JP2022103043A - Oxazoline-modified polypropylene - Google Patents

Abstract

To provide a substance useful for improving mechanical strength of a fiber-reinforced polypropylene composition.SOLUTION: There is provided oxazoline-modified polypropylene satisfying the following requirements (1), (1-a), and (2): (1) the oxazoline-modified polypropylene has an oxazoline group; (1-a) the content of the oxazoline group in 1 g of the oxazoline-modified polypropylene is 0.1×10-2 to 100×10-2 mmol/g; and (2) the melt mass flow rate of the oxazoline-modified polypropylene is 0.01 to 300 g/10 min.SELECTED DRAWING: None

Description

The present invention relates to an oxazoline-modified polypropylene, a method for producing the same, and a polypropylene composition containing the oxazoline-modified polypropylene.

A member made of a polypropylene composition is used for an automobile member, and a member made of a composition obtained by kneading a filler with polypropylene is used in order to improve the mechanical strength of the member. Carbon fiber, glass fiber and talc are used as the filler. Further, when kneading polypropylene and a filler, a coupling agent or polypropylene modified with a specific polar group is used.
For example, in International Publication No. 2016/188886 (Patent Document 1), tensile elasticity and tensile strength are improved by a composition containing polypropylene, carbon fibers, and polypropylene grafted with maleic anhydride as a coupling agent.

International Publication No. 2016/188886

The present invention is to solve the problem of providing a useful substance for improving the mechanical strength of a fiber-reinforced polypropylene composition.

The present inventor 1) that modified polypropylene is beneficial for improving the mechanical strength of the fiber-reinforced polypropylene composition, 2) using oxazoline-modified polypropylene as the modified polypropylene, and 3) the oxazoline group in the oxazoline-modified polypropylene. The present invention has been found by paying attention to the content and 4) melt mass florate (MFR) of oxazoline-modified polypropylene.
In addition, the present inventor 5) melt-kneaded polypropylene, an organic peroxide, and maleic acid or maleic anhydride, and 6) obtained polypropylene, an organic peroxide, and maleic acid or The present invention has been found by paying attention to the fact that an oxazoline compound is added to a melt-kneaded product with maleic anhydride and melt-kneaded.

The present invention relates to, but is not limited to:
[Invention 1]
Oxazoline-modified polypropylene that meets the following requirements (1), (1-a), and (2):
(1) Oxazoline-modified polypropylene has an oxazoline group.
(1-a) The content of the oxazoline group in 1 g of oxazoline-modified polypropylene is 0.1 × 10 − ² to 100 × 10 − ² mmol / g, and (2) the melt mass flow rate of (2) oxazoline-modified polyprilopylene is 0. 0.01-300 g / 10 minutes.
[Invention 2]
Oxazoline-modified polypropylene produced by a method comprising the following steps:
-A step of melt-kneading polypropylene, an organic peroxide, and maleic acid or maleic anhydride, and-in a melt-kneaded product of the obtained polypropylene, an organic peroxide, and maleic acid or maleic anhydride. , A step of adding an oxazoline compound and melt-kneading.
[Invention 3]
A method for producing oxazoline-modified polypropylene, which comprises the following steps:
-A step of melt-kneading polypropylene, an organic peroxide, and maleic acid or maleic anhydride.
-A step of adding an oxazoline compound to a melt-kneaded product of the obtained polypropylene, an organic peroxide, and maleic acid or maleic anhydride, and melt-kneading the mixture.
[Invention 4]
Polypropylene composition containing the following (component 1):
(Component 1) Oxazoline-modified polypropylene that satisfies the following requirements (1), (1-a), and (2):
(1) Oxazoline-modified polypropylene has an oxazoline group.
(1-a) The content of the oxazoline group in 1 g of oxazoline-modified polypropylene is 0.1 × 10 − ² to 100 × 10 − ² mmol / g, and (2) the melt mass flow rate of (2) oxazoline-modified polyprilopylene is 0. 0.01-300 g / 10 minutes.
[Invention 5]
Polypropylene composition containing the following (component 1):
(Component 1) Oxazoline-modified polypropylene produced by a method comprising the following steps:
-A step of melt-kneading polypropylene, an organic peroxide, and maleic acid or maleic anhydride, and-in a melt-kneaded product of the obtained polypropylene, an organic peroxide, and maleic acid or maleic anhydride. The process of adding an oxazoline compound and melt-kneading.
[Invention 6]
(Component 1): The polypropylene composition according to the invention 4 or 5, which contains 1 to 20% by mass of the content and the following (Component 2) and (Component 3):
(Component 2) Polypropylene: Content 30 to 98% by mass, and (Component 3) At least one filler selected from the group consisting of carbon fiber, glass fiber and talc: Content 1 to 50% by mass.
[Invention 7]
(Component 3) The polypropylene composition according to any one of Inventions 4 to 6, which contains carbon fiber as a filler.

Since the oxazoline-modified polypropylene has the characteristics of the present invention, it has succeeded in improving the mechanical strength of the polypropylene composition containing the oxazoline-modified polypropylene and the filler and the molded product containing the composition.

Definitions All numbers disclosed herein are approximations, whether or not the word "about" or "generally" is used in connection with it. They may vary by 1 percent, 2 percent, 5 percent, or sometimes 10-20 percent. Whenever a range of numbers with a lower bound ^RL and an upper bound ^RU is disclosed, any number contained within the range is specifically disclosed. In particular, the following numbers within the scope are specifically disclosed. R ^{= RL +} k ^* (RU- ^RL ) (In the equation, k is a variable in the range of 1 percent to 100 percent that increases by 1 percent, i.e. k is 1 percent, 2 percent, 3 percent. 4 percent, 5 percent, ..., 50 percent, 51 percent, 52 percent, ..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent). In addition, any numerical range defined by the two R numbers described above is also specifically disclosed.

The description of "lower limit to upper limit" indicating a numerical range represents "lower limit or higher and lower limit or lower", and the description of "upper limit to lower limit" represents "lower limit or lower limit or higher limit". That is, these descriptions represent a numerical range including a lower limit and an upper limit.

Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

Oxazoline-modified polypropylene "Oxazoline-modified polypropylene" means polypropylene modified with an oxazoline compound and has an oxazoline group.
The oxazoline-modified polypropylene of the present invention satisfies the following requirements (1), (1-a), and (2):
(1) Oxazoline-modified polypropylene has an oxazoline group.
(1-a) The content of the oxazoline group in 1 g of oxazoline-modified polypropylene is 0.1 × 10 − ² to 100 × 10 − ² mmol / g, and (2) the melt mass flow rate of (2) oxazoline-modified polyprilopylene is 0. 0.01-300 g / 10 minutes.

The above-mentioned "oxazoline group" may mean the oxazoline group itself, or may mean a ring-opened oxazoline group. The oxazoline group may have a substituent.

As described above, the content of the oxazoline group in 1 g of the oxazoline-modified polypropylene is in the range of 0.1 × 10 − ² to 100 × 10 − ² mmol / g, and the lower limit of the range is preferably 1.0 × 10 ⁻ . It is ² mmol / g, more preferably 2.5 × 10 − ² mmol / g, and the upper limit of the range is preferably 25 × 10 − ² mmol / g, more preferably 17 × 10 − ² mmol / g. be. The range is preferably 1.0 × 10 ⁻² to 25 × 10 − ² mmol / g, and more preferably 2.5 × 10 − ² to 17 × 10 − ² mmol / g.

