JPH06192509A - Polyolefinic resin composition having low luster - Google Patents

Abstract

PURPOSE:To obtain a polyolefinic resin composition providing a molded article having suppressed surface luster without using an inorganic filler. CONSTITUTION:A modified olefinic resin is mixed with a compound containing two or more groups having reactivity to the resin or a compound to gelatinize the resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition, particularly a polypropylene resin composition, having a low gloss, and more particularly to a composition which becomes a molded article whose surface gloss is suppressed when injection-molded.

[0002]

2. Description of the Related Art Polyolefin resin has a mechanical strength,
It has excellent moldability and chemical resistance, and is used in various applications such as interior and exterior parts of automobiles and housings of home appliances.
Above all, polypropylene resin reinforced with an inorganic filler such as talc, glass fiber fiber and calcium carbonate has excellent strength and heat resistance and is widely used for automobile parts such as instrument panels, bumpers and console boxes. Since the polyolefin resin reinforced with these inorganic fillers contains an inorganic filler, it gives a molded article with a naturally suppressed surface gloss.

On the other hand, there is also a polyolefin molded product which does not include an inorganic filler for the purpose of reducing the weight of the molded product. this is,
Its extremely high gloss limits its use for cosmetic reasons.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyolefin resin composition which gives a molded article having a low gloss regardless of the presence or absence of an inorganic filler.

[0005]

Means for Solving the Problems (A) 100 parts by weight of a polyolefin resin containing a modified olefin resin, and (B) a compound having at least two groups reactive with the above modified olefin resin or the above modified A low gloss polyolefin resin composition comprising 0.01 to 5 parts by weight of a compound that causes gelation of an olefin resin.

In the present invention, the polyolefin resin includes polyethylene resin and polypropylene resin, or ethylene-propylene copolymer resin, and is particularly polypropylene resin. Polypropylene is a crystalline polymer obtained by polymerizing a propylene monomer as a main component, and includes a block copolymer or a random copolymer of propylene and another α-olefin such as ethylene. A propylene-ethylene random copolymer is particularly preferable.
In the case of a random copolymer with ethylene, the ethylene content is preferably 1 to 10% by weight. Such polypropylenes usually have a melt flow rate (MFR, J
ISK7210, load 2.16 kg, 230 ℃). A propylene random copolymer containing a non-conjugated diene comonomer (hereinafter referred to as PPDM) may be used.

The modified olefin resin can be obtained by introducing a silyl group having a carboxyl group, an acid anhydride group, an epoxy group or a hydrolyzable substituent into the above polyolefin resin.

For this purpose, an unsaturated carboxylic acid or its anhydride, or an epoxy group-containing unsaturated monomer may be copolymerized with an olefin. Any of block copolymerization, graft copolymerization, random copolymerization and alternating copolymerization may be used.
The graft copolymer can be produced by either a solution method or a melt kneading method. In the case of melt-kneading method, polyolefin, unsaturated carboxylic acid for modification (or acid anhydride)
Alternatively, the epoxy group-containing unsaturated monomer and the catalyst are put into an extruder, a twin-screw kneader, or the like, and heated to a temperature of 150 to 250 ° C. to be kneaded while melting. In the case of the solution method, the above-mentioned starting material of an organic solvent such as xylene is dissolved and the reaction is carried out at a temperature of 80 to 140 ° C with stirring. In any case, a usual radical polymerization catalyst can be used as a catalyst, for example, benzoyl peroxide, lauroyl peroxide, ditert-butyl peroxide, acetyl peroxide, tert-butyl peroxybenzoic acid, dicumyl peroxide, Peroxides such as peroxybenzoic acid, peroxyacetic acid, tertiary butyl peroxypivalate, 2.5-dimethyl-2.5-ditertiary butyl peroxyhexyne and diazo compounds such as azobisisobutyronitrile are preferred. Examples of unsaturated carboxylic acids or anhydrides thereof include monocarboxylic acids such as acrylic acid and methacrylic acid, maleic acid, fumaric acid, itaconic acid, endo-bicyclo- [2,2,1]-
Dicarboxylic acids such as 5-heptene-2,3-dicarboxylic acid,
Maleic anhydride, itaconic anhydride, endo-bicyclo-
Examples thereof include dicarboxylic acid anhydrides such as [2,2,1] -5-heptene-2,3-dicarboxylic acid anhydride (hymic acid anhydride), and dicarboxylic acid and its anhydride are particularly preferable. Examples of the epoxy group-containing unsaturated monomer include methacrylic acid glycidyl ester and acrylic acid glycidyl ester. The amount of these comonomers is preferably in the range of 0.01 to 10% by weight based on the weight of the modified olefin resin.
If less than 0.01% by weight, sufficient low gloss cannot be obtained, and 10% by weight
If it exceeds the range, inconveniences such as deterioration of fluidity and poor appearance occur, which is not preferable.

