JP2008115305A - Propylene resin-molded article with modified surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylene resin-molded article having a surface modified by using a surface modification method by graft polymerization with a simple process at a low cost. <P>SOLUTION: The invention relates to the propylene resin-molded article with modified surface comprising a polymer A composed of a polypropylene and/or a propylene copolymer containing propylene as a principal component and having a crystal melting peak temperature higher than 140°C, and an elastomer B composed of an amorphous or a low crystallinity elastomer composed of hydrocarbons and/or a block copolymer or a graft copolymer containing an amorphous or low crystallinity elastomer block composed of hydrocarbons, and a radically polymerizable monomer chemically bonded to the surface of the molded article. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a propylene resin molded article having hydrophilicity and reactivity introduced on its surface.

  Polypropylene is used in various applications because of its excellent heat resistance, light weight, chemical resistance, and the like. However, depending on the application, the surface properties of the polypropylene molded article may be insufficient, and improvements in surface hydrophilicity, adhesiveness, paintability, plating properties, printability, etc. are often required.

  For such improvement, various methods have been studied so far (Non-Patent Document 1), and a method of generating a polar group by directly oxidizing a resin surface has been devised. Examples of such methods include flame treatment, corona discharge treatment, plasma treatment, electron beam irradiation, chemical treatment, and the like, and it is known that a hydroxyl group, a carbonyl group, a carboxyl group, and the like are generated on the surface of the molded body by these treatments. It has been. As a result, it has been found that the surface of the polypropylene molded body is modified due to improved hydrophilicity, but depending on the method, the modification effect is insufficient, and the resulting molded body is limited for printing and the like. May be used. In addition, even if the modification effect is sufficient and can be used in a wide range including adhesion, painting, plating, etc., when such a resin is directly oxidized, the surface characteristics deteriorate with time and the state before treatment It is known that the surface properties of the molded body cannot be maintained over a long period of time. In addition, plasma treatment and electron beam irradiation require special expensive equipment and are expensive, so that the use of the molded body treated in this way is limited. Further, since chemical treatment has problems such as danger and environmental pollution, the use of the molded body thus treated is limited to plating and the like.

  As a method for modifying the surface of a polypropylene molded body, a method of introducing a polar compound or polymer to the surface has been devised. Primer treatment in which a compound or polymer having a chemical structure having polarity and a chemical structure having affinity for polypropylene is applied to the surface of the polypropylene molded product corresponds to such a method. Since the primer treatment can be easily modified by coating, it is often used for painting or adhesion. However, in the molded body treated in this way, the primer and polypropylene are merely physically interacting with each other at the interface. Therefore, the adhesive force between them and the stability thereof are not necessarily sufficient, and the layer is formed by coating. Therefore, there is a problem that the unevenness is buried by coating on the surface having fine unevenness.

  As a method for introducing a compound structure having a polarity on the surface, a method of grafting a polar polymer by generating a radical on the surface and bonding a monomer having a polar group thereto can also be used. As a method for generating radicals on the surface, plasma treatment, electron beam irradiation, or the like is used. However, since the method using such expensive equipment increases the processing cost, there are cases where the use of the molded body thus treated is limited.

  Another method for generating radicals on the surface is to introduce a polymerization initiator to the surface and generate radicals by light or heat. This method allows surface modification at low cost with simple equipment. can do. In the prior art, a method of surface modification by grafting a polymer by generating radicals from a polymerization initiator on the surface of a substrate or support made of various resins and bringing them into contact with a monomer has been proposed ( Patent Documents 1 and 2). In these technologies, polypropylene is listed as the resin used for the substrate or support, but the resins actually used in the examples are silicone rubber, polyurethane, low density polyethylene, polyvinyl chloride (soft vinyl chloride). ) And the like, and polypropylene is not used. Considering the characteristics of the resins used in these examples, a flexible polymer with low crystallinity seems to be suitable for such graft polymerization, and a resin with high crystallinity and excellent solvent resistance such as polypropylene. In contrast, it is estimated that it is extremely difficult to cause a graft reaction to the surface. Also in the examples of the present invention, it was obtained that the graft reaction to the surface was extremely difficult with polypropylene alone.

