WO2023176255A1 - Polyolefin resin powder, resin composition, molded object, and method for producing molded object - Google Patents

Abstract

A polyolefin resin powder is provided from which a molded polyolefin resin object excellent in terms of coating-film adhesion thereto can be obtained without necessitating a surface treatment with a special device, coating with an adhesive layer, or a modification with a rubber ingredient. This polyolefin resin powder comprises a polyolefin resin modified with a compound having repeating units derived from an alkylene oxide.

Description

Polyolefin resin powder, resin composition, molded body, and method for producing molded body

The present invention relates to a polyolefin resin powder, a resin composition, a molded article, and a method for producing a molded article.
This application claims priority based on Japanese Patent Application No. 2022-043769 filed in Japan on March 18, 2022, the contents of which are incorporated herein.

Polyolefins such as propylene polymers and propylene-α-olefin copolymers are inexpensive and have excellent mechanical properties, heat resistance, chemical resistance, water resistance, etc., so they are used in a wide range of fields. . However, since polyolefins do not have polar groups in their molecules, they generally have low polarity, making it difficult to coat or adhere to substrates, and improvements in paintability and adhesiveness have been desired. In order to improve paintability and adhesion, the surface of the polyolefin molded body may be chemically treated with chemicals, etc., or the surface of the molded body may be oxidized using methods such as corona discharge treatment, plasma treatment, flame treatment, etc. Various methods have been tried. However, all of these treatment methods not only require special equipment, but also do not necessarily provide sufficient improvement in paintability or adhesiveness.

Therefore, as a relatively simple method for imparting good paintability and adhesion to polyolefins, such as propylene-based polymers, chlorinated polypropylene, acid-modified propylene-α-olefin copolymers, acid-modified chlorinated Modified polyolefins such as polypropylene have been proposed. Modified polyolefins generally have the characteristic that they can be applied as a surface treatment agent, adhesive, paint, etc. to the surface of a polyolefin molded article. Modified polyolefins are usually used by being applied in the form of a solution in an organic solvent or a dispersion in water, and an aqueous dispersion is usually preferably used from the standpoint of safety, hygiene, and environmental pollution.

Patent Document 1 describes that a resin dispersion in which a polymer in which a hydrophilic polymer is bonded to an acid-modified polyolefin is dispersed in an aqueous medium can be used as a paint, primer, or adhesive for polyolefin, and that a laminate as a coated product is described. has been done. However, since the method described in Patent Document 1 requires a large amount of energy during baking to obtain a dry coating film, problems remain in terms of environmental impact.

On the other hand, in order to facilitate the adhesion of the modified polyolefin to the base material, a method using a polyolefin molded article modified with a rubber component is also commonly used. For example, Patent Document 2 discloses that a block copolymer made of propylene and ethylene, an ethylene/α-olefin random copolymer rubber, and talc or calcium carbonate are used to produce a rubber material with excellent impact resistance, rigidity, paintability, etc. A propylene polymer composition is disclosed. However, although this method provides good paintability and adhesion, the rigidity of the molded product decreases, so there remains a problem in using it as a member that requires strength.

Japanese Patent Application Publication No. 2007-270122 Japanese Patent Publication No. 62-256856

The object of the present invention is to provide a polyolefin resin powder that can obtain a polyolefin resin molded article with excellent coating film adhesion without requiring surface treatment using special equipment, coating of an adhesive layer, or modification with a rubber component. An object of the present invention is to provide a resin composition, a molded article, and a method for producing the molded article.

That is, the gist of the present invention is as follows.
[1] A polyolefin resin powder containing a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide.
[2] Weight that passes through the sieve when 10 g of polyolefin resin powder is placed on a sieve with a diameter of 75 mm and an opening of 5.6 mm and shaken 20 times at an amplitude of 200 mm and a shaking speed of 1 time/sec from side to side. The polyolefin resin powder according to [1], wherein the proportion is 90% or more and 100% or less.
[3] The compound having a repeating unit derived from alkylene oxide is a compound having one or more repeating units selected from the group consisting of repeating units derived from ethylene oxide and repeating units derived from propylene oxide [1] or [2] ] Polyolefin resin powder.
[4] The polyolefin resin powder according to any one of [1] to [3], which has an average particle diameter of more than 1.0 μm and less than 5.6 mm.
[5] The polyolefin resin powder according to any one of [1] to [4], wherein the content of volatile components is 10% by weight or less.
[6] The polyolefin resin powder according to any one of [1] to [5], which has a melting point of 120° C. or less when measured using a polyolefin resin powder dried at 40° C. for 6 hours under reduced pressure of 5 mmHg or less as a sample.
[7] The polyolefin resin powder according to any one of [1] to [6], which has a weight average molecular weight of 50,000 or more, as measured by using a polyolefin resin powder dried at 40° C. for 6 hours under reduced pressure of 5 mmHg or less as a sample.
[8] A resin composition containing the polyolefin resin powder according to any one of [1] to [7].
[9] The resin composition according to [8], which further contains another olefin resin in addition to the polyolefin resin powder according to any one of [1] to [7].
[10] The resin composition of [8] or [9], wherein the content of the polyolefin resin powder of any one of [1] to [7] is 0.1 to 70% by weight.
[11] A polyolefin resin molded article having a water contact angle of 100° or less on the surface and containing a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide, which is an injection molded article.
[12] A polyolefin resin molded article containing the polyolefin resin powder according to any one of [1] to [7].
[13] A method for producing a polyolefin resin molded article, comprising injection molding of a compound containing the polyolefin resin powder according to any one of [1] to [7].

