JPH02191648A - Polypropylene composition - Google Patents

Abstract

PURPOSE:To provide an impact-resistant polypropylene composition having improved surface processability by compounding isotactic polypropylene with two kinds of specific ethylenic copolymers in a specific ratio. CONSTITUTION:A polypropylene composition containing a partially crosslinked component B is prepared by compounding (A) isotactic polypropylene with (B) a mixture of B1: a copolymer of ethylene with an alpha,beta-unsaturated carboxylic acid and/or the anhydride thereof or a copolymer of the monomers with an unsaturated carboxylic acid ester and B2: a copolymer of ethylene with an epoxy group-containing ethylenic unsaturated monomer (e.g. glycidyl methacrylate) or a copolymer of the monomers with an unsaturated carboxylic acid ester or a vinyl ester (preferably vinyl acetate) in such a ratio of 0.2-20mol of the epoxy group of B2 per mol of the COOH and/or the anhydride group thereof of B1 and in an A:B weight ratio of 90:10-70:30.

Description

[Detailed description of the invention]

(1) Industrial application field The present invention is directed to c′t (lii v
The present invention relates to a polypropylene composition. (2) Conventional technology Isotactic polypropylene is inexpensive and has various mechanical properties, transparency, heat resistance, surface gloss <1°, chemical resistance, acid resistance, and alkali resistance, and injection molding and blow molding. Because it is easy to mold using various molding methods such as various types of film molding, it is used in large quantities for a very wide range of applications, but compared to polyethylene, it has poor impact resistance, especially at low temperatures below room temperature. The magnetic strength is small, and the MR structure does not contain any polar groups, so it has good viewing properties and p
It has drawbacks such as difficulty in surface processing such as mounting and printability. First, as a method for improving the fMm resistance of isotactic polypropylene, it is generally well known to mix polypropylene with ethylene/propylene rubber (El)R), Er)R, and polyethylene (PE). . I-) Methods for mixing R and PE with polypropylene include a polymerization system using a two- or three-stage adhesive reactor, and a mechanical mixing method using a kneader or the like. be. The thus obtained mixture (or block copolymer) of polypropylene and EPR or of polypropylene, EPR and pr is known as HfP F' and isotactic. Compared to polypropylene, impact resistance is improved. On the other hand, in method No. 15 for improving surface adhesion properties, it has been investigated that the surface of a molded article is modified by etching it by a physical method or a chemical method. (:tsu) nM that the invention attempts to solve However, 1. I of F (I IF P's it VM
Extremely impact resistant.The Izotsu strength of the 1st generation is about 5 to 7 cra/cm at most, and is used for applications that require extremely high impact resistance such as car bumpers, motorcycle fender helmets, etc. However, it is still insufficient. Furthermore, methods for improving surface workability such as adhesion, paintability, and printability by etching have problems such as not only insufficient effects but also deformation of the molded product. It is therefore an object of the present invention to provide a propylene composition which has even better impact resistance than what is currently known as high impact polypropylene (HIPP) and at the same time has improved surface processability. (4) Means for solving the ff1 problem As a result of various studies in order to solve all of the above tMM problems, the present inventors determined that ethylene, α, β - Unsaturated carboxylic acids and/or hydrothermal products thereof, or copolymers (1) of these and unsaturated carboxylic esters, and ethylenically unsaturated monomers containing ethylene and epoxyno&, or these and unsaturated carboxylic acid esters. Component (I3) obtained by mixing copolymer (U) with acid ester or vinyl ester
of. (A) : (R) = 90810 to 70:30 (weight ratio), it is surprising that a propylene composition in which a portion of component 1) traces back to the Chinese soil is obtained L:,
#We discovered that not only does it have consistently high l+8tw impact resistance, but it also has excellent surface processability such as adhesion, paintability, and printability without the need for surface treatments such as etching, leading to the completion of the present invention. Ta. The isotactic polypropylene used in the present invention (
A) Copolymers of ethylene and α, β-unsaturated carboxylic acids and/or their anhydrides, or copolymers of these and unsaturated carboxylic esters (LL and ethylene and ethylenically unsaturated monomers containing epoxy groups, or Copolymers (II) of these with unsaturated carbon layer esters and vinyl esters will be explained in detail. It includes a copolymer with an olefin, and can be purchased by a known method using a Ziegler-Natsuta catalyst.Ethylene and α, β-unsaturated carboxylic acid and/or its anhydride used in the present invention As α,β-unsaturated carboxylic acids and their anhydrides which are comonomer components in the copolymer (1) of monomers or unsaturated carboxylic acid esters, those shown in F are preferred.

