JP2643388B2 - Modified polyolefin resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyolefin resin composition modified with an unsaturated carboxylic acid or a derivative thereof or an unsaturated epoxy monomer.

[Prior art] Polyolefin resins represented by polypropylene and polyethylene have various excellent physical properties, chemical properties, mechanical properties, moldability, and are inexpensive, in addition to being inexpensive. It is widely used in many industrial fields.

However, since polyolefin resin is non-polar, it has poor adhesion and affinity with metals, glass, polar polymer materials, and the like, and it is difficult to form a composite with these various substrates.

For this reason, it has been well known that a polyolefin resin is conventionally modified by introducing a polar group by graft-modifying an unsaturated carboxylic acid such as acrylic acid or maleic anhydride or a derivative thereof using, for example, acrylic acid or maleic anhydride. Is widely and generally practiced.

However, in the conventional method, since the grafting efficiency of the unsaturated carboxylic acid or a derivative thereof is low, there are many residual unreacted monomers, and further, the flowability (metroflow rate) of the polyolefin before and after grafting is largely changed. There is a disadvantage that the physical properties of the graft-modified product decrease.

JP-A-55-50040 discloses a method of adding rubber, and JP-A-53-1291 discloses an aromatic hydrocarbon having a tertiary alkyl group or a secondary alkyl group, or a method of adding a rubber. A method of kneading in the presence of an aromatic hydrocarbon having at least one primary alkyl group and a method of performing a radical reaction in the presence of a polyalkylbenzene have been proposed in JP-A-52-93495. I have.

However, in the method described in JP-A-55-50040, an improvement in the grafting amount (addition amount) is recognized, but since the grafting monomer and the radical generator are dividedly added and the reaction time is required to be long, economical use is required. Not only is there a problem with the properties and profitability, but also the drawback is that the fluidity (melt flow rate) after the graft modification is significantly increased. Also,
In the method described in JP-A-53-1291, an effect is recognized in a crosslinked polyolefin mainly composed of ethylene, but the effect is not clarified in a decomposed polyolefin mainly composed of propylene. No significant improvement is expected.

Furthermore, the method described in JP-A-52-93495 shows an improvement in the amount of graft, but the change in fluidity (melt flow rate) after graft modification is not clarified. Not only is not expected, but also has the drawback that the polyalkylbenzene tends to remain in the polymer due to the high boiling point of the melt-kneading method.

Further, Japanese Patent Application Laid-Open No. 46-1679 (U.S. Pat.
No.) proposes reacting a mixture of maleic anhydride and styrene with a polyolefin resin.However, since a large proportion of styrene is used with respect to maleic anhydride and no radical initiator is used, Since the grafted amount of maleic anhydride is small, and the formation of homopolymer of styrene and the unreacted material of maleic anhydride are contained in a large amount, a modified polyolefin resin composition having low mechanical strength and practical use can be obtained. I can't.

[Problems to be Solved by the Invention] The object of the present invention is to provide an unsaturated carboxylic acid or a derivative thereof or an unsaturated epoxy monomer by a melt kneading method in which an unsaturated aromatic monomer is present in a specific ratio. An object of the present invention is to provide a modified polyolefin resin composition having a large graft amount of a monomer, a small change in fluidity (melt flow rate) before and after graft modification, and excellent physical properties.

[Means for Solving the Problems] The present inventors have conducted various studies on a method of melt-kneading a polyolefin resin and an unsaturated carboxylic acid or a derivative thereof or an unsaturated epoxy monomer, and as a result, a specific ratio of unsaturated By graft modification in the presence of an aromatic monomer and a radical initiator, the graft amount is large,
In addition, the inventors have found that a modified polyolefin resin composition having a small change in fluidity (melt flow rate) before and after the graft modification and excellent physical properties can be obtained, and arrived at the present invention.

That is, the present invention relates to 100 parts by weight of a polyolefin resin (A) having a melt flow rate of 0.05 to 60 g / 10 minutes, at least one compound selected from unsaturated carboxylic acids, derivatives thereof and unsaturated epoxy monomers ( B) 0.1 to 5 parts by weight, an unsaturated aromatic monomer (C) 0.1 to 5 parts by weight, and a radical initiator (D) 0.0
A mixture comprising from 1 to 2 parts by weight and having a molar ratio of (B) / (C) of 1 mol (B) to 0.1 mol or more and less than 1 mol of (C) is melt-kneaded. And a modified polyolefin resin composition.

The melt flow rate used in the present invention is 0.05 to 60 g /
Examples of the polyolefin resin (A) for 10 minutes include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, crystalline polypropylene, and crystalline propylene.
Ethylene random copolymer, crystalline propylene-ethylene block copolymer, polybutene-1, propylene-butene-1 copolymer, poly-4-methylpentene-1, propylene-4-methylpentene-1 copolymer, Propylene-ethylene-butene-1 terpolymer, ethylene-vinyl acetate copolymer, ethylene-methyl (meth) acrylate copolymer, ethylene-ethyl (meth) acrylate copolymer, ethylene- (meth) Butyl acrylate copolymer,
Ethylene- (meth) bacrylic acid or its partial metal salt copolymer, ethylene- (meth) acrylic acid- (meth) acrylate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate-vinyl alcohol copolymer Various olefin homopolymers and copolymers such as a polymer and an ethylene-styrene copolymer can be used. Further, these polyolefin resins may be used as a mixture of two or more kinds.

