler which can be used in the present invention include light calcium carbonate, heavy calcium carbonate, basic calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, kaolin, clay and pyro. Ferrite, sericite, talc,
Calcium silicate (wollastonite, xonotlite, petal-like calcium silicate), diatomaceous earth, aluminum silicate, anhydrous silicic acid, hydrous silicic acid, mica, magnesium silicate (asbestos, PFM (Processed)
Mineral Fiber), sepiolite), potassium titanate, elestadite, gypsum senui, glass balun, silica balun, fly ash balun, silas balun, carbon balun, phenol resin, urea resin,
Styrene resin, organic balun such as Saran resin, silica, alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, graphite, glass fiber (chopped strand, roping, milled glass fiber, glass flake, etc.), cut fiber , Rock fiber, microfiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, coumarone indene resin, petroleum resin and the like.

Specific examples of the colorant usable in the present invention include carbon black, titanium oxide, zinc white, red iron oxide, ultramarine blue, dark blue, azo pigment, nitroso pigment,
Examples thereof include lake pigments and phthalocyanine pigments.

In the present invention, known heat-resistant stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based or amine-based stabilizers, antiaging agents,
A weather resistance stabilizer, an antistatic agent, a metal soap, a lubricant such as a wax, and the like can be compounded to the extent of being used in an olefin plastic or an olefin copolymer rubber.

The propylene-based polymer composition of the present invention is produced by melt-kneading the above-mentioned components, and the above-mentioned components are dynamically heat-treated in the presence of an organic peroxide to partially crosslink. You may.

In the present invention, dynamically heat-treating in the presence of an organic peroxide to partially crosslink means kneading in a molten state in the presence of an organic peroxide. Specific examples of the organic peroxide used in the present invention include dicumylperoxide, di-tert-butylperoxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane. 2,5-dimethyl-2,5-di-
(Tert-Butylperoxy) hexyne-3,1,3
-Bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) benzene
-3,3,5-Trimethylcyclohexane, n-butyl
-4,4'-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate,
Examples thereof include tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butyl cumyl peroxide.

Among these, from the aspect of odor, etc., 2,5
-Dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (ter
t-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)-
3,3,5-Trimethylcyclohexane, n-butyl-
4,4'-bis (tert-butylperoxy) valerate is preferred.

The content of the organic peroxide is 0.001 to 3% by weight, preferably 0.005 to 5% by weight based on the total amount of the components.
It is preferably within the range of 1% by weight. In the present invention, sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenyl are used in the partial crosslinking treatment with the organic peroxide. Cross-linking aids such as guanidine, trimethylolpropane-N, N-m-phenylenedimaleimide; or divinylbenzene; triallyl cyanurate; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, A polyfunctional methacrylate monomer such as allyl methacrylate; a polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate can be incorporated. With such a compound, a uniform and mild crosslinking reaction can be expected. In particular, in the present invention, when divinylbenzene is used, it is easy to handle and has good compatibility with the olefin-based plastic which is the main component of the object to be treated, and has an organic peroxide-soluble action, Since it functions as a dispersion aid for peroxides, the crosslinking effect by heat treatment is uniform, and a composition in which fluidity and physical properties are well balanced is obtained, which is most preferable. In the present invention, the compounding amount of such a crosslinking aid or a polyfunctional vinyl monomer is preferably in the range of 0.1 to 2% by weight, particularly 0.3 to 1% by weight, based on the whole object to be treated.

In order to accelerate the decomposition of organic peroxide, triethylamine, tributylamine, 2,4,6
-Tertiary amines such as tris (dimethylamino) phenol, and decomposition accelerators such as naphthenates such as aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead and mercury can also be used.

The kneading is preferably carried out in a non-open type apparatus, and is preferably carried out under an atmosphere of inert gas such as nitrogen or carbon dioxide. The kneading temperature is a temperature at which the half-life of the organic peroxide used is 1 minute, usually 150 to 280 ° C, preferably 170 to 240 ° C, and the kneading time is usually 1 to 2
It is 0 minutes, preferably 1 to 10 minutes.

As a kneading device, a mixing roll, an intensive mixer (for example, Banbury mixer, kneader), a single-screw or twin-screw extruder can be used, but a non-open type device is preferable.

The composition thus obtained is usually molded into pellets, and the injection molding method, the extrusion molding method and the injection molding method, which are generally used in the field of each thermoplastic resin,
A desired molded product is produced by a molding method such as a calender molding method.

The molded article formed from the propylene polymer composition of the present invention has excellent coatability with respect to urethane resin paints and amino resin paints. Urethane resin-based paints are generally paints that form a coating film by the reaction of a polyisocyanate and a polyol compound, and there are one-pack type and two-pack type, and there are also powder paints using a block-type isocyanate. The molded product made of the propylene polymer composition of the present invention has a good affinity with any of these urethane resin paints.