The content of oxazoline groups in 1 g of oxazoline-modified polypropylene is determined by infrared (IR) spectroscopy. For example, when oxazoline-modified polypropylene is produced by modifying maleic anhydride-modified polypropylene with an oxazoline compound, the content is determined by the method described in Examples.

As described above, the melt mass flow rate of the oxazoline-modified polyprilopylene is in the range of 0.01 to 300 g / 10 minutes, preferably in the range of 0.1 to 300 g / 10 minutes, and more preferably in the range of 0.8 to 180 g. It is in the range of / 10 minutes.

The above-mentioned "melt mass flow rate" means a melt mass flow rate measured at a measurement temperature of 230 ° C. and a load of 2.16 kg according to the method specified in JIS K 7210.

Method for Producing Oxazoline-Modified Polypropylene The oxazoline-modified polypropylene of the present invention may be produced by a method comprising the following steps:
-A step of melt-kneading polypropylene, an organic peroxide, and maleic acid or maleic anhydride, and-in a melt-kneaded product of the obtained polypropylene, an organic peroxide, and maleic acid or maleic anhydride. The process of adding an oxazoline compound and melt-kneading.
Further, at the time of producing the oxazoline-modified polypropylene of the present invention, polypropylene and / or at least one filler may be contained.

Ｒ^１は二価の有機基を表し、例えば、
メチレン基（－ＣＨ_２－）、エチレン基（－ＣＨ_２ＣＨ_２－）、プロピレン基（－ＣＨ_２ＣＨ_２ＣＨ_２－）などのアルキレン基、
エテニレン基（－ＣＨ＝ＣＨ－）、プロペニレン基（－ＣＨ＝ＣＨ－ＣＨ_２－）などのアルケニレン基、
１，２－フェニレン基、１，３－フェニレン基、１，４－フェニレン基などのフェニレン基、

等が挙げられる。 Oxazoline compound Examples of the oxazoline compound include a compound of formula 1 having two oxazoline groups.

R ¹ represents a divalent organic group, for example,
An alkylene group such as a methylene group (-CH _2- ), an ethylene group (-CH ₂ CH _2- ), and a propylene group (-CH ₂ CH ₂ CH _2- ),
Alkenylene groups such as ethenylene group (-CH = CH-) and propenylene group (-CH = CH-CH _2- ),
Phenylene groups such as 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group,

And so on.

The kneading method is not particularly limited, but for example, polypropylene, an organic peroxide, maleic acid or maleic anhydride, and an oxazoline compound are simultaneously or sequentially used, for example, a henschel mixer, a V-type blender, or a tumbler. Examples thereof include a method of supplying and kneading to a blender, a ribbon blender, or the like, and then melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, or the like. Among these, it is preferable to use an apparatus having excellent kneading performance such as a single-screw extruder, a multi-screw extruder, a kneader, and a Banbury mixer because each component is more uniformly dispersed.

As a supply of polypropylene, organic peroxide, maleic acid or maleic anhydride, and an oxazoline compound to an extruder,
1) The extruder is equipped with three hoppers, polypropylene is supplied from the first hopper along the resin flow, and organic peroxide and maleic acid or maleic anhydride are supplied together from the second hopper. , A method of supplying an oxazoline compound from a third hopper,
2) The extruder is equipped with two hoppers, polypropylene and organic peroxide, maleic acid or maleic anhydride are supplied together from the first hopper along the resin flow, and the oxazoline compound is supplied from the second hopper. How to supply,
3) The extruder is equipped with two hoppers, polypropylene and organic peroxide, and maleic acid or maleic anhydride are supplied together from the first hopper along the resin flow, and the organic peroxide is supplied from the second hopper. A method of supplying an oxide, an oxazoline compound and maleic acid or maleic anhydride together,
It is also possible to adopt any of the above methods.

Regarding the temperature at which each of the above components is melt-kneaded, it is preferable to melt-knead each component at the highest melting point or higher of the melting points of the components to be mixed. Specifically, melt kneading is carried out in the range of preferably 120 to 300 ° C, more preferably 180 to 280 ° C, and even more preferably 200 ° C to 270 ° C.

Polypropylene composition The polypropylene composition of the present invention is
It contains the oxazoline-modified polypropylene of the present invention (sometimes referred to as "component 1").
The polypropylene compositions of the present invention are polypropylene (sometimes referred to as "component 2"), fillers (sometimes referred to as "component 3"), and other modified polypropylenes (sometimes referred to as "component 4"). It may contain at least one component selected from the group consisting of.
In one aspect, the polypropylene composition of the present invention contains "component 2" and "component 3". In one embodiment, "component 4" may be further contained.

Polypropylene (component 2)
Examples of polypropylene (component 2) include:
Propylene homopolymer,
Propylene-ethylene random copolymer,
Propylene-α-olefin random copolymer,
Propylene-ethylene-α-olefin copolymer,
Copolymerization of propylene homopolymer component or copolymer component mainly composed of propylene (hereinafter, also referred to as polymer component I), at least one of the monomers selected from ethylene and α-olefin, and propylene. A heterophasic propylene polymerization material composed of a copolymer (hereinafter, also referred to as polymer component II) obtained in the above.
These polypropylenes may be used alone or in combination of at least two.

Examples of the α-olefin used in the production of component 2 include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, and more preferably 1-decene. Examples include butene, 1-hexene and 1-octene.

Examples of the propylene-α-olefin random copolymer include a propylene-1-butene random copolymer, a propylene-1-hexene random copolymer, and a propylene-1-octene random copolymer.

Examples of the propylene-ethylene-α-olefin copolymer include a propylene-ethylene-1-butene copolymer, a propylene-ethylene-1-hexene copolymer, a propylene-ethylene-1-octene copolymer and the like. Can be mentioned.

The content of ethylene or α-olefin contained in the propylene-ethylene random copolymer, the propylene-α-olefin random copolymer, and the propylene-ethylene-α-olefin copolymer is usually 0.01 to 30 weight by weight. %, Preferably 0.1 to 20% by weight. However, the total amount of the copolymer is 100% by weight.

When the polymer component I of the heterophasic propylene polymerization material is a copolymer component mainly composed of propylene, the polymer component I is selected from ethylene and an α-olefin having 4 to 12 carbon atoms. At least one olefin is contained, and the content thereof is usually 0.01 to 30% by weight. However, the total amount of the polymer component I is 100% by weight.

When the polymer component I is a copolymer component mainly composed of propylene, for example, a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, a propylene-1-hexene copolymer component, or the like may be used. Can be mentioned.

Examples of the polymer component II of the heterophasic propylene polymerization material include a propylene-ethylene copolymer component, a propylene-ethylene-1-butene copolymer component, and a propylene-ethylene-1-hexene copolymer component. Examples thereof include a propylene-ethylene-1-octene copolymer component, a propylene-1-butene copolymer component, a propylene-1-hexene copolymer component, a propylene-1-octene copolymer component and the like.

The content of at least one olefin selected from ethylene and α-olefin having 4 to 12 carbon atoms contained in the polymer component II is usually 1 to 80% by weight, preferably 20 to 70% by weight. %, More preferably 30-60% by weight. However, the total amount of the polymer component II is 100% by weight.

The content of the polymer component II contained in the heterophasic propylene polymerization material is usually 1 to 70% by weight, preferably 5 to 50% by weight, and more preferably 10 to 40% by weight. However, the total amount of the heterophasic propylene polymerized material is 100% by weight.