Thus, the surface modification method by graft polymerization using a polymerization initiator is promising because of its excellent cost and simplicity, but it has not yet been able to modify the polypropylene surface, while having the properties of polypropylene. Low-cost molded articles having hydrophilicity, adhesiveness, printability and the like on the surface are widely demanded for applications such as daily necessities, containers, sheets, and films.
Edited by the Society of Polymer Science, Japan “Study on New Polymer Experiments 10: Physical Properties of Polymers (3) Surfaces / Interfaces and Membranes / Transport” Special table 2003-510378 Special table 2005-51419 2

  In view of the prior art, an object of the present invention is to provide a propylene resin molded body whose surface is modified easily and inexpensively using a surface modification method by graft polymerization.

  The propylene resin molded article of the present invention is a propylene copolymer having a main component of polypropylene and / or propylene, a polymer A having a crystal melting peak temperature of 140 ° C. or higher, and an amorphous or low crystalline property comprising a hydrocarbon. A block copolymer containing an amorphous or low-crystalline elastomer block made of an elastomer and / or a hydrocarbon, and an elastomer B made of a graft copolymer, and a radically polymerizable monomer is formed on the surface of the molded body It is characterized by being chemically bonded to.

  The crystal melting peak temperature of the polymer A is preferably 140 ° C. or higher so that the propylene resin molded article of the present invention can be used in ordinary polypropylene applications. The crystal melting peak temperature is measured by a differential scanning calorimeter or the like.

  Elastomer B uses its amorphous or low crystallinity and is added to facilitate the introduction of a polymerization initiator on the surface of the propylene resin molded article and to facilitate the graft reaction. From the viewpoint of compatibility with the polymer A, the elastomer B is preferably an amorphous or low-crystalline elastomer made of hydrocarbon. Monomers constituting the elastomer B include alkenes such as ethylene and propylene, and dienes composed of hydrocarbons, but are not particularly limited as long as they are monomers composed of hydrocarbons. The elastomer B may be a block copolymer or a graft copolymer containing an amorphous or low-crystalline elastomer block made of hydrocarbon from the viewpoint of compatibility.

  The monomer capable of radical polymerization is not particularly limited, and acrylic acid derivatives, methacrylic acid derivatives, and the like can be used freely.

When the radically polymerizable monomer is chemically bonded to the surface of the molded body, it is preferable to use a polymerization initiator.
The polymerization initiator is preferably a photopolymerization initiator, and can be freely selected from photopolymerization initiators such as benzoin ether, ketal, acetophenone, benzophenone, and thioxanthone.

  As a method of bonding a radically polymerizable monomer to the surface of a propylene resin molded article using a polymerization initiator, after contacting the propylene resin molded article with a polymerization initiator for a certain period of time, A method of heating and / or irradiating with light for a certain period of time while contacting is mentioned.

  As a method of bringing the surface of the propylene resin molded body into contact with the polymerization initiator, after immersing in a polymerization initiator solution or a liquid polymerization initiator for a certain time, the molded body is pulled up from the liquid to remove excess liquid on the surface. A method is mentioned. Further, a method in which a gel sheet impregnated with a polymerization initiator solution or a liquid polymerization initiator is brought into contact with a propylene resin molded article can also be used.

  As a method of bringing the radically polymerizable monomer into contact with the surface of the propylene resin molded body, there is a method of immersing the molded body in a monomer solution or a liquid monomer, or applying the solution or liquid. Can be mentioned. Moreover, you may make it contact by putting a propylene resin molded object in the container with which the gaseous monomer was satisfy | filled.

The content of elastomer B in the propylene resin constituting the propylene resin molded article of the present invention is preferably 10 to 70% by weight.
Since the elastomer B is added to improve the graft reactivity as described above, it is preferable that the content of the elastomer B is large from the viewpoint of surface modification. However, if the elastomer B is too much, the heat resistance of the propylene resin molded body is high. This is not preferable because the properties and rigidity are lowered and the moldability of the resin constituting the propylene resin molded product is lowered. Therefore, the content of the elastomer B is preferably in the range of 10 to 70% by weight, and more preferably in the range of 15 to 60% by weight.

  The method for preparing the resin constituting the propylene resin molded article of the present invention is not particularly limited, but melt kneading using a twin screw extruder is preferably used from the viewpoint of productivity and resin dispersibility. Moreover, the method of shape | molding a propylene resin molded object is not specifically limited, Injection molding, blow molding, compression molding, extrusion molding, etc. can be used suitably.