The melt flow rate of the polyolefin resin (A) is 0.05 to 60 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes, but the melt flow rate of the resulting modified polyolefin resin composition is 0.1 to 100 g / 10 minutes. Need to be selected.

For this reason, more preferred melt flow rates are crystalline polypropylene, which is a decomposable polyolefin resin, crystalline propylene-ethylene random copolymer, crystalline propylene-ethylene block copolymer, polybutene-1, poly-4-methyl. For pentene-1 etc., 0.1 ~ 4
0 g / 10 min, polyethylene, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylate-based copolymer, ethylene which is a cross-linked polyolefin resin, ethylene-
In the case of a vinyl alcohol copolymer or the like, the amount is 1 to 50 g / 10 minutes.

Here, the melt flow rate is based on ASTM D1238, and the polypropylene resin is 230 ° C. and 2.16 kg, the polyethylene resin and the polybutene-1 resin are 190 ° C. and 2.16 k.
g, and poly-4-methylpentene-1 based resin is 260
It was measured under conditions of ° C and 5 kg.

If the melt flow rate of the polyolefin resin (A) is less than 0.05 g / 10 minutes, the fluidity becomes small, and it is difficult to produce a modified polyolefin resin composition. On the other hand, if it exceeds 60 g / 10 minutes, the mechanical properties of the modified polyolefin resin composition are lowered, which is not preferable.

In the present invention, the number average molecular weight of the polyolefin resin (A) is preferably from 7,000 to 800,000, more preferably from 10,000 to 700,000.

In the present invention, polypropylene is crystalline polypropylene, and in addition to propylene homopolymer,
A block copolymer obtained by copolymerizing propylene in the step, ethylene and propylene, and α-olefin such as butene-1 in the second step, or propylene and ethylene;
And random copolymers obtained by copolymerizing α-olefin such as butene-1.

The propylene homopolymer, block or random copolymer can be obtained, for example, by reacting in the presence of a catalyst in combination with titanium trichloride and an alkylaluminum compound usually called a Ziegler-Natta type catalyst.

The polymerization can be carried out up to 0 ° C to 300 ° C. However, in the highly stereoregular polymerization of α-olefin such as propylene, the polymerization is usually performed in the range of 0 ° C. to 100 ° C. because a polymer having a high degree of stereoregulation cannot be obtained at 100 ° C. or higher. Is preferred.

The polymerization pressure is not particularly limited, but a pressure of about 3 to 100 atm is desirable from the viewpoint of industrial and economical use.

The polymerization method may be either a continuous type or a batch type.

As the polymerization method, slurry polymerization with an inert hydrocarbon solvent such as butane, pentane, hexane, heptane, and octane, solvent polymerization in which the produced polymer is polymerized while being dissolved in the inert hydrocarbon solvent, and no solvent Bulk polymerization in a liquefied monomer and gas phase polymerization in a gaseous monomer are possible.

In order to adjust the molecular weight of the polymer, a chain transfer agent such as hydrogen can be added.

The polypropylene used in the present invention can be produced using an isospecific Ziegler-Natta catalyst. The catalyst used is isospecific (Is
Those having high ospecificity) are preferred.

A catalyst that can be suitably used is a composite solid compound of a titanium compound or a titanium compound whose transition metal catalyst component has a layered crystal structure and a titanium compound, and a typical metal component is an organoaluminum compound. The catalyst can contain a known electron donating compound as the third component.

As titanium trichloride, those produced by reducing titanium tetrachloride with various reducing agents can be used. As the reducing agent, metals such as aluminum and titanium, hydrogen, and organometallic compounds are known. A typical example of titanium trichloride produced by metal reduction is titanium tetrachloride reduced by metallic aluminum,
It is a titanium trichloride composition (TiCl ₃ AA) containing aluminum chloride which has been activated by grinding in an apparatus such as a ball mill or a vibration mill. For the purpose of improving iso-specificity, polymerization activity and / or particle properties, a compound selected from ether, ketone, ester, aluminum chloride, titanium tetrachloride and the like can be co-present during pulverization.

When the modified polyolefin resin composition of the present invention is used particularly for applications requiring heat resistance, rigidity, scratch resistance, etc., polypropylene is a propylene homopolymer and a block copolymer of the first segment polymerized in the first step. The isotactic pentad fraction of the boiling heptane-insoluble portion of a certain homopolymer portion is 0.970 or more, and the content of the boiling heptane-soluble portion is 5.0% by weight or less,
It is preferable to use a highly crystalline polypropylene having a xylene-soluble portion at 20 ° C. of 2.0% by weight or less.