Examples of the heterophasic propylene polymerization material composed of the polymer component I and the polymer component II include:
(Propene)-(Propene-Ethylene) Polymerizing Material,
(Propene)-(Propene-Ethylene-1-Butene) Polymerizing Material,
(Propene)-(Propene-Ethylene-1-Hexene) Polymerizing Material,
(Propene)-(Propene-1-butene) Polymerizing Material,
(Propene)-(Propene-1-hexene) Polymerizing material,
(Propene-Ethylene)-(Propene-Ethylene) Polymerizing Material,
(Propene-Ethylene)-(Propene-Ethylene-1-Butene) Polymerizing Material,
(Propene-Ethylene)-(Propene-Ethylene-1-Hexene) Polymerizing Material,
(Propene-Ethylene)-(Propene-1-Butene) Polymerizing Material,
(Propene-Ethylene)-(Propene-1-Hexene) Polymerizing Material,
(Propene-1-butene)-(Propene-Ethylene) Polymerized Material,
(Propene-1-Butene)-(Propene-Ethylene-1-Butene) Polymerized Material,
(Propene-1-Butene)-(Propene-Ethylene-1-Hexene) Polymerizing Material,
(Propene-1-Butene)-(Propene-1-Butene) Polymerized Material,
(Propene-1-butene)-(Propene-1-hexene) Polymerization material.

Filler (ingredient 3)
Examples of the filler (component 3) include the following.

Carbon fiber (component 3-1)
As the carbon fiber (component 3-1), various conventionally known carbon fibers can be used. Specific examples thereof include polyacrylic nitrile-based, rayon-based, pitch-based, polyvinyl alcohol-based, regenerated cellulose-based, and pitch-based carbon fibers manufactured from mesophase pitch.
Further, as the carbon fiber (component 3-1), recycled carbon fiber can be used. Specifically, it is possible to use recycled carbon fiber that is reused by firing carbon fiber used for aircraft and the like.

The fiber diameter of the component 3-1 is not particularly limited, but in order to strengthen the fiber, improve the productivity of the reinforced fiber bundle, reduce the trouble of connecting the fiber bundles in the continuous production of pellets, and improve the productivity. It is preferably 3 μm or more, more preferably 8 μm or more. Further, in order to improve the aspect ratio of the fiber when the pellet length is fixed, the fiber diameter is preferably 30 μm or less, more preferably 20 μm or less.

The aspect ratio of the component 3-1 is not particularly limited, but 5 or more is preferable for strengthening the fiber. Further, in order to improve the moldability, the aspect ratio is preferably 6000 or less. The aspect ratio of component 3-1 can be obtained from the average fiber diameter and the average fiber length by (average fiber length) ÷ (average fiber diameter).

As a raw material for component 3-1 a continuous fiber bundle is used, which is commercially available as tow. Usually, the average fiber diameter is 3 to 30 μm, and the number of filaments focused is 500 to 24,000. The average fiber diameter is preferably 4 to 10 μm, and the number of focused fibers is 6,000 to 15,000.

Alternatively, chopped strands can be used as the component 3-1. The length of the chopped strand is usually 1 to 20 mm, and the diameter of the fiber is about 3 to 30 μm, preferably 4 to 10 μm.

The fiber length of the component 3-1 constituting the polypropylene composition of the present invention is usually 0.05 to 200 mm, preferably 0.2 to 50 mm, and more preferably 4 to 20 mm.

The average aspect ratio (fiber length / fiber diameter) is usually 5 to 6000, preferably 10 to 3000, and more preferably 15 to 2000.

The surface of component 3-1 may be surface-treated by oxidative etching or coating. Oxidative etching treatment includes air oxidation treatment, oxygen treatment, oxidation gas treatment, ozone treatment, corona treatment, flame treatment, (atmospheric pressure) plasma treatment, and oxidizing liquid (sulfuric acid, hypochlorite alkali metal salt). An aqueous solution, potassium dichromate-sulfuric acid, potassium permanganate-sulfuric acid) and the like can be mentioned. Examples of the substance that coats the carbon fiber include carbon, silicon carbide, silicon dioxide, silicon, plasma monomer, ferrocene, iron trichloride, and the like.

Further, if necessary, a sizing agent such as urethane-based, olefin-based (polypropylene or the like), acrylic-based, nylon-based, butadiene-based and epoxy-based (including special epoxy), polyester-based sizing agent may be used.

Carbon fiber surface The carbon fiber (component 3-1) which may be contained in the polypropylene composition of the present invention has a CO bond, a C = O bond, on the surface thereof so as to increase the mechanical strength of the polypropylene composition. OC = O bonds, CC bonds, and CN bonds may be included in predetermined amounts. In either of the above and the following embodiments, the "CO bond" does not include the CO bond in the "OC = O bond", and the "C = O bond" is the "OC = O bond". Does not include the C = O bond in.

In one embodiment, component 3-1 comprises a C—O bond, a C = O bond, an OC = O bond, a CC bond and a CN bond, a C—O bond, a C = O bond, O. The total spectral area of each of -C = O bond, CC bond and CN bond is 100%, and the content of CO bond is 1 to 24%, preferably 3 to 20%, more preferably. It is in the range of 5 to 15%.

In one embodiment, component 3-1 comprises a C—O bond, a C = O bond, an OC = O bond, a CC bond and a CN bond, a C—O bond, a C = O bond, O. The total content of each of C = O bond and OC = O bond is 4 to 15%, where the total spectral area of each of -C = O bond, CC bond and CN bond is 100%. It is preferably in the range of 5 to 12%, more preferably 5 to 8%.

In one embodiment, component 3-1 comprises a C—O bond, a C = O bond, an OC = O bond, a CC bond and a CN bond, a C—O bond, a C = O bond, O. The total spectral area of each of -C = O bond, CC bond and CN bond is 100%, and the content of CO bond is 5 to 24%, preferably 3 to 20%, more preferably. It is in the range of 5 to 15%, and the total content of each of C = O bond and OC = O bond is 4 to 15%, preferably 5 to 12%, and more preferably 5 to 8%. It is a range.

Calculation Method of Bonding Component on Carbon Fiber Surface Each bond amount on the carbon fiber surface can be measured by an X-ray photoelectron spectroscopy device. If necessary, pretreatment such as removal of unreacted sizing agent may be performed before measurement.
As the excitation source, characteristic X-rays such as monochromatic Al Kα rays (1486.6 eV) and Mg Kα rays (1253.6 eV) can be used.
The obtained spectrum can be waveform-separated into each bond by a known method.
For example, the amount of each bonded component on the surface of the carbon fiber can be calculated by the method described in Examples.

Glass fiber (ingredient 3-2)
The polypropylene composition of the present invention may contain glass fiber (component 3-2).
The glass fiber used is not particularly limited. Examples of the type of glass used for the fiber include E glass, C glass, A glass, S glass and the like, and E glass is preferable. The method for producing the glass fiber is not particularly limited, and the glass fiber is produced by various known production methods.
In addition, two or more types of glass fibers can be used in combination.

The fiber diameter of the glass fiber is not particularly limited, but is usually 3 to 25 μm. The fiber length of the glass fiber is not particularly limited, but is usually 0.1 to 20 mm.

The glass fiber may be treated with a sizing agent and / or a surface treating agent. The glass fibers can be bound by the treatment with the sizing agent.