The amino resin-based paint includes melamine resin-based paint, benzoguanamine resin-based paint, and urea resin-based paint. These coatings form a coating film by reacting a starting material having an amino group with formaldehyde to produce a monomer having high reactivity, and reacting a methylol group produced by addition condensation of this with a hydroxyl group of an alcohol. It is a paint to be formed, and is used as a mixture with a plasticized oil-modified alkyd resin, oil-free alkyd resin, oil varnish, acrylic resin, epoxy resin, epoxy ester resin.

Of the above-mentioned coating materials, for example, a coating method using a urethane resin coating material will be described by way of example. A molded article formed from the propylene polymer composition of the present invention is washed with water and generally Washing with various industrial detergents is performed at least once, followed by washing with water and heating and drying. That is, when coating a molded article formed from the propylene-based polymer composition of the present invention, it is not always necessary to perform conventional cleaning (surface treatment) using a chlorine-based solvent vapor. . A urethane resin coating film can be formed by applying a urethane resin-based paint to the thus-dried molded body and heating it as necessary. The coating film formed in this way has very good adhesion to the molded product, even though it is not washed with chlorine-based solvent vapor.

[0065]

The propylene-based polymer composition of the present invention is
Excellent coatability for urethane resin-based paints, amino resin-based paints, etc.

The propylene-based polymer composition of the present invention has excellent moldability and can be molded by an apparatus used for usual thermoplastics, and is suitable for extrusion molding, calender molding, injection molding and the like. There is.

Utilizing the above characteristics, the propylene polymer composition of the present invention can be used for automobile parts, motorcycle parts, electric equipment parts, daily necessities, civil engineering building materials, general industrial materials, office information equipment, packaging materials. It can be widely used for applications to which paint is applied such as sports equipment and medical equipment.

The present invention will be described below with reference to examples.
The invention is not limited to these examples.
Various properties of the propylene polymer composition used in the present invention were measured as follows. (1) Flexural Modulus (FM) Using a test piece having a thickness of 1/8 inch, ASTM D-7
90. (2) Coating test ○ Preparation of test piece The following paint was applied to a square plate molded by a 50-ton injection molding machine. In addition, in Examples 1 to 5 and Comparative Examples 1 to 4, the surface of the rectangular plate was wiped with a cloth impregnated with isopropanol before coating with the following paint. ○ Coating Two-component urethane resin-based paint [trade name R-271, manufactured by Nippon Bee Chemical Co., Ltd.] was applied with an air gun so that the dry film thickness was 60 μm. The baking was performed at 100 ° C. for 30 minutes. ○ Cross-cut test A cross-cut test piece was prepared in accordance with the method of the cross-cut test described in JIS K5400, and cellophane tape (manufactured by Nichiban Co., Ltd., trade name) was attached to the test piece. Was rapidly pulled in the direction of 90 ° for peeling, and the number of cross-cuts was counted and used as an index of adhesion. Peeling strength test A coating film was prepared on a base material, a 1 cm width was cut with a cutter blade until the blade reached the base material, and the edges were peeled off.
180 at the speed of 50 mm / min.
The peel strength was measured by pulling in the direction of ° until the coating film peeled.

[0069]

Reference Example 1 [Production of Conjugated Diene Polymer Having Hydroxyl Group at At least One of Molecular Ends] An autoclave having a capacity of 500 ml was charged with 100 g of 1,3-butadiene, 70 g of isopropyl alcohol and 10 g of 60% hydrogen peroxide solution, and a nitrogen atmosphere Below, it heated at 90 degreeC for 5 hours. Then, the reaction solution was cooled, unreacted 1,3-butadiene was removed, and the produced polymer was taken out and dried.

The resulting butadiene polymer (hereinafter referred to as PB
(Sometimes abbreviated as D) is Vapor Osmom
The molecular weight measured by eter was 3,360, and the hydroxyl value was 48. [Production of Hydrogenated Product of Conjugated Diene Polymer Having Hydroxyl Group on At least One of Molecular Ends] 50 g of the above PBD and 5 g of carbon-supported ruthenium catalyst (5%) were added to a volume of 200
After being charged in a ml autoclave and replacing the air in the system with nitrogen, hydrogen gas was fed until the total pressure in the system reached 50 kg / cm ² . Then, this autoclave
The temperature was raised to 0 ° C., hydrogen gas was supplied into the autoclave so that the total pressure in the system was maintained at 50 kg / cm ² , and the hydrogenation reaction was carried out for 8 hours. After completion of the reaction, hydrogen was removed, the catalyst was filtered off, and the produced hydrogenated product was precipitated in methanol and dried.