The isotacticity of the boiling heptane insoluble part
Pentad fraction, boiling heptane solubles content and 20
The content of the polymer soluble in xylene at ℃ is determined as follows.

After completely dissolving 5 g of polypropylene in 500 ml of boiling xylene, the temperature is lowered to 20 ° C. and left for 4 hours. Thereafter, this is separated by filtration, and a xylene-insoluble part at 20 ° C. is separated. Concentrate the filtrate,
After drying to evaporate xylene, it is further dried at 60 ° C. under reduced pressure to obtain a polymer soluble in xylene at 20 ° C. The value obtained by dividing the dry weight by the weight of the charged sample and expressed as a percentage is the content of the xylene-soluble portion at 20 ° C. After the xylene-insoluble part at 20 ° C is dried, it is subjected to Soxhlet extraction with boiling n-heptane for 8 hours. This extraction residue is referred to as a boiling heptane-insoluble part, and the dry weight is used as the sample weight (5
The value obtained by dividing the value subtracted from g) by the weight of the charged sample and expressing the result as a percentage is the content of the boiling heptane-soluble portion.

Isotactic pentad fraction is defined as A. Zambelli
Et al., Macromolecules 6 , 925 (1973), i.e., an isotactic chain of pentad units in a polypropylene molecular chain measured using ¹³ C-NMR, in other words, 5 units of propylene monomer units. It is the fraction of propylene monomer units at the center of a chain of continuous and mameli bonds. However, regarding the assignment of the NMR absorption peak, Macromolecules 8 , 687 published later
(1975).

Specifically, the isotactic pentad fraction is measured as the area fraction of the mmmm peak in all the absorption peaks in the methyl carbon region of the ¹³ C-NMR spectrum. By this method, NPL reference material CRM No. of NATIONAL PHYSICAL LABORATORY, UK
M19-14 polypropylene PP / MWD / 2 isotactic
The measured pentad fraction was 0.994.

The highly crystalline polypropylene is described in, for example, JP-A-60-28405.
And JP-A-60-228504, JP-A-61-218606, JP-A-61-287917, and the like.

When the modified polyolefin resin composition of the present invention is used for applications requiring impact resistance, the polypropylene is a homopolymer portion of propylene, which is the first segment polymerized in the first step, and the second polymer is polymerized in the second step. Α- such as ethylene and propylene and butene-1 which are two segments
It is preferable to use a propylene block copolymer obtained by copolymerizing olefin.

The propylene block copolymer can be produced by a slurry polymerization method and a gas phase polymerization method. Particularly when used for applications requiring high impact resistance, it is necessary to increase the amount of the second segment, and the second segment is suitably produced by a gas phase polymerization method.

The high impact polypropylene by the gas phase polymerization method can be produced, for example, by the method exemplified in JP-A-61-287917.

In the propylene block copolymer, the propylene homopolymer portion polymerized in the first step is a propylene homopolymer, and the content of propylene in the polymer formed in the step is 0 to 6 mol%, preferably 0 to 3 mol%. May be a copolymer with ethylene or α-olefin having 4 to 6 carbon atoms. The second segment copolymer portion polymerized in the second step is polymerized solely with ethylene,
Alternatively, the ethylene content in the polymer produced in the process is 10
It is preferably a copolymer of ethylene and propylene having an amount of at least 20 mol%, preferably 20 to 70 mol%, or a copolymer of α-olefin having 4 to 6 carbon atoms. The polymer produced in the second step is 10 to 95% by weight based on the total weight.

In the slurry polymerization method, the second segment is suitably produced in the range of 10 to 30% by weight, and in the gas phase polymerization method, it is suitably produced in the range of 10 to 95% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight. .

In the gas phase polymerization method, a propylene block copolymer having a large amount of the second segment can be produced by the method exemplified in Japanese Patent Application No. 62-256015, and is suitably used for applications requiring ultra-high impact resistance. .

The intrinsic viscosity of the second segment in a 135 ° C. tetralin solvent must be changed depending on the productivity during production, the powder properties of the polymer, or the intrinsic viscosity of the first segment.
In the slurry polymerization method, it is generally 2 to 8 dl / g, and in the gas phase polymerization method, it is 1 to 5 dl / g.

Among the at least one compound (B) selected from the unsaturated carboxylic acids, derivatives thereof and unsaturated epoxy monomers used in the present invention, examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, Maleic acid, itaconic acid, citraconic acid, hymic acid, bicyclo (2,2,
2) oct-5-ene-2,3-dicarboxylic acid, 4-methylcyclohex-4-ene-1,2 dicarboxylic acid, 1,2,3,4,
5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid, bicyclo (2,2,1) oct-7-ene-2,3,5,6-tetracarboxylic acid, 7-oxabicyclo ( 2,2,1) hepta-5-ene-2,3-dicarboxylic acid and the like, and unsaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides and metal salts, for example, Maleic anhydride, itaconic anhydride, citraconic anhydride, hymic anhydride, monoethyl maleate, monoethyl fumarate, monomethyl itaconate, monomethyl fumarate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylamide, acrylamide, Methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N- Diethylamide,
Maleic acid-N-monobutylamide, maleic acid-N, N
-Dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N,
N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutylamide, maleimide, N
-Butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate and the like.