The glass fiber is preferably surface-treated with a surface-treating agent from the viewpoint of improving the dispersibility with respect to polypropylene (component 2). Examples of surface treatment agents include organic silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling agents, silicone compounds, higher fatty acids, fatty acid metal salts, and fatty acid esters.

Examples of organic silane coupling agents include vinyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane. Can be mentioned.

Examples of titanate coupling agents include isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, and isopropyltri (N-aminoethyl) titanate.

Examples of the aluminate coupling agent include acetalkoxyaluminum diisopropyrate.

Examples of zirconeate coupling agents include tetra (2,2-diallyloxymethyl) butyl, di (tridecylic) phosphite zirconate, and neopentyl (diallyl) oxytrineoneodecanoyl zirconeate.

Examples of the silicone compound include silicone oil and silicone resin.

Examples of higher fatty acids include oleic acid, capric acid, lauric acid, palmitic acid, stearic acid, montanic acid, linoleic acid, loginic acid, linolenic acid, undecanoic acid, and undecenoic acid.

Examples of higher fatty acid metal salts include sodium salts, lithium salts, calcium salts, magnesium salts, zinc salts, and aluminum salts of fatty acids having 9 to 30 carbon atoms (eg, stearic acid, montanic acid). .. Of these, calcium stearate, aluminum stearate, calcium montanate, and sodium montanate are preferred.

Examples of fatty acid esters include esters of fatty acids having 9 to 30 carbon atoms, and more specifically, polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, alpha sulfo fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and the like. Examples include sorbitan fatty acid esters, polyethylene fatty acid esters, and sucrose fatty acid esters.

The amount of the surface treatment agent used is not particularly limited. The amount of the surface treatment agent used can be preferably 0.01 parts by weight to 5 parts by weight, more preferably 0.1 parts by weight to 3 parts by weight, based on 100 parts by weight of the glass fiber.

Examples of the sizing agent include an epoxy-based sizing agent, an aromatic urethane-based sizing agent, an aliphatic urethane-based sizing agent, an acrylic-based sizing agent, and a maleic anhydride-modified polyolefin-based sizing agent.

As the sizing agent, a converging agent that melts at a temperature in the manufacturing process of the polypropylene composition is preferable, and a converging agent that melts at 200 ° C. or lower is more preferable.

As the glass fiber, a so-called chopped strand obtained by cutting a glass strand may be used.

As the glass fiber, a resin pellet containing glass fiber (glass fiber-containing resin pellet) may be used. In such a glass fiber-containing pellet, the length of the glass fiber (fiber length) is usually substantially the same as the length of the glass fiber-containing resin pellet in the extrusion direction.

The glass fiber-containing resin pellets can be produced by a conventionally known arbitrary suitable production method using a conventionally known arbitrary suitable resin selected in consideration of the composition of the polypropylene composition to be produced.

The glass fiber-containing resin pellets can be produced, for example, by a pultrusion method. In the pultrusion method, a bundle of glass fibers is impregnated into a resin by melt-extruding a conventionally known arbitrary suitable resin which is a material for glass fiber-containing resin pellets from an extruder while drawing out a plurality of continuous glass fibers. This is a method in which a bundle of glass fibers impregnated with a resin is cooled, cut with a pelletizer, and a plurality of bundles of glass fibers are integrated.

The content of glass fiber in the glass fiber-containing resin pellet is preferably 50 to 99.9% by mass.

As the glass fiber, a glass fiber having a water-soluble base component amount of 0.1 mmоl / g or less and a water-soluble weak acid salt amount of 0.1 mmоl / g or less can be selected and used from commercially available products. Specific examples of commercially available products include "CS-249A-10C" (trade name, manufactured by Owens Corning Co., Ltd.), "ECS10-03-508H" (trade name, manufactured by Giant Stone JAPAN Co., Ltd.), and "T480H". (Product sheet, manufactured by Nippon Electric Glass Co., Ltd.).

Talc (ingredient 3-3)
The propylene composition of the present invention may contain talc (component 3-3), which is a silicate mineral.

The propylene composition of the present invention may contain only one type of talc, or may contain two or more types of talc.

The shape of the talc may be plate-like, needle-like, or fibrous. From the viewpoint of rigidity, impact resistance and dimensional stability of the molded body, plate-shaped talc is more preferable.

The average particle size D50 [L] of talc is preferably 20.0 μm or less, and more preferably 15.0 μm or less, from the viewpoint of rigidity, impact resistance and dimensional stability of the molded product. The average particle size D50 [L] of talc may be 2.0 μm or more, and may be 4.0 μm or more. The average particle size D50 [L] of the component C is preferably 2.0 to 20.0 μm, more preferably 4.0 to 15.0 μm.
The average particle size D50 [S] of talc is preferably 5.0 μm or less, and more preferably 3.0 μm or less, from the viewpoint of rigidity, impact resistance and dimensional stability of the molded product.
The average particle size D50 [S] of the component C may be 0.5 μm or more, or 1.0 μm or more. The average particle size D50 [S] of the component C is preferably 0.5 to 5.0 μm, more preferably 1.0 to 3.0 μm.
The ratio (D50 [L] / D50 [S]) of the average particle diameter D50 [L] of the talc to the average particle diameter D50 [S] is 1.5 or more from the viewpoint of the rigidity of the molded body and the dimensional stability. It may be 2.5 or more. D50 [L] / D50 [S] may be 10 or less, or may be 8 or less. D50 [L] / D50 [S] may be 1.5 to 10, 1.5 to 8, 2.5 to 10, and 2.5 to 8. There may be.

The "average particle size D50 [L]" is determined based on the volume-based particle size distribution measurement data measured by the laser diffraction method according to the method specified in JIS R1629, and the particle size is determined. In the distribution measurement data, it means the particle size (particle size equivalent to 50%) when the cumulative number of particles from the side with the smaller particle size reaches 50%. The particle size defined in this way is generally referred to as "50% equivalent particle size" and is represented by "D50".
In the present specification, the "average particle size D50 [S]" is determined based on the volume-based particle size distribution measurement data measured by the centrifugal sedimentation method according to the method specified in JIS R1619. In the particle size distribution measurement data, it means the particle size (particle size equivalent to 50%) when the cumulative number of particles from the side with the smaller particle size reaches 50%.

Other modified polypropylene (component 4)
The propylene composition of the present invention may further contain other modified polypropylene other than the oxazoline-modified polypropylene (component 1).
The other modified polypropylene (component 4) is not particularly limited as long as it is modified to impart polarity, but for example, polypropylene modified with (maleic) carboxylic acid, epoxy, isocyanate, carbodiimide or the like, and component 1 Examples thereof include oxazoline-modified polypropylene which does not satisfy the conditions, and preferred examples include maleic anhydride-modified polypropylene, carbodiimide-modified polypropylene, and epoxy-modified polypropylene.

Maleic anhydride-modified polypropylene (polypropylene MM)
Examples of the maleic anhydride-modified polypropylene (sometimes referred to as polypropylene MM) as the component 4 include the following 1 to 4:
1. 1. Modified polypropylene obtained by graft-polymerizing an unsaturated carboxylic acid and / or a derivative thereof to a homopolymer of propylene,
2. 2. Modified polypropylene obtained by graft-polymerizing an unsaturated carboxylic acid and / or a derivative thereof to a propylene copolymer composed of at least two kinds of monomers.
3. 3. Modified propylene obtained by graft-polymerizing an unsaturated carboxylic acid and / or a derivative thereof to a block copolymer obtained by homopolymerizing propylene and then copolymerizing at least two kinds of olefins.
4. Modified polypropylene obtained by random copolymerization or block copolymerization of propylene, optionally at least one olefin, an unsaturated carboxylic acid and / or a derivative thereof.