The radically polymerizable monomer chemically bonded to the surface of the propylene resin molded article of the present invention is a hydroxyl group, carboxyl group, epoxy group, amino group, amide group, aldehyde group, methylol group, isoacinate group, oxazoline group, alkoxysilane. It is preferable to include at least one monomer having one or two or more functional groups selected from a group, a sulfo group, a pyridine group, and a pyrrolidone group.
In the surface modification of the propylene resin molded article, it is often required to improve hydrophilicity and reactivity. Therefore, it is preferable to use a monomer having the functional group that is excellent in hydrophilicity and reactivity.

Examples of such monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, cinnamic acid, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-isopropylacrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid,
N-isobutoxymethyl acrylamide, maleamide, 2-aminoethyl vinyl ether, N-methylol acrylamide, N-methylol methacrylamide, hydroxyethylated diacetone acrylamide, methoxymethylated acrylamide, methoxymethylated methacrylamide, butoxymethylated acrylamide, Butoxymethylated methacrylamide, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, 4-vinylcyclohexane monoepoxide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxy Butyl acrylate, 4-hydroxybutyl methacrylate, allyl alcohol Coal, monoallyl ether of polyhydric alcohol, acrolein, crotonaldehyde, diacetone acrylamide, m-isopropenyl-α, α-dimethylbenzyl isocyanate, 3-chloro-2-hydroxypropyl methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane , Vinyltrismethoxyethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, vinyloxazoline, 2-propenyl 2-oxazoline, acrylamide glycolic acid, methacrylamide glycolic acid, N-methylol derivatives of allyl carbamate, 2- Vinyl pyridine, 4-vinyl pyridine, N-vinyl pyrrolidone, polyethylene glycol acrylate, polyethylene glycol methacrylate Rate, and the like.

  The elastomer B of the present invention is a block copolymer and / or a graft copolymer comprising a polymer X obtained by hydrogenating a polymer of a conjugated diene, and a polymer X and a polymer Y that is incompatible with the polymer A. It is more preferable.

  The polymer X is a polymer obtained by hydrogenating a polymer of a conjugated diene selected so that the compatibility between the polymer A and the elastomer B is better. The conjugated diene used in the polymer X is preferably butadiene or isoprene, and includes a structure in which the polymer X is hydrogenated with 1,2 bonds other than cis-1,4 bonds (including 3-4 bonds in isoprene). It is more preferable from the viewpoint of the compatibility between the polymer A and the elastomer B. The compatibility of the polymer A and the elastomer B is good because the transparency of the composition obtained by mixing the polymer A and the elastomer B is superior to the transparency of the polymer A alone. it can.

  The polymer Y is a block copolymer or graft copolymer with the polymer X from the viewpoint of facilitating the melt kneading of the polymer A and the elastomer B by adjusting the melt viscosity of the elastomer B or improving the handleability of the elastomer B. Copolymerized. The bond structure of polymer X and polymer Y is not particularly limited. For diblock copolymers, polymer X-polymer Y, for triblock copolymers, polymer Y-polymer X-polymer Y, polymer In the case of X-polymer Y-polymer X and multi-block copolymer, polymer X and / or polymer Y is the terminal, polymer X and polymer Y are alternately connected, etc. Examples of the polymer include a structure in which the polymer X is a trunk and the polymer Y is a branch, and a structure in which the polymer Y is a trunk and the polymer X is a branch.

The type of the polymer Y is not particularly limited, but a vinyl aromatic polymer such as polystyrene, a (meth) acrylic polymer, a polyolefin, and the like are preferable from the viewpoint of polymerization and availability.
In the elastomer B, it is preferable that the amount of the polymer X is larger from the viewpoint of compatibility with the polymer A and improvement of graft reactivity by an amorphous or low crystalline polymer. However, if the amount of the polymer X is too large, the polymer A and the elastomer B Therefore, the ratio of the polymer X of the elastomer B is preferably in the range of 40 to 95% by weight.

  The surface-modified propylene resin molded body of the present invention has hydrophilicity and reactivity on the surface, so that it can be processed for adhesion, painting, printing, plating, etc. Will also be available. Further, by utilizing the reactivity of the surface, various functional substances such as DNA, protein, antibody, enzyme, and fluorescent substance can be bound to the surface, and the propylene resin molded product can be highly functionalized.