Further, examples of the unsaturated epoxy monomer include unsaturated glycidyl esters and unsaturated glycidyl ethers represented by the following general formulas (1) and (2).

(R is a hydrocarbon group having 2 to 18 carbon atoms having an ethylenically unsaturated bond.) (R ′ is a hydrocarbon group having 2 to 18 carbon atoms having an ethylenic unsaturated bond, and X is —CH ₂ —O— or It is. Specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, allyl glycidyl ether, 2-methylacryl glycidyl ether, styrene-p-glycidyl ether and the like.

These unsaturated carboxylic acids or derivatives thereof or unsaturated epoxy monomers may be used as a mixture of two or more.

Of these, maleic anhydride, glycidyl acrylate or glycidyl methacrylate is most preferably used.

As the unsaturated aromatic monomer (C) used in the present invention, styrene is most preferred, but o-methylstyrene,
p-Methylstyrene, m-methylstyrene, α-methylstyrene, vinyltoluene, divinylbenzene and the like can also be used, and these can be used in combination.

The radical initiator (D) used in the present invention includes:
Known ones can be used. For example, azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4,4-trimethylvaleronitrile), methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,5,5 -Trimethylcyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t
-Butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, 1,3-bis (t-butylperoxide Oxyisopropyl) benzene, 2,5
-Dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy)
Hexane-3, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, t-butyl peracetate, t-butyl peroxyisobutyrate, t-butyl peroxyvivalate, t-butyl Peroxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate,
Various organic peroxides such as polystyrene peroxide are exemplified.

In the method for producing the modified polyolefin resin composition of the present invention, the amount of each component is at least one selected from unsaturated carboxylic acids, derivatives thereof and unsaturated epoxy monomers per 100 parts by weight of the polyolefin resin (A).
0.1 to 5 parts by weight of the compound (B), preferably 0.2 to 3 parts by weight, 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight of the unsaturated aromatic monomer (C) and the radical initiator (D) 0.01
To 2 parts by weight, preferably 0.02 to 1 part by weight, and
The molar ratio of (B) / (C) is in the range of 1 / 0.1 to less than 1/1.

Here, if the addition amount of the component (B) is less than 0.1 part by weight, there is no significant reforming effect, and if it exceeds 5 parts by weight, the reforming effect reaches saturation and not only a further remarkable effect is not exhibited, but also unreacted effect is exhibited. As a large amount of the substance remains in the polymer, it is not practically preferable due to odor, reduced adhesiveness, corrosion of a molding machine, and the like.

When the amount of the component (C) is less than 0.1 part by weight, no significant modification effect is obtained. When the amount exceeds 5 parts by weight, not only a remarkable effect is not exerted, but also homopolymer production is increased and the modified polyolefin This results in a decrease in the mechanical strength of the resin.

Further, when the addition amount of the component (D) is less than 0.01 part by weight, the graft reaction amount of the component (B) is low, and a large amount of unreacted product of the component (B) remains in the polymer, which is not practically preferable.
If it exceeds 2 parts by weight, no further remarkable effect is exerted on the graft reaction of the component (B), and
Decomposition or cross-linking of polyolefin resin increases,
Fluidity (melt flow rate) change is large, which is not preferable for practical use.

When the (B) / (C) molar ratio is less than 1 / 0.1,
Since the effect of improving the graft amount of the component (B) is small and the change in the melt flow rate is large, a practically preferable modified polyolefin resin composition which is the object of the present invention cannot be obtained.
If it is 1 or more, the production of the homopolymer of the component (C) increases, and the mechanical strength of the modified polyolefin resin composition is greatly reduced, so that the modified polyolefin resin composition cannot be used practically.

The melt flow rate of the modified polyolefin resin composition thus obtained is 0.1 to 100 g / 10 minutes, preferably 0.5
5050 g / 10 min, more preferably 1-30 g / 10 min.

The method for producing the modified polyolefin resin composition of the present invention comprises the steps of: preparing a polyolefin resin (A), at least one compound (B) selected from unsaturated carboxylic acids, derivatives thereof, and unsaturated epoxy monomers; In the presence of the monomer (C) and the radical initiator (D), 150
Melt kneading can be carried out using an extruder, a Banbury mixer, a kneader or the like at a temperature of from 300 to 300 ° C, preferably from 190 to 280 ° C, and a residence time of from 0.3 to 10 minutes, preferably from 0.5 to 5 minutes.

Industrially, with a single-screw or twin-screw extruder, the ventro section is kept in a vacuum state, and unreacted components (B), (C),
Advantageously, there is provided a method of continuously producing while removing (D) and its side products such as oligomers and decomposition products.
The reaction atmosphere may be air, but preferably in an inert gas such as nitrogen or carbon dioxide. In order to further remove trace amounts of unreacted components and reaction products contained in the obtained modified polyolefin resin composition, heat treatment at a temperature of 60 ° C. or more, solvent extraction, and vacuum drawing under melting are performed. You can also.