For the production of polypropylene MM, for example, "Practical Polymer Alloy Design" (written by Fumio Ide, Kogyo Chosakai (1996)), Prog. Polym. Sci. , 24, 81-142 (1999), JP-A-2002-308497, and the like, and various other methods can be used. That is, any of a solution method, a bulk method, and a melt-kneading method may be used. Moreover, you may use these methods in combination.

Examples of unsaturated carboxylic acids used in the production of polypropylene MM include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid and the like. Examples of the unsaturated carboxylic acid derivative include acid anhydrides, ester compounds, amide compounds, imide compounds, metal salts and the like derived from the unsaturated carboxylic acid, and specific examples thereof include maleic anhydride. , Anhydrous itaconic acid, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, monoethyl maleic acid ester, diethyl maleic acid, fumaric acid Examples thereof include monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, maleimide, N-butylmaleimide, and sodium methacrylate. Further, a compound such as citric acid or malic acid which is dehydrated in the step of graft polymerization to polypropylene to generate an unsaturated carboxylic acid may be used.
The unsaturated carboxylic acid and / or its derivative is preferably acrylic acid, a glycidyl ester of methacrylic acid, or maleic anhydride.

Examples of the organic peroxide used for producing polypropylene MM include disetylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, and bis (4-tert-. Butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, tert-butylperoxyisopropylcarbonate, dimyristylperoxycarbonate, 1,1,3,3-tetramethylbutylneodecanoate, α-cumylperoxy Neodecanoate, tert-butylperoxy Neodecanoate, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane, 1,1-bis (tert-butylperoxy) cyclododecane, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, 2 , 5-Dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxyacetate, 2,2-bis (tert-butylperoxy) butene, tert-butylperoxybenzoate, n-butyl-4 , 4-bis (tert-butylperoxy) valerate, di-tert-butylperoxyisophthalate, dicumyl peroxide, α-α'-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5 -Dimethyl-2,5-di (tert-butylperoxy) hexane, 1,3-bis (tert-butylperoxydiisopropyl) benzene, tert-butylcumyl peroxide, di-tert-butyl peroxide, p-menthane Hydroperoxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin-3, and bis (tert-butylperoxyisopropyl) benzene include disetylperoxydicarbonate and 1, 3-Bis (tert-butylperoxyisopropyl) benzene is preferred.

Preferred as polypropylene MM,
(1) Modified polypropylene obtained by graft-polymerizing maleic anhydride on polypropylene whose main constituent unit is a propylene monomer and optionally an ethylene monomer.
(2) Modified polypropylene obtained by copolymerizing a propylene monomer, an olefin containing an ethylene monomer as a main component, and a methacrylic acid glycidyl ester or maleic anhydride.
Can be mentioned.

Further, from the viewpoint of mechanical strength such as impact strength, fatigue characteristics, and rigidity of the fiber-reinforced resin molded product, polypropylene MM preferably contains a polymerization monomer unit derived from an unsaturated carboxylic acid and / or a derivative thereof. Maleic anhydride-modified polypropylene containing 01 to 10% by weight. In particular, in the case of polypropylene MM obtained by random copolymerization or block copolymerization using an unsaturated carboxylic acid and / or a derivative thereof, a polymerization monomer unit derived from the unsaturated carboxylic acid and / or a derivative thereof. The content is preferably 3 to 10% by weight, and in the case of polypropylene MM obtained by graft polymerization, the content of the polymerization monomer unit derived from the unsaturated carboxylic acid and / or its derivative is 0.01 to 10% by weight. % Is preferable.

Content The content of oxazoline-modified polypropylene (component 1) contained in the polypropylene composition of the present invention is not particularly limited, but is preferably 1 to 20% by mass, with the total mass of the polypropylene composition of the present invention being 100% by mass. %, More preferably 3 to 20% by weight, still more preferably 5 to 20% by weight.
The content of polypropylene (component 2) that can be contained in the polypropylene composition of the present invention is not particularly limited, but is preferably in the range of 30 to 98% by mass, with the total mass of the polypropylene composition of the present invention being 100% by mass. Yes, more preferably in the range of 50-90% by weight.
The content of the filler (component 3) that can be contained in the polypropylene composition of the present invention is not particularly limited, but is preferably in the range of 1 to 50% by mass, with the total mass of the polypropylene composition of the present invention being 100% by mass. , More preferably in the range of 3 to 40% by weight, still more preferably in the range of 15 to 30% by weight.
The content of other modified polypropylene (component 4) that can be contained in the polypropylene composition of the present invention is not particularly limited.

In one embodiment, the polypropylene composition of the present invention contains the following (component 1):
(Component 1) Oxazoline-modified polypropylene that satisfies the following requirements (1), (1-a), and (2):
(1) Oxazoline-modified polypropylene has an oxazoline group.
(1-a) The content of the oxazoline group in 1 g of oxazoline-modified polypropylene is 0.1 × 10 − ² to 100 × 10 − ² mmol / g, and (2) the melt mass flow rate of (2) oxazoline-modified polyprilopylene is 0. 0.01-300 g / 10 minutes.

In one embodiment, the polypropylene composition of the present invention contains the following (component 1):
(Component 1) Oxazoline-modified polypropylene that satisfies the following requirements (1), (1-a), and (2): Content 1 to 20% by mass:
(1) Oxazoline-modified polypropylene has an oxazoline group.
(1-a) The content of the oxazoline group in 1 g of oxazoline-modified polypropylene is 0.1 × 10 − ² to 100 × 10 − ² mmol / g, and (2) the melt mass flow rate of (2) oxazoline-modified polyprilopylene is 0. 0.01-300 g / 10 minutes.

In one embodiment, the polypropylene composition of the present invention contains the following (component 1), (component 2) and (component 3):
(Component 1) Oxazoline-modified polypropylene that satisfies the following requirements (1), (1-a), and (2): Content 1 to 20% by mass:
(1) Oxazoline-modified polypropylene has an oxazoline group.
(1-a) The content of the oxazoline group in 1 g of oxazoline-modified polypropylene is 0.1 × 10 − ² to 100 × 10 − ² mmol / g, and (2) the melt mass flow rate of (2) oxazoline-modified polyprilopylene is 0. .01-300g / 10 minutes,
(Component 2) Polypropylene: Content 30 to 98% by mass, and (Component 3) At least one filler selected from the group consisting of carbon fiber, glass fiber and talc: Content 1 to 50% by mass.