In order to produce the propylene resin molded article of the present invention, a resin as a raw material was prepared. As polymer A, Mitsui Polypro PP grade, J105F manufactured by Mitsui Polyolefin Co., Ltd., J-3021GR manufactured by Idemitsu Petrochemical Co., Ltd., and Hibler 7311S manufactured by Kuraray Co., Ltd. (polystyrene-polyisoprene-polystyrene triblock copolymer) as elastomer B A polymer obtained by hydrogenating a polymer having a styrene content of 12% and a tensile modulus of 100% of 0.6 MPa) was used.
When the crystal melting peak temperature of the J105F pellet was measured using a differential scanning calorimeter DSC7 manufactured by PerkinElmer, the value was 167 ° C. Further, J105F was molded into a molded body having a length of 7 cm, a width of 5 cm, and a thickness of 2.5 mm by hot pressing, and the haze was measured using a direct reading haze computer manufactured by Suga Test Instruments Co., Ltd., and the value was 50.5%. there were. Moreover, when the same molded object was used and the infrared absorption spectrum of the surface was measured by ATR method (using DuraScope made by ST Japan Co., Ltd.) using FT / IR-680 made by JASCO Corporation, FIG. Spectra typical of polypropylene were obtained.
The crystal melting peak temperature and haze of J-3021GR were measured in the same manner as described above, and the values were 152 ° C. and 39.8%. Further, when an infrared absorption spectrum of J-3021GR was measured in the same manner as described above, a spectrum typical for polypropylene similar to that in FIG. 1 was obtained.
J105F or J-3021GR pellets and Hibler 7311S pellets are mixed in the composition shown in FIG. 2 and melted by a 16 mm segment type twin screw extruder (manufactured by Kawabe Seisakusho) under the conditions of a screw speed of 250 rpm and a cylinder temperature of 200 ° C. The mixture was kneaded to produce a pellet of the mixture. The obtained pellets were molded into a shape having a length of 7 cm, a width of 5 cm, and a thickness of 2.5 mm by hot pressing, and formed bodies a to e in FIG. When the infrared absorption spectrum of the compact e was measured in the same manner as described above, the spectrum shown in FIG. 3 was obtained.
When the haze of the molded body was measured in the same manner as described above, as shown in FIG. 2, all the values of the molded bodies a to e were smaller than the value of the component J105F or J-3021GR, and the molded bodies a to e were configured. It was revealed that the resin is excellent in compatibility.

Using the molded product e, a graft reaction to the surface was performed using 2-hydroxyethyl methacrylate as a monomer capable of radical polymerization. The grafting reaction was performed as follows. Prepare a molded body, wash the surface with methanol, dry it, and put it in 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba DAROCUR 1173 manufactured by Ciba Specialty Chemicals) in a glass container. After immersion for 24 hours, the molded body was taken out of the glass container and the surface was dried. As shown in FIG. 4, a monomer solution of 2-hydroxyethyl methacrylate / distilled water = 10/90 (weight ratio) (2 in FIG. 4) was used on the molded body (1 in FIG. 4). ) And a glass slide (3 in FIG. 4) was placed thereon so that the monomer solution spread over the entire upper surface of the molded body. An ultraviolet lamp (LUV-16, 22W, manufactured by ASONE Corporation) was placed on the molded body, monomer solution, and slide glass thus formed at a height of 2 cm from the top surface of the slide glass, and irradiated with ultraviolet rays for 10 minutes. After irradiation, the molded body was taken out, washed with methanol and dried.
When the infrared absorption spectrum of the surface of the molded product e thus graft-reacted was measured in the same manner as described above, the spectrum shown in FIG. 5 was obtained. When this spectrum was compared with the spectrum of the molded product e surface before grafting (see FIG. 3), it characteristic broad absorption peak to a hydroxyl group is observed in the vicinity in FIG. 5 3400 cm ^-1, also 1170cm around ^-1 , 1260 cm ⁻¹ and 1730 cm ⁻¹ have characteristic absorptions in the methacryloyl group, confirming that the 2-hydroxyethyl methacrylate polymer is bonded to the surface of the molded product e.

Using the molded body e and using methacrylic acid as a monomer capable of radical polymerization, a graft reaction to the surface was carried out in the same manner as in Example 1. When the infrared absorption spectrum of the surface of the molded product e subjected to the graft reaction was measured in the same manner as in Example 1, the spectrum shown in FIG. 6 was obtained. When this spectrum is compared with the spectrum of the surface of the molded product e before grafting (see FIG. 3), in FIG. 6, a broad absorption characteristic of the hydroxyl group of the acid associated in the vicinity of 2400-3700 cm ⁻¹ is observed, In addition, since absorption characteristic of the methacryloyl group of methacrylic acid is observed near 1170 cm ⁻¹ , 1260 cm ⁻¹ and 1720 cm ⁻¹ , it is confirmed that the methacrylic acid polymer is bonded to the surface of the molded product e. did.