Further, for the modified polyolefin resin composition of the present invention, an antioxidant, a heat stabilizer, a light stabilizer, a nucleating agent, a lubricant, an antistatic agent, an inorganic or organic filler, an inorganic or organic Various additives such as a coloring agent, a rust inhibitor, a cross-linking agent, a foaming agent, a lubricant, a plasticizer, a fluorescent agent, a surface smoothing agent, and a surface gloss improving agent can be added during the manufacturing process or in the subsequent processing process. .

The modified polyolefin resin composition of the present invention thus obtained is used alone or with a specific magnesium oxide, and further by blending an unmodified polyolefin resin to form an adhesive resin composition.
It can be widely used as coatings, binders and laminating adhesives for various substrates.

Further, application to a polymer alloy is also possible. Polyolefin resins, particularly polypropylene, are widely used as general-purpose resins in films, home appliances, and the like, and are also being used in automobiles due to compounding of rubber, fillers, and the like.

In recent years, the need for higher performance and higher functionality has increased due to the alloying with engineering plastics.
In order to respond to the diversifying demands of the market, improvement and reforming are being studied in various ways. Therefore, in order to alloy polypropylene and engineering plastic, it is necessary to introduce polar groups while maintaining the original excellent physical properties of polypropylene. From such a viewpoint, the modified polyolefin resin composition of the present invention has excellent reactivity and compatibility with engineering plastics, and retains the excellent physical properties of polyolefins, so that it is used for alloying engineering plastics with polypropylene. be able to.

By using the modified polyolefin resin composition of the present invention and applying a known processing technique, various composite materials having excellent adhesiveness, such as a coated body, a laminated body, and a reinforced resin, can be produced. For example, in the production of coatings and laminates, fluid immersion method, electrostatic coating method, powder coating method such as spraying method, solution coating method, extrusion coating method, dry lamination method, heat compression method, insert molding method, Furthermore, a combination of these is applied according to the purpose. In addition, a filler-reinforced resin, a fiber-reinforced resin, or the like can be manufactured by an extrusion molding method, an injection molding method, or the like.

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

 Next, methods for measuring physical properties in the examples are described below.

(1) Melt flow rate According to the method specified in JIS K6758. Measurement temperature is 230 ℃
And the load is measured at 2.16 kg unless otherwise noted.

(Same as ASTM D1238) (2) Bending test According to the method specified in JIS K7203. The thickness of the test piece is
The flexural modulus and the flexural strength are evaluated under the conditions of 3.2 mm, a span length of 50 mm, and a load speed of 1.5 mm / min. The measurement temperature is 23 ° C unless otherwise specified. In the case of other temperatures, measurement is performed after adjusting the state in a constant temperature bath at a predetermined temperature for 30 minutes.

(3) Izod impact strength According to the method specified in JIS K7110. The thickness of the test piece is
It is 3.2 mm, and the impact strength with a notch is evaluated. The measurement temperature is 23 ° C unless otherwise specified. In the case of other temperatures, the condition is adjusted after adjusting the condition in a constant temperature bath at a predetermined temperature for 2 hours.

(4) Addition amount of glycidyl methacrylic anhydride maleic anhydride and styrene The addition amount of maleic anhydride in the modified polypropylene resin composition was determined by dissolving a small amount of a sample in heated cheresin and precipitating the same with anhydrous acetone, followed by xylene again. The solution was determined by titration with a NaOH methanol solution while heating (110 to 120 ° C.) using phenolphthalein as an indicator.

The amount of glycidyl methacrylate added was determined by first opening the epoxy with a xylene-methanol-hydrochloric acid solution and heating the excess hydrochloric acid with phenolphthalein as an indicator (11).
0-120 ° C.) It was determined by back titration with a methanol solution of NaOCH ₃ .

The amount of styrene added was determined using the intensity of the peak corresponding to the substituted benzene ring appearing in the infrared absorption spectrum measured using the purified product.

(5) to produce ethylene content pressed sheet, methyl appearing in the measured infrared absorption spectrum (-CH ₃₎ and methylene (-CH ₂ -) by using the absorbance of characteristic absorption of was determined by a calibration curve method.

The above test pieces for evaluating physical properties were produced under the following injection molding conditions unless otherwise specified. The composition is heated in a hot air dryer 12
After drying at 0 ° C. for 2 hours, injection molding was performed using an IS150E-V injection molding machine manufactured by Toshiba Machine Co., Ltd. at a molding temperature of 240 ° C., a mold cooling temperature of 70 ° C., an injection time of 15 sec, and a cooling time of 30 sec.