In one embodiment, the polypropylene composition of the present invention contains the following (component 1):
(Component 1) Oxazoline-modified polypropylene produced by a method comprising the following steps:
-A step of melt-kneading polypropylene, an organic peroxide, and maleic acid or maleic anhydride, and-in a melt-kneaded product of the obtained polypropylene, an organic peroxide, and maleic acid or maleic anhydride. Step of adding oxazoline compound and melt-kneading,

In one embodiment, the polypropylene composition of the present invention contains the following (component 1):
(Component 1) Oxazoline-modified polypropylene produced by a method comprising the following steps: Content 1 to 20% by mass:
-A step of melt-kneading polypropylene, an organic peroxide, and maleic acid or maleic anhydride, and-in a melt-kneaded product of the obtained polypropylene, an organic peroxide, and maleic acid or maleic anhydride. Step of adding oxazoline compound and melt-kneading,

In one embodiment, the polypropylene composition of the present invention contains the following (component 1), (component 2) and (component 3):
(Component 1) Oxazoline-modified polypropylene produced by a method comprising the following steps: Content 1 to 20% by mass:
-A step of melt-kneading polypropylene, an organic peroxide, and maleic acid or maleic anhydride, and-in a melt-kneaded product of the obtained polypropylene, an organic peroxide, and maleic acid or maleic anhydride. Step of adding oxazoline compound and melt-kneading,
(Component 2) Polypropylene: Content 30 to 98% by mass, and (Component 3) At least one filler selected from the group consisting of carbon fiber, glass fiber and talc: Content 1 to 50% by mass.

Molded article The polypropylene composition of the present invention is used, for example, for producing a molded article by the following method.
Examples of the method for producing a molded product include a method for producing a molded product, which comprises a step of melting the polypropylene composition and molding the product to obtain a molded product.
Examples of the molding method include an extrusion molding method and an injection molding method. By extrusion molding, for example, a sheet-shaped molded product can be obtained. Injection molding gives an injection molded body.
Examples of the injection molding method include a general injection molding method, an injection foam molding method, a supercritical injection foam molding method, an ultrahigh speed injection molding method, an injection compression molding method, a gas assisted injection molding method, a sandwich molding method, and a sandwich foaming method. Examples include a molding method and an insert / outsert molding method.

Applications The polypropylene composition and molded body of the present invention are, for example, automobile parts such as automobile interior parts and exterior parts, automobile parts, two-wheeled automobiles / automobile parts, housing-related parts, medical equipment, robot parts, aircraft parts, home appliance parts, and the like. It can be used as electrical and electronic parts, mechanical mechanism parts, electric tool parts, food containers, sporting goods, and building material related parts.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Calculation method of binding component on carbon fiber surface

Removal of sizing agent The set temperature of the high-speed solvent extraction device ASE-200 manufactured by Dionex Co., Ltd. was set to 80 ° C., 0.2 g of carbon fiber was placed in an extraction cell container having a volume of 11 ml, and the high-speed solvent extraction device ASE-200 was installed. .. After injecting 11 ml of tetrahydrofuran (Kanto Chemical Co., Inc., special grade, stabilizer-free) into the extraction cell container, the pressure in the extraction cell container was pressurized to 1000 psi and held for 15 minutes. About half of the tetrahydrofuran was expelled from the discharge port of the extraction cell container using nitrogen, and after injecting again until the amount of tetrahydrofuran in the extraction cell container reached 11 ml, the pressure in the extraction cell container was pressurized to 1000 psi and held for 10 minutes. .. Once again, use nitrogen to expel about half of the tetrahydrofuran from the outlet of the extraction cell container, inject again until the amount of tetrahydrofuran in the extraction cell container reaches 11 ml, and then pressurize the pressure in the extraction cell container to 1000 psi. Held for minutes. Then, nitrogen was injected into the extraction cell container for 2 minutes, and tetrahydrofuran was expelled from the discharge port of the extraction cell container. Carbon fibers were removed from the extraction cell container and vacuum dried at 40 ° C. for at least 15 hours.

X-ray photoelectron spectroscopy (XPS) analysis Next, the carbon fiber subjected to the above-mentioned work was installed in an X-ray photoelectron spectroscopy apparatus (Shimadzu / AXIS ULTRA DLD manufactured by KRATOS). As an X-ray source, monochromatic Al Kα (1486.6 eV) was used and used as excitation light. The output was measured with the tube current set to 10 mA and the tube voltage set to 15 kV, respectively, and the photoelectron extraction angle defined by the angle between the sample normal and the photoelectron extraction direction was set to 0 °. The background of the obtained carbon 1s spectrum was removed by the Schillley method.

A Gauss-Lorentz complex function with a Lorentz function ratio of 30% to the carbon 1s spectrum from which the background has been removed is used and is described in Functions: Part A 90 (2016) 653-661 (Bo Gao et al.). The waveforms were separated into peaks derived from the CC-binding component, the CN-binding component, the CO-binding component, the C = O-binding component, and the OC = O-binding component, respectively.

Obtain the spectral areas of each of the CC bond component, the CN bond component, the CO bond component, the C = O bond component, and the OC = O bond component obtained by waveform separation, and obtain the CC bond component. The ratio of the area of the spectrum of the C—O bond component to 100% of the total amount of the CN bond component, the CO bond component, the C = O bond component, and the OC = O bond component and the C = O bond component. The ratio of the total amount of the area of the spectrum and the area of the spectrum of the OC = O bond component was calculated.

Examples of Oxazoline-Modified Polypropylene

Example M1: Oxazoline-modified polypropylene-1

M1-1) Maleic anhydride-modified polypropylene-1
Maleic anhydride-modified polypropylene-1 was produced using Synthesis Example 2 described in WO2020 / 909090.

M1-2) Oxazoline-modified polypropylene-1
100 parts by mass of maleic anhydride-modified polypropylene-1 synthesized above, 0.46 parts by mass of an oxazoline compound (trade name CP Resin A 1,3-PBO manufactured by Mikuni Pharmaceutical Co., Ltd.), and antioxidant 1 0.2 parts by mass of (Sumilyzer GA80 manufactured by Sumitomo Chemical Co., Ltd.) and 0.2 parts by mass of antioxidant 2 (Sumilyzer GP manufactured by Sumitomo Chemical Co., Ltd.) are mixed, and a twin-screw kneader (Technobel Co., Ltd., KZW12TW) is mixed. While degassing from the vacuum vent at -60 / 75 mg-NH, screw diameter 12 mm, L / D = 75, cylinder temperature 250 ° C., rotation speed 300 rpm, discharge 2 kg / hr), melt-kneaded and kneaded with oxazoline-modified polypropylene-1. Got The MFR (230 ° C., 2.16 kg load) of the obtained oxazoline-modified polypropylene-1 was 152 g / 10 minutes.

Examples M2-M4: Oxazoline-modified polypropylene-2 to oxazoline-modified polypropylene-4
Oxazoline-modified polypropylene-2 to oxazoline-modified polypropylene-4 of Examples M2 to M4 were produced in the same manner as in oxazoline-modified polypropylene-1 except that the materials shown in Table 1 were used.

Examples M5 to M7: Oxazoline-modified polypropylene-5 to oxazoline-modified polypropylene-7
Oxazoline-modified polypropylene-5 to oxazoline-modified polypropylene-7 of Examples M5 to M7 were produced in the same manner as in oxazoline-modified polypropylene-1 except that the materials shown in Table 2 were used.