[Used twice. α,
β-unsaturated carboxylic acid. The anhydride usually has at most 20 carbons. In particular, 3 to 16 are preferred, and typical examples include acrylic acid, methacrylic acid, crotonic acid, monoalkylphate, monoalkyl fumarate, maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, examples of the unsaturated carboxylic acid ester as a comonomer component include alkyl (meth)acrylate and alkoxyalkyl (meth)acrylate. Among these, the alkyl (meth)acrylate generally has 4 to 30 carbon atoms, and preferably 4 to 20 carbon atoms. Examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. Also, for alkoxyalkyl (meth)acrylates, the number of carbon atoms is usually at most 20. Here, the alkyl group and alkoxy group preferably have 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Examples include methoxyethyl acrylate, ethoxyethyl acrylate, and butoxyethyl acrylate. The epoxy monomer that is a comonomer component in the ethylenically unsaturated monomer containing ethylene and an oxydoxy group or the copolymer of these with an unsaturated carboxylic acid ester or vinyl ester (■) used in the present invention is generally Formula (a), (1)) R-C-0-CH2-CH-C
H2 (,) R-0-CH2-CH-CH2 (b) (wherein, R may be the same or JffIN, a vinyl group,
A hydrocarbon group having an ethylenically unsaturated bond and having a carbon number of 2 to 811N, such as an allyl (^LLYL) group. )
Examples of the epoxy monomers include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methacryl glycidyl ether, etc. The unsaturated carboxylic acid ester that is a comonomer component is the same as that used for copolymer (1).The vinyl ester that is a comonomer component generally has at most 20 carbon atoms, and 4 to 4 carbon atoms. Preferably 16 pieces;
Examples include vinyl #acid, vinyl propionate, vinyl butyrate, and vinyl acetate is particularly preferred. The copolymer composition of the above copolymer (1) or If) is not particularly limited, but the following comonomer composition is preferable. First, for copolymer (I), α
, β-unsaturated carboxylic acid, copolymer chain of its anhydride, or
0.1-15 mol%, particularly preferably 0.1-10 mol%, when the copolymerization composition ratio of α2β-unsaturated carboxylic acid and/or its anhydride is less than 0.1 mol%,
The crosslinking density of components (I) and (II) becomes low, resulting in insufficient impact strength and lack of polarity, making it impossible to obtain sufficient surface properties.On the other hand, if it exceeds 15 mol%, This is not only undesirable because it makes it difficult to manufacture the combined product and makes stable production difficult, but also because the acid anhydride absorbs a lot of moisture in the air, causing foaming during molding. The copolymerization composition ratio of the acid ester is preferably 0.5 to 50 mol%.
), the copolymerization composition of the epoxy comonomer is
The content is preferably from 0.2 to 15 mol%, and preferably from O,S to 12 mol%. Furthermore, the copolymerization composition of unsaturated carboxylic acid ester and vinyl ester is preferably 0 to 50 mol%. Further, the molecular weight, molecular weight distribution, melt flow index, and density of the copolymers (1), (II) are not particularly limited. The mixing ratio of polypropylene (A) and component (B) of the present invention is not particularly limited, but (A): (B)
=90:10-70:30 is preferable. In the component (B) of the present invention, the ratio of the epoxy group in the copolymer (L) to 1 mole of carboxyl group and/or its anhydride group in the copolymer (1) is 0.1 to 20 moles. , particularly preferably 0.2 to 15 mol, more preferably 0.5 to 2 mol. less than 0.1 mole and 20
If the amount exceeds mol, the crosslinking density will be low and sufficient we strength will not be obtained. The mixture of polypropylene (A) and component (B) of the present invention is
It can be carried out by any general method, for example, mixing can be carried out using a Banbury mixer, a kneader or an extruder at a temperature at which both components melt. Further, in order to promote the crosslinking reaction, a reaction accelerator may be added at the time of mixing. Typical examples of reaction accelerators include ethanolamine, jetanolamine, triethanolamine, dimethylamine, diethylamine, n- propylamine,
Isopropylamine, n-butylamine, N,N-dimethylaminoethanol, N,N-diethylaminoethanol, morpholine, piperidine, pyridine+
N,N-dimethylaminoethyl acrylate, N,1
ll-dimethylaminomethacrylate), N,N-diethylaminoethyl acrylate, trimethylamine, triethylamine, tri-n-butylamine, N
, N-dimethylbenzylamine, hexamethylenetetramine, triethylenediamine, tertiary amines such as N,N-dimethylpiperazine and N-methylmorpholine, acidic or alkaline compounds such as p-toluenesulfonic acid and potassium hydroxide, and trimethyl Ammonium halogen salts such as benzylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride and cetyltrimethylammonium chloride, plus chloride +1! One example is lead. Particularly preferred are N,N-dimethylbenzylamine and P-toluenesulfonic acid. Additionally, additives such as antioxidants, ultraviolet absorbers, lubricants, antistatic agents, electrical property improvers, flame retardants, processability improvers, St additives, talc, calcium carbonate, barium sulfate, etc., as necessary. Inorganic fillers such as mica and calcium silicate can be blended. Although the al structure by which the polypropylene composition of the present invention exhibits IwtgJ impact properties is not clear, the I' in the copolymer <1)
[1 Anhydride and the epoxy groups in the copolymer (11) partially react to form a 1M bridge tR structure, which is thought to contribute to rubber elasticity. The reason why the surface properties of the polypropylene composition of the present invention are so poor is thought to be that the polar groups in the copolymers (1) and (II) activated the surface. (5) Examples Next, the polypropylene composition of the present invention will be explained in more detail with reference to Examples. [Isotactic polypropylene] MFR = 7.2, g/10+*in [Ethylene and α
, β-unsaturated carboxylic acid, its anhydride, or a copolymer of these and an unsaturated carboxylic acid ester (I)] Using high-pressure process low-density polyethylene manufacturing equipment. Terpolymer consisting of ethylene (E), maleic anhydride and (MAh) methyl methacrylate (MMA) and 1$ consisting of ethylene (E) and acrylic/fjI (AA)
Various compositions of polymer (1) were prepared. Composition (IIo 1%) and MFR (g
/10m1. n) is shown below. (1-L)E/M^h/HMA= 60.0/3.0/
37. ONPR= 2.5(1-2) E/HAh/呵に＾= 98.710.8/2.5 -FR=17(1
-3) E/^A= 98.8/3.4 MPR= 8
．． 2t Ethylene and epoxy group-containing ethylenically unsaturated monomers or copolymers of these with unsaturated carboxylic acid esters and vinyl esters (■) l^ Using high-pressure method low-density polyethylene manufacturing equipment, ethylene (E) Various compositions of terpolymers (■) consisting of glycidyl methacrylate (GMA) and vinyl butyrate (VA) were prepared. Set Jli (IIo) of copolymer (II) used in Examples
1%) and MFR (710 m1n) are shown below. (II-1) E/GM^/VA= 97.5/2.51
0 to FR=3(II -2) E/GNA/V^=
95.1'! /2.3/1.9 NPR= 7