Example 1 Melt flow rate as polyolefin resin (A)
Is 3 g / 10 min of crystalline propylene-ethylene block copolymer
Maleic anhydride is added to 100 parts by weight of the combined (A-1).
(B) 1.0 part by weight, styrene (C) 0.5 part by weight, radical
1,3-Bis (tertiary-butylpar) as an initiator (D)
-Oxyisopropyl) benzene (D-1, Sanken Chemical)
Samperocus Co., Ltd. -TY1.3) 0.048 parts by weight
And Irganox as a stabilizer 1010 (Ciba Geigy
0.1 parts by weight of Hensiel mixer
Temperature, 230 ° C, average residence time in a 30mmφ single screw extruder
Melt and knead in 1.8 minutes, graft-modified polyolefin resin
I got Melt flow resin of this modified polyolefin resin
The rate is 3.2 g / 10 min and the content of maleic anhydride is 0.2
It was 5% by weight.

 Table 1 shows the results.

Comparative Example 1 The same method as in Example 1 was repeated except that styrene was not used in Example 1. The results were as shown in Table 1.

Examples 2 and 3 The method of Example 1 was repeated except that the mixing ratio of styrene and maleic anhydride was changed to the ratio shown in Table 1.
The results were as shown in Table 1.

Comparative Example 2 The procedure of Example 2 was repeated except that styrene was not used in Examples 2 and 3. The results were as shown in Table 1.

Example 4 The method of Example 1 was repeated except that a crystalline polypropylene (A-2) having a melt flow rate of 1.5 g / 10 min was used as the polyolefin resin (A). The results were as shown in Table 1.

Comparative Example 3 The same method as in Example 4 was repeated except that styrene was not used in Example 4. The results are as shown in Table 1.

Example 5 t-butyl peroxyl as a radical initiator (D)
Urate (D-2, manufactured by NOF CORPORATION; perbutyl
L) 0.6 parts by weight and 0.5 parts by weight of maleic anhydride
Except for this, the same method as in Example 1 was repeated. This result
It is shown in Table 1.

Comparative Example 4 The same method as in Example 5 was repeated except that styrene was not used in Example 5. Table 1 shows the results.

Example 6 1,3-Bis (tert-butylperoxyisopropyl) benzene (D-1) as a radical initiator (D)
Is used in an amount of 1.0% by weight (substantially 0.08% by weight) in which 8 wt% is supported on crystalline polypropylene (A-2).
A modified polyolefin resin was obtained by repeating the same method as in Example 1 except that the mixture was melted and mixed at a temperature of 270 ° C. and an average residence time of 0.8 minutes using a twin-screw extruder. The melt flow rate of the modified polyolefin resin was 6.9 g / 10 minutes, and the maleic anhydride content was 0.29% by weight.

Example 6, Comparative Example 5 A modified polyolefin resin composition was produced by the following method.
Built. Melt flow rate is 1.3 (g / 10min), 135 ℃,
Intrinsic viscosity in tetralin solvent is 2.45 (dl / g), cold at 20 ℃
Xylene solubles content 2.9% by weight, boiling heptane available
The content of the melting part is 6.7% by weight.
Slurry with a sotactic pentad fraction of 0.955
-Manufactured by a polymerization method as exemplified in JP-A-60-28405.
Of the crystalline polypropylene (A-3)
I did. 100 parts by weight of crystalline polypropylene (A-3)
In contrast, 1.0 part by weight of maleic anhydride and 0.5 part by weight of styrene
Part, as a radical initiator, 1,3-bis (tertiary
Butyl peroxyisopropyl) benzene (Sanken Chemical)
Samperocus Co., Ltd. −TY1 ・ 3) is propylene
0.6% by weight of 8% by weight supported on the homopolymer
And Irganox as a stabilizer 1010 (Ciba Geigy
0.1 parts by weight of Hensiel mixer
After that, TEX 44SS-30BW-2V type twin screw extrusion made by Nippon Steel Corporation
Kneading at 220 ° C with an average residence time of 1.5 minutes
And maleic anhydride addition 0.15% by weight, styrene addition
0.07% by weight, melt flow rate 21 (g / 10min) anhydrous
A maleic acid / styrene modified polypropylene was produced.

As Comparative Example 5, except that styrene was not used,
Produced in exactly the same manner as above, with a maleic anhydride loading of 0.
A maleic anhydride-modified polypropylene with a melt flow rate of 36 (g / 10 minutes) at 08% by weight was obtained.

 Table 2 shows the results of these evaluations.

Example 7 A modified polyolefin resin was produced by the following method. At 135 ° C, the intrinsic viscosity in tetralin solvent is 2.42 (dl /
g), melt flow rate 1.6 (g / 10 min), content of cold xylene soluble part at 20 ° C 0.6 wt%, boiling heptane soluble part content 2.9 wt%, boiling heptane insoluble part isotactic .Pentad fraction of 0.980, JP-A-60
No. 228504, using a highly crystalline polypropylene (A-4) produced by a slurry polymerization method as exemplified in JP-A-228504, modified in the same manner as in Example 6 to obtain a maleic anhydride addition amount of 0.15% by weight and a styrene addition amount of 0.07% by weight. , Melt flow rate 21 (g / 10
Min), a highly crystalline polypropylene modified with maleic anhydride / styrene was obtained.