As the maleic anhydride-modified polypropylene-2, the following maleic anhydride-modified polypropylene was used.
Maleic anhydride-modified polypropylene-2: Bondyram 1001 manufactured by Polyram Plastic Industries.
MFR (230 ° C, load 21.2N): 315g / 10 minutes

Comparative Example M8: Oxazoline-modified polypropylene-8
Maleic anhydride-modified polypropylene-3 by 100 parts by mass, oxazoline compound (manufactured by Mikuni Pharmaceutical Co., Ltd., trade name CP Resin A 1,3-PBO) by 2.35 parts by mass, antioxidant 1 (Sumitomo Chemical Co., Ltd.) 0.2 parts by mass of Sumilyzer GA80 manufactured by the company and 0.2 parts by mass of antioxidant 2 (Sumilyzer GP manufactured by Sumitomo Chemical Co., Ltd.) are mixed, and a twin-screw kneader (KZW12TW-60 / 75 mg manufactured by Technobel Co., Ltd.) is mixed. -NH, screw diameter 12 mm, L / D = 75, cylinder temperature 200 ° C., rotation speed 300 rpm, discharge 1.5 kg / hr) while degassing from the vacuum vent, melt-kneaded to obtain oxazoline-modified polypropylene-8. rice field. The MFR (230 ° C., 2.16 kg load) of the obtained oxazoline-modified polypropylene-8 was 648 g / 10 minutes.

As the maleic anhydride-modified polypropylene-3, the following maleic anhydride-modified polypropylene was used.
Maleic anhydride-modified polypropylene-3: Youmex 1010 manufactured by Sanyo Chemical Industries, Ltd.

Relationship between oxazoline-derived normalized absorbance derived from oxazoline groups and oxazoline group content in oxazoline-containing polypropylene homopolymers Oxazoline compounds (manufactured by Mikuni Pharmaceutical Co., Ltd., trade name CP Resin A 1,3-PBO) and polypropylene homopolymers 1 (Noblen HR100EG manufactured by Sumitomo Chemical Co., Ltd.) was melt-kneaded using a kneader (Laboplast Mill manufactured by Toyo Seiki Co., Ltd.). A plurality of oxazoline-containing polypropylene homopolymers were obtained by changing the compounding ratio of the oxazoline compound and the polypropylene homopolymer 1. From the content of the oxazoline compound in the obtained oxazoline-containing polypropylene homopolymer, the content of the oxazoline group in the oxazoline-containing polypropylene homopolymer was calculated. Next, the obtained sample was preheated at 210 ° C. for 5 minutes, and a pressure of 5 MPa was applied for 5 minutes to prepare a sample having a thickness of 300 μm by press molding. A transmission spectrum having a wave number of 600 to 4000 cm ^-1 was measured using a Fourier transform infrared spectrophotometer (FT / IR, 6200 manufactured by Nippon Spectroscopy Co., Ltd.) for the produced molded product. Absorbance derived from the oxazoline group in the oxazoline _- containing polypropylene homopolymer according to the following formula (1) using the absorbance _IA of 1655 cm ^-1 derived from the oxazoline group of the obtained IR spectrum and the absorbance IB of 841 cm ^-1 . Was standardized, and the standardized absorbance was defined as α _A. Using the content of oxazoline groups in the α _A and oxazoline-containing polypropylene homopolymer, a calibration curve of the content of α _A and oxazoline groups was prepared. From the prepared calibration curve, the content of α _A and the oxazoline group X mmol / g had the relationship of the following equation (2).
α _A = _IA / _IB (1)
X = 0.3849 × α _A (2)

Calculation method of oxazoline group content in 1 g of oxazoline-modified polypropylene Preheat maleic anhydride-modified polypropylene used for synthesizing oxazoline-modified polypropylene at 190 ° C. for 5 minutes, apply pressure of 5 MPa for 5 minutes, and make a sample with a thickness of 100 μm. Was produced by press molding. 0.3 g was cut out from the prepared press-molded product, and the cut-out molded product was put into 30 ml of ethanol. Then, the sample was allowed to stand at 30 ° C. for 60 hours, the sample was collected by filtration, air-dried, and then vacuum-dried at room temperature for at least 18 hours. The obtained sample was preheated at 210 ° C. for 5 minutes, and a pressure of 5 MPa was applied for 5 minutes to prepare a sample having a thickness of 100 μm to 300 μm by press molding. The produced press-molded body was measured with a transmission spectrum having a wave number of 600 to 4000 cm ^-1 using a Fourier transform infrared spectrophotometer (FT / IR, 6200 manufactured by Nippon Spectroscopy Co., Ltd.). The absorbance IC having a wave number of 1655 cm ^-1 in the obtained spectrum was normalized by the following equation (3) using the _absorbance ID of ₈₄₁ cm ^-1 , and the normalized absorbance was defined as α _B.
For oxazoline-modified polypropylene, a press-molded product was prepared by the same procedure, and the transmission spectrum was measured using FT / IR. Using the _{absorbance IE} with a wave number of 1655 cm ^-1 and the absorbance IF of 841 cm ^-1 in the obtained spectrum, the absorbance derived from the oxazoline group in the oxazoline-modified polypropylene was standardized and standardized by the following equation (4). The absorbance was determined to be α _C. Using α _B and α _C , the absorbance α _D derived from the oxazoline group in the oxazoline-modified polypropylene was calculated by the following equation (5). From α _D and the formula (2), the content Y mmol / g of the oxazoline group in 1 g of the oxazoline-modified polypropylene was calculated.
α _B = _IC / _ID (3)
α _C = _IE / _IF (4)
α _D = α _C -α _B (5)
Y = 0.3849 × α _D (mmol / g) (6)

Materials used In the examples and comparative examples, the following materials were used.

1. 1. Oxazoline-modified polypropylene (ingredient 1)
Oxazoline-modified polypropylene 1
Oxazoline-modified polypropylene-1 of the above example
MFR (230 ° C, load 21.2N): 152 g / 10 minutes Oxazoline group content: 2.0 × 10 ^-2 mmol / g

Oxazoline-modified polypropylene 2
Oxazoline-modified polypropylene-2 of the above example
MFR (230 ° C, load 21.2N): 41 g / 10 minutes Oxazoline group content: 11.2 × 10 ^-2 mmol / g

Oxazoline-modified polypropylene 3
Oxazoline-modified polypropylene-3 of the above example
MFR (230 ° C, load 21.2N): 6.9 g / 10 minutes Oxazoline group content: 19.0 × 10 ^-2 mmol / g

Oxazoline-modified polypropylene 4
Oxazoline-modified polypropylene-4 of the above example
MFR (230 ° C, load 21.2N): 2.3 g / 10 minutes Oxazoline group content: 20.7 × 10 ^-2 mmol / g

Oxazoline-modified polypropylene 5
Oxazoline-modified polypropylene-5 of the above example
MFR (230 ° C, load 21.2N): 275 g / 10 minutes Oxazoline group content: 0.2 × 10 ^-2 mmol / g

Oxazoline-modified polypropylene 6
Oxazoline-modified polypropylene-6 of the above example
MFR (230 ° C, load 21.2N): 238 g / 10 minutes Oxazoline group content: 3.1 × 10 ^-2 mmol / g

Oxazoline-modified polypropylene 7
Oxazoline-modified polypropylene-7 of the above example
MFR (230 ° C, load 21.2N): 162 g / 10 minutes Oxazoline group content: 6.4 × 10 ^-2 mmol / g

Modified Polypropylene of Comparative Example C1 Maleic anhydride-modified polypropylene-1 used in synthesizing the above Example M1
MFR (230 ° C, load 21.2N): 199 g / 10 min Oxazoline group content: 0.0 × 10 ^-2 mmol / g

Comparative Examples C2 and C3 Modified Polypropylene Oxazoline Modified Polypropylene-8
MFR (230 ° C, load 21.2N): 648 g / 10 minutes Oxazoline group content: 14.9 × 10 ^-2 mmol / g