The obtained hydrogenated product (hereinafter sometimes abbreviated as HPBD) had an iodine value of 1.2 and a hydroxyl value of 45.

[0072]

[Reference Example 2] [Production of maleic anhydride-modified propylene homopolymer] 50 g of propylene homopolymer (MFR: 10 g / 10 minutes)
And p-xylene (500 ml) were put in a glass separable flask having a volume of 1 liter and heated to 130 ° C.
-Propylene homopolymer was dissolved in xylene. Next, 5 g of maleic anhydride and 0.5 g of dicumyl peroxide were added dropwise to this solution over 4 hours, and the solution was further heated for 2 hours. Thereafter, this solution was allowed to cool and then poured into acetone to obtain a propylene homopolymer graft-modified with maleic anhydride.

The amount of maleic anhydride grafted in the obtained modified propylene homopolymer (hereinafter sometimes abbreviated as MPP) was 3% by weight, and the intrinsic viscosity [η] measured in decalin at 135 ° C. Is 0.4 dl / g (MF
R: 3 × 10 ⁴ g / 10 minutes).

[0074]

Examples 1 to 5 and Comparative Examples 1 to 4 The components shown in Table 1 were melt-kneaded at a predetermined temperature with a twin-screw extruder to produce a propylene polymer composition. This composition was molded by an injection molding machine to prepare a square plate, and each test piece of the above test was obtained and the above test was performed.

The results are shown in Table 1. The components in Table 1 are as follows. Propylene polymer ○ Propylene homopolymer (PP-1) MFR: 20 g / 10 minutes, density: 0.91 g / cm ³ ○ Propylene-ethylene block polymer (PP-2) MFR: 14 g / 10 minutes, ethylene content : 12 mol% Density: 0.91 g / cm ³ Olefin-based elastomer ○ Ethylene / propylene copolymer rubber (EPR) Mooney viscosity ML _{1 + 4} (100 ° C.): 60 MFR: 0.7 g / 10 min, ethylene content: 81 mol% Thermoplastic resin other than the above ○ Linear low-density polyethylene (LLDPE) Comonomer: butene-1, butene-1 content: 2 mol%, MFR: 25 g / 10 min, density: 0.92 g / cm ³ ○ Styrene / butadiene / styrene block copolymer hydrogenated product (SEBS) Styrene content: 30% by weight, MFR: 4 g / 10 min at least one Conjugated Diene Having a Hydroxyl Group at One End
Polymer or hydrogenated product thereof Hydrogenated product of butadiene polymer (PBD) (HPB
D) See Reference Example 1 above. Graft-modified with polar group-containing ethylenically unsaturated compound
Olefin-based polymer ○ Maleic anhydride-modified propylene homopolymer (MPP) See Reference Example 2 above. Organotin compound ○ Dibutyltin dilaurate (DBTDL)

[0076]

[Table 1]

[0077]

Example 6 The procedure of Example 1 was repeated, except that the surface of the test piece was coated with a cloth impregnated with isopropanol without being wiped to conduct a coating test.

The results are shown in Table 2.

[0079]

Example 7 Example 1 was repeated except that the surface of the test piece was wiped with a cloth impregnated with isopropanol in the same manner as in Example 1 except that the surface-treated test piece shown below was applied for the coating test. It carried out similarly to.

[Surface treatment] After the test piece was washed with water, it was washed with a 4% aqueous solution (60 ° C) of a general industrial detergent ID-112 [trade name, manufactured by Tosoh Corporation] for 1.5 minutes. did.
Furthermore, this test piece was used as a general industrial cleaning agent ID-113.
It was washed for 1 minute with a 1% aqueous solution of Tosoh Corp. (trade name) (55 ° C.), washed with water, and dried at 80 ° C. for 10 minutes.

The results are shown in Table 2.

[0082]

[Table 2]

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Claims (2)

[Claims] 1. A propylene polymer (a) 99 to 10 parts by weight, a olefin elastomer (b) 1 to 90 parts by weight [wherein the total amount of the components (a) and (b) is 10].
0 parts by weight], and (c) a conjugated diene polymer having a hydroxyl group at at least one molecular end or a hydrogenated product thereof, relative to 100 parts by weight of the total amount of the components (a) and (b). 0.01 to 20 parts by weight, (d) 0.01 to 20 parts by weight of an olefin polymer graft-modified with a polar group-containing ethylenically unsaturated compound is a composition comprising a propylene polymer composition. object. 2. The propylene polymer composition according to claim 1, wherein the polar group-containing ethylenically unsaturated compound is a carboxyl group- or acid anhydride group-containing ethylenically unsaturated compound.