 Table 2 shows the evaluation results.

Although ordinary modified polypropylene Example 6 also shows good physical properties, the use of the modified highly crystalline polypropylene increases the flexural modulus and provides favorable results in rigidity and heat resistance.

Examples 8 and 9, Comparative Examples 6 and 7 Modified polyolefin resins were produced using the following propylene block copolymer as a raw material. Melt flow rate
3.0 (g / 10min), 135 ℃, intrinsic viscosity in tetralin solvent
3.19 (dl / g), the ratio of the propylene homopolymer portion (hereinafter abbreviated as P part) which is the first segment polymerized in the first step is 74% by weight, and the second segment polymerized in the second step is 74% by weight. A copolymer of ethylene and propylene (hereinafter referred to as EP
Part is abbreviated to 26% by weight, and part P is 135%
℃, intrinsic viscosity in tetralin solvent is 1.64 (dl / g), 20 ℃
The content of the cold xylene-soluble portion of 1.6% by weight, the content of the boiling point heptane-soluble portion of 4.6% by weight, the isotactic pentad fraction of the boiling heptane-insoluble portion of 0.975, and the EP
Part is 135 ° C, the intrinsic viscosity in tetralin solvent is 7.58 (dl /
g), the ratio of ethylene / propylene in the EP part is 48/52
The highly crystalline propylene ethylene block copolymer (A-5) polymerized by the slurry polymerization method exemplified in JP-A-60-228504 was modified by the following method.

 For 100 parts by weight of raw material propylene block copolymer
1.0 part by weight of maleic anhydride, 0.5 part by weight of styrene,
1,3-bis (t-butyl peroxy) as a radical initiator
(Siisopropyl) benzene (manufactured by Sanken Kako Co., Ltd .; Sampe)
Roxcus -8 to TY1.3) in propylene homopolymer
0.6% by weight supported by weight and stabilizer
Irganoitus 1010 (Ciba-Geigy) 0.1 weight
Parts are evenly mixed with a Hensiel mixer.
With TEX 44 SS-30BW-2V twin screw extruder
At 220 ° C and an average residence time of 1.5 minutes.
Acid addition 0.33% by weight, styrene addition 0.14% by weight,
Maleic anhydride, styrene with a lithoflow rate of 10 (g / 10 minutes)
Len-modified high crystalline propylene ethylene block copolymer
Was manufactured.

Except that styrene was not used, it was produced in exactly the same manner as described above to obtain a maleic anhydride-modified high crystalline propylene ethylene block copolymer having a maleic anhydride addition of 0.20% and a melt flow rate of 39 (g / 10 minutes). Was.

A modified polyolefin resin composition was produced using the following propylene ethylene block copolymer (A-6) as a raw material. Melt flow rate is 1.3 (g / 10 min), 135 ° C, intrinsic viscosity in tetralin solvent is 2.59 (dl / g), homopolymer part of propylene which is the first segment polymerized in the first step (hereinafter P part) Abbreviated as 69% by weight, the second
The proportion of a copolymer of ethylene and propylene (hereinafter abbreviated as “EP part”) as the second segment polymerized in the step is 31% by weight, and the P part has an intrinsic viscosity of 135 ° C. and a tetralin solvent of 2.16 ( dl / g), content of cold xylene soluble part at 20 ° C is 1.0% by weight, content of boiling heptane soluble part is 4.4% by weight, isotactic pentad fraction of boiling heptane insoluble part is 0.975, EP Part is 135 ° C., the intrinsic viscosity in a tetralin solvent is 3.55 (dl / g), and the ethylene / EP in the EP part is
JP-A-62-287, in which the proportion of propylene is 27/73% by weight.
A highly crystalline propylene ethylene block copolymer (A-6) polymerized by a gas phase polymerization method exemplified in No. 917 is modified in the same manner as in Example 8 to obtain a maleic anhydride addition amount of 0.37% by weight and a styrene addition amount of 0.16% by weight. %, Melt flow rate 29
(G / 10 minutes) to produce a maleic anhydride / styrene modified high crystalline propylene ethylene block copolymer.

Except that styrene was not used, a maleic anhydride-modified high-crystalline propylene ethylene block copolymer having a maleic anhydride addition of 0.22% and a melt flow rate of 35 (g / 10 minutes) was obtained in exactly the same manner as described above. Was.

Comparative Examples 8 to 9 Modified polyolefin resins were produced by the following methods. The same raw materials as those used in Example 7 were used for the highly crystalline polypropylene and other raw materials, and the amounts of maleic anhydride, styrene, radical initiator and stabilizer were blended in the proportions shown in Table 2 and A modified polypropylene was produced in the same manner.

 Table 2 shows the results of these evaluations.