2. 2. Polypropylene (component 2)
Polypropylene homopolymer 1 (Nobren HR100EG manufactured by Sumitomo Chemical Co., Ltd.)
MFR (230 ° C, load 21.2N): 23g / 10 minutes Melting point: 164 ° C

3. 3. Filler (ingredient 3)
Carbon Fiber 1 (CFRI T8S103C manufactured by Carbon Fiber Recycling Industry Co., Ltd.)
CO bond: 5.2%, total of C = O bond and OC = O bond: 5.8%

Glass fiber 1 (CS 249A-10C manufactured by Owes Corning)

4. Other Materials Antioxidant 3: Made by BASF Japan Ltd. Ilganox 1010
Antioxidant 4: BASF Japan Co., Ltd. Irgafos 168
Neutralizer: San Ace Co., Ltd. Calcium stearate

Melt kneading and manufacturing of injection molded products

Example C1
Polypropylene homopolymer 1 70% by mass, oxazoline-modified polypropylene 1 10% by mass, carbon fiber 1 20% by mass, polypropylene homopolymer 1, oxazoline-modified polypropylene 1 and carbon fiber 1 in total 100 parts by mass. The antioxidant 3 0.2 parts by mass and the antioxidant 4 0.2 parts by mass were mixed to obtain a mixture. The mixture is melt-kneaded with a 40 mm single-screw extruder (VS40-28 type bent extruder, manufactured by Tanabe Plastics Co., Ltd.) at a cylinder temperature of 220 ° C. and a screw rotation speed of 100 rpm to pelletize and obtain a polypropylene composition. rice field. The obtained polypropylene composition was injection-molded using an injection molding machine (M-70CSJ manufactured by Meiki Seisakusho Co., Ltd.) under the conditions of a cylinder temperature of 220 ° C., a mold temperature of 50 ° C., and an injection speed of 20 mm / sec. An injection molded article of an ISO test piece was obtained.

Examples C2 to C7 and Comparative Examples C1 to C2
Polypropylene compositions of Examples C2 to C7 and Comparative Examples C1 to C2 were produced in the same manner as in Example C1 except that the materials shown in Table 4 were used. The maleic anhydride-modified polypropylene used for producing the polypropylene of Comparative Example 1 is described in the frame of "Component 1" for convenience.

Example C8
Polypropylene homopolymer 1 58.5% by mass, oxazoline-modified polypropylene 2 1.5% by mass, glass fiber 1 40% by mass, polypropylene homopolymer 1, oxazoline-modified polypropylene 2 and glass fiber 1 in total 100 parts by mass 3 0.2 parts by mass of the antioxidant, 0.2 parts by mass of the antioxidant 4 and 0.05 parts by mass of the neutralizing agent were mixed to obtain a mixture. The mixture was melt-kneaded by a 32 mm twin-screw extruder (two-screw extruder ZSK32Mc18, manufactured by Coperion) at a cylinder temperature of 230 ° C. and a screw rotation speed of 400 rpm, and pelletized to obtain a polypropylene composition. The obtained polypropylene composition was injection-molded using an injection molding machine (M-70CSJ manufactured by Meiki Seisakusho Co., Ltd.) under the conditions of a cylinder temperature of 220 ° C., a mold temperature of 50 ° C., and an injection speed of 20 mm / sec. An injection molded article of an ISO test piece was obtained.

Comparative Example C3
The polypropylene composition of Comparative Example C3 was produced in the same manner as in Example C8 except that the materials shown in Table 5 were used.

Evaluation of physical properties 1. Melt mass flow rate (MFR) (Unit: g / 10 minutes)
The melt mass flow rate was measured at a measurement temperature of 230 ° C. and a load of 2.16 kg according to the method specified in JIS K 7210.

2. 2. Density (Unit: g / cm ³ )
The A method specified in JIS K7112 is used as a test piece obtained by cutting a molded product into a size of 80 mm × 10 mm × 4 mm, which is formed by the molding method described in the above-mentioned “Melting kneading and manufacturing of injection molded product”. The density was measured according to the underwater substitution method.

3. 3. Tensile breaking strength (unit: MPa)
Using a test piece having a thickness of 4 mm molded by the molding method described in the above-mentioned "melt kneading and manufacturing of an injection molded product", a tensile speed of 50 mm / min is performed according to the method specified in ISO 527-2. , The tensile breaking strength (US) was measured.

4. Bending strength (unit: MPa)
Using a test piece having a thickness of 4 mm molded by the molding method described in the above-mentioned "melt kneading and manufacturing of an injection molded product", a load rate of 2.0 mm / min is used according to the method specified in ISO 178. , Bending strength (FS) was measured.

5. Charpy impact strength with notch (unit: kJ / m ² )
The molded product formed by the molding method described in the above-mentioned "melt kneading and production of injection molded product" is cut into a size of 80 mm × 10 mm × 4 mm, and the notched product is used as a test piece to ISO 179-1. Notched Sharpy impact strength due to edgewise impact was measured according to the method specified in. The shape of the notch was the shape A described in ISO 179-1.

Claims (7)

Oxazoline-modified polypropylene that meets the following requirements (1), (1-a), and (2):
(1) Oxazoline-modified polypropylene has an oxazoline group.
(1-a) The content of the oxazoline group in 1 g of oxazoline-modified polypropylene is 0.1 × 10 − ² to 100 × 10 − ² mmol / g, and (2) the melt mass flow rate of (2) oxazoline-modified polyprilopylene is 0. 0.01-300 g / 10 minutes. Oxazoline-modified polypropylene produced by a method comprising the following steps:
-A step of melt-kneading polypropylene, an organic peroxide, and maleic acid or maleic anhydride, and-in a melt-kneaded product of the obtained polypropylene, an organic peroxide, and maleic acid or maleic anhydride. , A step of adding an oxazoline compound and melt-kneading. A method for producing oxazoline-modified polypropylene, which comprises the following steps:
-A step of melt-kneading polypropylene, an organic peroxide, and maleic acid or maleic anhydride.
-A step of adding an oxazoline compound to a melt-kneaded product of the obtained polypropylene, an organic peroxide, and maleic acid or maleic anhydride, and melt-kneading the mixture. Polypropylene composition containing the following (component 1):
(Component 1) Oxazoline-modified polypropylene that satisfies the following requirements (1), (1-a), and (2):
(1) Oxazoline-modified polypropylene has an oxazoline group.
(1-a) The content of the oxazoline group in 1 g of oxazoline-modified polypropylene is 0.1 × 10 − ² to 100 × 10 − ² mmol / g, and (2) the melt mass flow rate of (2) oxazoline-modified polyprilopylene is 0. 0.01-300 g / 10 minutes. Polypropylene composition containing the following (component 1):
(Component 1) Oxazoline-modified polypropylene produced by a method comprising the following steps:
-A step of melt-kneading polypropylene, an organic peroxide, and maleic acid or maleic anhydride, and-in a melt-kneaded product of the obtained polypropylene, an organic peroxide, and maleic acid or maleic anhydride. The process of adding an oxazoline compound and melt-kneading. (Component 1): The polypropylene composition according to claim 4 or 5, which contains 1 to 20% by mass and contains the following (component 2) and (component 3):
(Component 2) Polypropylene: Content 30 to 98% by mass, and (Component 3) At least one filler selected from the group consisting of carbon fiber, glass fiber and talc: Content 1 to 50% by mass. (Component 3) The polypropylene composition according to any one of claims 4 to 6, which contains carbon fiber as a filler.