It is known to introduce silyl groups having hydrolyzable substituents into polyolefins, eg
To ethylene-based resin such as polyethylene or a copolymer containing ethylene as a main component or propylene-based resin such as polypropylene or a copolymer containing propylene as a main component,
A method of graft-copolymerizing an ethylenically unsaturated silane in the presence of a radical generator (see, for example, JP-B-47-1711 or JP-A-59-36115), or ethylene and an ethylenically unsaturated silane or Is typically produced by a method of high-pressure radical copolymerization with another radically polymerizable monomer (see, for example, Japanese Patent Publication No. 62-23777).

Alternatively, various methods such as a method obtained by reacting a maleic anhydride-modified olefin resin with γ-aminopropyltrimethoxysilane can be applied. Further, the modifying silicon compound is not limited to the ethylenically unsaturated silane (JP-A-4-76051).
As the modifying silicon compound, a silicon compound having a reactive group capable of being graft-polymerized with an olefin resin, a silicon compound having a group capable of reacting with a functional group introduced into an olefin resin, or a reactivity capable of being copolymerized with an olefin monomer There is a silicon compound having a group and the like, and examples thereof include compounds generally represented by the following formula: R′SiR _n Y _3-n where R ′ is, for example, vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or γ-. A carbon-carbon double bond-containing group such as (meth) acryloyloxypropyl. R is a hydrocarbon group such as an alkyl group such as methyl, ethyl, propyl or decyl, Y is a hydrolyzable organic group or a hydroxyl group, and n is 0, 1 or 2
Is. Examples of Y include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, alkyl or arylamino groups and the like.

As a silicon compound for modification, a compound represented by the general formula CH ₂ ═CHSi (OA) ₃ (wherein A represents an alkyl group having 1 to 8 carbon atoms), specifically, Examples include vinyltrimethoxysilane and vinyltriethoxysilane.

The above-mentioned modified olefin resin constitutes the component (A) together with the unmodified polyolefin resin, and the proportion thereof is 5 to 30% by weight, particularly 10 to 25% by weight, based on the total amount of (A). Is preferred. If it is less than 5% by weight, low gloss may not be obtained. On the other hand, if it exceeds 30% by weight, the inherent properties of the polyolefin such as rigidity and heat resistance may be impaired.

Next, among the components (B), as a compound having at least two groups reactive with the modified olefin resin. Two or more amino groups or epoxy groups in one molecule, or carboxyl group (or its acid anhydride group)
And a compound having The compound having two or more amino groups in the molecule is, for example, polymethylenediamine,
Polyetherdiamine, diethylenetriamine, triethylenetetramine, N-aminoethylethanolamine and other aliphatic polyvalent amines, metaphenylenediamine, xylenediamine, 4,4'-diaminodiphenyl ether, 4,
Aromatic polyvalent amines such as 4'-diaminodiphenylamine, alicyclic polyamines such as 4,4'-diaminodicyclohexylmethane and 4,4'-diaminodicyclohexyl ether, and heterocyclic polyamines such as melamine and benzoguanamine , Α, ω-bis (aminopropyl) polydimethylsiloxane and other organosilane compounds. 2 in the molecule
The compound having at least one carboxyl group (or acid anhydride) is, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, Aliphatic carboxylic acid compounds such as malic acid and citric acid (or their salts or anhydrides), phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid,
It is an aromatic polyvalent carboxylic acid such as naphthalene tricarboxylic acid (or a salt or anhydride thereof), or a carboxylic acid group-containing copolymer (for example, polystyrene, polyolefin, etc.).