Example 10 A modified polyolefin resin composition was produced using the following propylene ethylene block copolymer (A-7) as a raw material. Melt flow rate is 0.1 (g / 10 min), 135 ° C, intrinsic viscosity in tetralin solvent is 3.0 (dl / g), homopolymer part of propylene which is the first segment polymerized in the first step (hereinafter referred to as P part) 23% by weight, the second
The ratio of the non-polymer of ethylene and propylene as the second segment polymerized in the step (hereinafter abbreviated as “EP part”) is 77% by weight, and the P part has an intrinsic viscosity of 135 ° C. and a tetralin solvent of 2.00 ( dl / g), the content of the cold xylene soluble part at 20 ° C is 2.8% by weight, the content of the boiling heptane soluble part is 6.4% by weight, the isotactic pentad fraction of the boiling heptane insoluble part is 0.960, EP Part is 135 ° C., intrinsic viscosity in tetralin solvent is 3.30 (dl / g), ethylene / EP in EP part
Japanese Patent Application No. 62-256 wherein the proportion of propylene is 20/80% by weight.
No. 015, a propylene ethylene block copolymer (A-7) polymerized by a gas phase polymerization method was modified in the same manner as in Example 8 to obtain a maleic anhydride addition amount of 0.67% by weight, styrene addition amount of 0.29% by weight, Flow rate 0.1 (g / 10
), A maleic anhydride / styrene-modified propylene ethylene block copolymer was produced.

 Table 3 shows the evaluation results.

Example 11, Comparative Example 11 A polyolefin resin composition of Example 11 was produced in exactly the same manner as in Example 7, except that glycidyl methacrylate (B-1) was used instead of maleic anhydride.

Further, a polyolefin resin composition of Comparative Example 11 was produced in the same manner as in Example 11 except that styrene was not used.

 Table 3 shows the evaluation results.

The modified polyolefin resin of this example was dissolved in heated xylene, precipitated with acetone, and purified.The IR spectrum showed the characteristic absorption attributed to styrene, so styrene was converted to polyolefin resin in the same manner as maleic anhydride. It is considered that graft copolymerization was performed.

Further, the modified polyolefin resin of this example had a better hue than the modified polyolefin resin of the comparative example, and the effect of reducing coloring by coexisting ethylene was also recognized.

[Effects of the Invention] As described above, the modified polyolefin resin obtained by the production method of the present invention has a large amount of unsaturated carboxylic acid or a derivative thereof or an unsaturated epoxy monomer, and has a high flow rate before and after graft modification. The modified polyolefin resin, which has a small change in properties, has excellent mechanical strength, and is improved in hue by being graft-modified with an unsaturated aromatic monomer, and is provided by the present invention. Can be.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication C08F 220: 32 222: 06) (72) Inventor Kentaro Yamaguchi 5-1 Anesaki Beach, Ichihara-shi, Chiba Sumitomo Inside Chemical Industry Co., Ltd. (72) Inventor Kouji Tsuji 5-1 Anesaki Kaigan, Ichihara-shi, Chiba Prefecture Inside Sumitomo Chemical Co., Ltd. (56) References JP-A-63-268712 (JP, A) JP-A-51-7719 (JP, B1) JP 45-33905 (JP, B1) European publication 225186 (EP, A1) West German publication 2023154 (DE, A)

Claims (8)

(57) [Claims] (1) at least one compound selected from the group consisting of 100 parts by weight of a polyolefin resin (A) having a melt flow rate of 0.05 to 60 g / 10 min, an unsaturated carboxylic acid, a derivative thereof and an unsaturated epoxy monomer; B) 0.1 to 5 parts by weight, 0.1 to 5 parts by weight of an unsaturated aromatic monomer (C) and 0.01 to 2 parts by weight of a radical initiator (D), and (B) / (C)
Wherein the molar ratio of (C) is 0.1 mol or more and less than 1 mol with respect to 1 mol of (B). 2. The modified polyolefin resin composition according to claim 1, wherein the unsaturated carboxylic acid and its derivative (B) are maleic anhydride. 3. The modified polyolefin resin composition according to claim 1, wherein the unsaturated epoxy monomer (B) is glycidyl acrylate or glycidyl methacrylate. 4. The modified polyolefin resin composition according to claim 1, wherein the unsaturated aromatic monomer (C) is styrene. 5. The modified polyolefin resin composition according to claim 1, wherein the polyolefin resin (A) is a crystalline propylene polymer. 6. The modified polyolefin resin composition according to claim 1, wherein the melt flow rate of the modified polyolefin resin is from 0.1 to 100 g / 10 minutes. 7. The crystalline polypropylene polymer is a copolymer whose propylene homopolymer portion has a boiling heptane-insoluble portion having an isotactic pentad fraction of 0.970.
6. The modified polyolefin resin composition according to claim 5, wherein the content of the boiling heptane-insoluble portion is 5.0% by weight or less based on the homopolymer portion. 8. A propylene-ethylene block copolymer produced by a gas phase polymerization method, wherein the crystalline polypropylene polymer is a copolymer and the amount of the copolymer portion is 20 to 80% by weight. 6. The modified polyolefin resin composition according to claim 5, wherein