[Physical property test method]

(1) HFR: JIS 7210 (2) 8141%@a Strength: JIS K 7113
(3) 7 (Jit impact strength: [5K 711O (4
) Hardness: ASTM-D-2240 (5) Paintability: Spray paint (Flexene 101 manufactured by Nippon Paint) and bake at 120°C for 30 minutes, JIS K
5400 goban tests were conducted. (6) Gel fraction: 1 g of sample was placed in a 300 mesh stainless steel wire and boiled in xylene at 8 o'clock. Thereafter, it was dried in a vacuum dryer for 24 hours, and the remaining xylene-insoluble matter was expressed as a gel fraction as a percentage of the sample. Examples 1 to 12 "Isotactic polypropylene (A) and components (
When the above-mentioned physical property tests were conducted on a composition in which copolymer (1) (B) and copolymer (U) were blended as shown in Table 1, the impact strength and paintability were improved. The results are shown in Table 111. Comparative Examples 1 to 6 "-Isotactic polypropylene (A) and components (
B) copolymer (I) and copolymer (II) in 1a
The above physical property tests were conducted on the compositions formulated as shown in . The results are shown in Table 1.As is clear from the table, compositions such as those shown in the comparative examples may have good paintability, but have poor impact resistance and are not practical. (Left below) (6) Effects The polypropylene composition of the present invention is mainly used in fields that require high impact resistance and paintability, such as automobile bumpers, motorcycle fenders, and helmets, and in soft materials such as various hose parts for home appliances. It can be used in a wide range of fields. Patent applicant Showa Denko Co., Ltd.

Claims (2)

[Claims] (1) For isotactic polypropylene (A), copolymer (I) of ethylene and α, β-unsaturated carboxylic acid and/or its anhydride, or these and unsaturated carboxylic acid ester, and ethylene and an ethylenically unsaturated monomer containing an epoxy group or a copolymer of these with an unsaturated carboxylic acid ester or vinyl ester (II)
Component (B) obtained by mixing (A):(B)=9
A partially crosslinked polypropylene composition obtained by blending component (B) in a ratio of 0:10 to 70:30 (weight ratio). (2) In component (B), the ratio of epoxy groups in copolymer (II) to 1 mole of carboxyl groups and/or their anhydride groups in copolymer (I) is 0.1 to 20 moles. The polypropylene composition according to claim (1).