Using the molded product e and using 3-methacryloxypropyltrimethoxysilane as a radical polymerizable monomer, the surface graft reaction was carried out in the same manner as in Example 1. When the infrared absorption spectrum of the surface of the molded product e subjected to the graft reaction was measured in the same manner as in Example 1, the spectrum shown in FIG. 7 was obtained. When this spectrum was compared with the spectrum of the surface of the molded product e before grafting (see FIG. 3), in FIG. 7, a strong absorption peak characteristic of alkoxysilane was observed in the vicinity of 1080 cm ⁻¹ , and 1730 cm ^−1. Since a peak considered to be a carbonyl group of a methacryloyl group was observed in the vicinity, it was confirmed that the 3-methacryloxypropyltrimethoxysilane polymer was bonded to the surface of the molded product e.

Using the molded product e, a graft reaction to the surface was performed using glycidyl methacrylate as a radical polymerizable monomer. The grafting reaction was performed as follows. Prepare a molded body, wash the surface with methanol, dry it, and put it in 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba DAROCUR 1173 manufactured by Ciba Specialty Chemicals) in a glass container. After immersion for 24 hours, the molded body was taken out of the glass container and the surface was dried. Using the molded body thus formed, a glycidyl methacrylate monomer (2 in FIG. 4) is placed on the molded body (1 in FIG. 4) as shown in FIG. 4, and then a slide glass (3 in FIG. 4) is placed thereon. ) To spread the monomer over the entire top surface of the molded body. An ultraviolet lamp (LUV-16, 22W, manufactured by ASONE Corporation) was placed on the molded body, monomer, and slide glass thus formed at a height of 2 cm from the top surface of the slide glass, and irradiated with ultraviolet rays for 10 minutes. After irradiation, the molded body was taken out, washed with acetone and dried.
When the infrared absorption spectrum of the surface of the molded product e thus grafted was measured in the same manner as in Example 1, the spectrum shown in FIG. 8 was obtained. When this spectrum was compared with the spectrum of the molded product e surface before grafting (see FIG. 3), it is observed a characteristic absorption peaks in the epoxy ring in the vicinity in FIG. 8 910 cm ^-1, also 1170cm around ^-1, Absorption characteristic of the methacryloyl group was observed in the vicinity of 1260 cm ⁻¹ and 1730 cm ⁻¹ , so that it was confirmed that the glycidyl methacrylate polymer was bonded to the surface of the molded product e.

Using the molded body e and using vinyl acetate as a monomer capable of radical polymerization, a graft reaction to the surface was carried out in the same manner as in Example 4. However, washing after irradiation with ultraviolet rays was performed using methanol. When the infrared absorption spectrum of the surface of the molded product e subjected to the graft reaction was measured in the same manner as in Example 1, the spectrum shown in FIG. 9 was obtained. A comparison of this spectrum with the spectrum of the molded product e surface before grafting (see FIG. 3), since the observed characteristic peaks at acetoxylation group near 1240 cm ^-1 and near 1740 cm ^-1 in FIG. 9, acetate It was confirmed that the vinyl polymer was bonded to the surface of the molded body e.

  Using the molded product d and using 2-hydroxyethyl methacrylate as a radical polymerizable monomer, a graft reaction to the surface was carried out in the same manner as in Example 1. When the infrared absorption spectrum of the surface of the molded product d subjected to the graft reaction was measured in the same manner as in Example 1, the spectrum of FIG. 10 was obtained. When this spectrum was compared with the spectrum of Example 1 (see FIG. 5), an absorption peak was observed at substantially the same wave number, and it was confirmed that the 2-hydroxyethyl methacrylate polymer was bonded to the surface of the molded product d. did.

  Using the molded product c and using 2-hydroxyethyl methacrylate as a radical polymerizable monomer, a graft reaction to the surface was carried out in the same manner as in Example 1. When the infrared absorption spectrum of the surface of the molded product c subjected to the graft reaction was measured in the same manner as in Example 1, the spectrum shown in FIG. 11 was obtained. When this spectrum was compared with the spectrum of Example 1 (see FIG. 5), an absorption peak was observed at substantially the same wave number, and it was confirmed that the 2-hydroxyethyl methacrylate polymer was bonded to the surface of the molded product c. did.