As the compound having two or more epoxy groups in the molecule, for example, bisphenol type epoxy compound obtained by reacting bisphenol A and epicryhydrin at various ratios, novolac resin and epicryhydrin are used. Novolak type epoxy compound obtained, polyglycidyl esters obtained from polycarboxylic acid and epichlorohydrin, alicyclic compounds, for example fatty compound type epoxy compounds obtained from dicyclopentane, aliphatic compounds having an alcoholic hydroxyl group (eg butanediol, Glycidyl ethers obtained from glycerin and the like and epichlorohydrin, epoxidized polybutadiene, and epoxy group compound-containing copolymers composed of an unsaturated monomer having an epoxy group and another unsaturated monomer. Examples of the bisphenol A type epoxy compound as a preferred example of these polyvalent epoxy compounds include, for example,

[0015]

[Chemical 1] (However, n is a number from 0 to 10), and as the epoxy group-containing copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer , Ethylene / carbon monoxide / glycidyl methacrylate copolymer, ethylene / acrylic acid copolymer and the like, among which ethylene / glycidyl methacrylate copolymer is preferable.

When the modified olefin resin is modified with a silyl group having a hydrolyzable substituent, a known silanol condensation catalyst is used as a compound which causes gelation thereof. These compounds include tin carboxylates such as tin octylate; organic tin carboxylates such as dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diphthalate; organic tin oxide and its reaction products; organic compounds such as tetrabutyl titanate. Examples include titanic acid esters and the like.

The component (B) may be added in an amount sufficient to cause gelation of the modified olefin resin,
Ordinarily 0.01 to 5% by weight based on the sum of (A) and (B), especially
0.1 to 2% by weight is preferable. A blending amount exceeding 5% by weight is not preferable because it causes bleed-out and lowers heat resistance. If it is less than 0.01% by weight, a sufficient effect cannot be obtained.

The resin composition of the present invention may contain various stabilizers, colorants, elastomer components, other resins and the like as optional components.

The present invention will be further described below with reference to examples.

[0020]

EXAMPLES The components used are as follows.

(A) Unmodified polypropylene: Ube Polypro B101H (trademark, Ube Industries, Ltd.) Modified polypropylene 1: Tufmer MP0610 (trademark, Mitsui Petrochemical Co., Ltd.), maleic anhydride group-modified polypropylene Modified polyethylene 2: Bondfast E (Trademark, Sumitomo Chemical Co., Ltd.), ethylene-glycidyl methacrylate copolymer Modified polypropylene 3: Linklon (trademark, Mitsubishi Petrochemical Co., Ltd.), silyl group modified polypropylene (B) Polyvalent epoxy compound: triglycidyl isocyanurate Divalent amino compound: m-phenylenediamine silanol condensation catalyst: dibutyltin dilaurate Each component is in the proportions (parts by weight) shown in Table 1 at 230 ° C.
Pellets were prepared by melt-kneading with a shaft extruder. Using the pellet, a sample for each measurement was injection-molded. The results are shown in Table 1.

The measuring method is as follows.

Surface gloss: (According to JIS K-7105, the gloss at 60 ° C. of a 50 mm square molded product was measured.

Izod impact strength: ASTM D256, notched Heat distortion temperature: ASTM D648, 4.6 kg / cm ² load

[0025]

[Table 1] As can be seen from the table, in Comparative Example 1, the surface gloss is high, whereas in the Example, the gloss is suppressed, the impact strength is high, and the decrease in heat distortion temperature is at an acceptable level.

Claims (3)

[Claims] 1. A compound of (A) 100 parts by weight of a polyolefin resin containing a modified olefin resin, and (B) a compound having at least two groups reactive with the above modified olefin resin or the above modified olefin resin. A low gloss polyolefin resin composition comprising 0.01 to 5 parts by weight of a compound which causes gelation. 2. The composition according to claim 1, wherein the modified olefin resin is modified with a carboxyl group, an acid anhydride group, an epoxy group, or a silyl group having a hydrolyzable substituent. 3. A modified olefin resin, wherein the compound having at least two groups reactive with the modified olefin resin is a compound having at least two amino groups, epoxy groups, or carboxyl groups or acid anhydride groups thereof. The composition of claim 2, wherein the compound that causes gelation of the resin is a silanol condensation catalyst.