  Using the molded product b and using 2-hydroxyethyl methacrylate as a radical polymerizable monomer, a graft reaction to the surface was carried out in the same manner as in Example 1. When the infrared absorption spectrum of the surface of the molded product b subjected to the graft reaction was measured in the same manner as in Example 1, the spectrum shown in FIG. 12 was obtained. When this spectrum was compared with the spectrum of Example 1 (see FIG. 5), an absorption peak was observed at substantially the same wave number, and it was confirmed that the 2-hydroxyethyl methacrylate polymer was bonded to the surface of the molded product b. did.

Using the molded product a and using 2-hydroxyethyl methacrylate as a radical polymerizable monomer, a graft reaction to the surface was carried out in the same manner as in Example 1. When the infrared absorption spectrum of the surface of the molded product a subjected to the graft reaction was measured in the same manner as in Example 1, the spectrum shown in FIG. 13 was obtained. When this spectrum was compared with the spectrum of Example 1 (see FIG. 5), an absorption peak was observed at almost the same wave number, and it was confirmed that the 2-hydroxyethyl methacrylate polymer was bonded to the surface of the molded product a. did.
(Comparative Example 1)

  A graft reaction to the surface was carried out in the same manner as in Example 1 using the J105F molded product and using 2-hydroxyethyl methacrylate as a radical polymerizable monomer. When the infrared absorption spectrum of the surface of the molded body of J105F subjected to the graft reaction was measured in the same manner as in Example 1, the spectrum shown in FIG. 14 was obtained. When this spectrum was compared with the spectrum of Example 1 (see FIG. 5) and the spectrum of J105F (see FIG. 1), no 2-hydroxyethyl methacrylate polymer peak was observed in FIG. 14, and the spectrum was almost the same as that of J105F. Therefore, it was confirmed that the graft polymer was not bonded to the surface of the J105F molded body subjected to the graft reaction.

  The propylene resin molded article provided by the present invention is a container, case, sheet, film, pipe, daily necessities, vehicle parts, etc. that can be subjected to post-processing such as adhesion, painting, printing, plating, etc. by utilizing its surface characteristics. It can be widely used as various molded products such as medical devices. In addition, DNA, protein, antibody, enzyme, fluorescent substance, etc. can be introduced by binding a specific functional group to the surface of the molded body, so a microchip comprising a sensor substrate, DNA chip, microchannel, microwell, etc. , And so on.

The example of the infrared absorption spectrum of the polymer used for the Example is shown. The composition and haze of the molded product used in the examples are shown. The infrared absorption spectrum example of a molded object is shown. An example of a graft polymerization method will be shown. The infrared absorption spectrum of Example 1 is shown. The infrared absorption spectrum of Example 2 is shown. The infrared absorption spectrum of Example 3 is shown. The infrared absorption spectrum of Example 4 is shown. The infrared absorption spectrum of Example 5 is shown. The infrared absorption spectrum of Example 6 is shown. The infrared absorption spectrum of Example 7 is shown. The infrared absorption spectrum of Example 8 is shown. The infrared absorption spectrum of Example 9 is shown. The infrared absorption spectrum of the comparative example 1 is shown.

Claims (5)

  A propylene copolymer mainly composed of polypropylene and / or propylene, a polymer A having a crystal melting peak temperature of 140 ° C. or higher, and an amorphous or low-crystalline elastomer and / or hydrocarbon composed of hydrocarbon. A block copolymer containing an amorphous or low-crystalline elastomer block and an elastomer B made of a graft copolymer, wherein a radically polymerizable monomer is chemically bonded to the surface of the molded product , Propylene resin moldings.   2. The propylene resin molded article according to claim 1, wherein a polymerization initiator is used when a radical polymerizable monomer is chemically bonded to the surface of the molded article.   3. The propylene resin molded article according to claim 1, wherein the content of elastomer B in the propylene resin constituting the propylene resin molded article is 10 to 70% by weight.   Free-radically polymerizable monomers that can be chemically bonded to the surface of the propylene resin molded article are hydroxyl groups, carboxyl groups, epoxy groups, amino groups, amide groups, aldehyde groups, methylol groups, isoacinate groups, oxazoline groups, alkoxysilane groups, sulfones. The propylene resin molded article according to claim 1, comprising at least one monomer having one or more functional groups selected from a group, a pyridine group, and a pyrrolidone group.   The elastomer B is a block copolymer and / or a graft copolymer comprising a polymer X obtained by hydrogenating a polymer of a conjugated diene and a polymer Y and a polymer Y that is incompatible with the polymer A. The propylene resin molded product according to claim 1.

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