According to the present invention, there is provided a polyolefin resin powder capable of obtaining a polyolefin resin molded article with excellent coating film adhesion without requiring surface treatment using special equipment, coating of an adhesive layer, or modification with a rubber component. It is possible to provide a resin composition obtained using the present invention, a molded article, and a method for producing a molded article.

In this specification, "~" means to include the numbers before and after it.
In this specification, "powder" includes primary particles, secondary particles formed by agglomeration of primary particles, and aggregates formed by aggregation of these particles.
In the present invention, "(meth)acrylic" means a generic term for acrylic and methacryl.

[Polyolefin resin powder]
In the present invention, polyolefin resin powder means powder containing a polyolefin polymer. A powder form is preferable from the viewpoint of improving the paintability and adhesion of the molded article. The polyolefin polymer refers to a polymer using olefin as a raw material monomer, and includes olefin polymers such as olefin homopolymers and copolymers.

In the polyolefin resin powder of the present invention, the polyolefin polymer (hereinafter sometimes referred to as "olefin polymer (A)") includes, for example, an olefin polymer (A1) that does not have a reactive group. (Hereinafter, it may be written as "polymer (A1)"), a modified olefin polymer (A2) having a reactive group (hereinafter, it may be written as "polymer (A2)"). can be mentioned. The olefin polymer (A) is preferably a polymer (A2).

In the polyolefin resin powder of the present invention, preferred embodiments of the olefin polymer (A) include olefin polymers that satisfy one or both of the following (1) and (2).
(1) In terms of good compatibility with propylene resin, the content of propylene-derived repeating units relative to all repeating units of the olefin polymer is preferably 50 mol% or more, more preferably 60 mol% or more, More preferably, the olefin polymer has a content of 70 mol% or more.
(2) The melting point [Tm] is preferably 120°C or lower, more preferably 100°C or lower, even more preferably 90°C or lower, particularly preferably 80°C, in order to improve the paintability and adhesion of the resin molded article. An olefin polymer that is: Further, the temperature is preferably 60°C or higher from the viewpoint of excellent blocking properties. For example, the temperature is preferably 60 to 120°C, more preferably 60 to 100°C, even more preferably 60 to 90°C, and particularly preferably 60 to 80°C.

The polyolefin resin powder of the present invention preferably has a melting point of 120°C or lower, more preferably 100°C or lower, even more preferably 90°C or lower, and even more preferably 80°C or lower when dried at 40°C for 6 hours under reduced pressure of 5 mmHg or lower. The following are particularly preferred. Further, the temperature is preferably 60°C or higher. For example, the temperature is preferably 60 to 120°C, more preferably 60 to 100°C, even more preferably 60 to 90°C, and particularly preferably 60 to 80°C. If it is below the above-mentioned upper limit, the paintability and adhesion of the resin molded article will be good, and if it is above the above-mentioned lower limit, it will have excellent blocking properties. The melting point of a sample obtained by drying polyolefin resin powder at 40° C. for 6 hours under reduced pressure of 5 mmHg or less indicates the peak top temperature of the crystal melting peak when measured using a differential scanning calorimeter.

[Olefin polymer (A1) without reactive group]
As the polymer (A1), known olefin polymers and olefin copolymers that do not have reactive groups can be used. In this specification, the reactive group means a carboxyl group and its anhydride, an amino group, an epoxy group, an isocyanate group, a sulfonyl group, and a hydroxyl group.
The polymer (A1) is not particularly limited, but includes, for example, a homopolymer of ethylene or propylene; a copolymer of ethylene and propylene; one or more types of ethylene and propylene, and other monomers such as butene. -1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene, and norbornene. copolymer with two or more types of other olefin monomer (M); other olefin monomer (M) and, for example, a copolymer with vinyl acetate, acrylic ester, or methacrylic ester; a copolymer of another olefin monomer (M) and, for example, an aromatic vinyl monomer, or a hydrogenated product thereof; Examples include conjugated diene block copolymers or hydrogenated products thereof.

Since the polymer (A1) provides good paintability and adhesion of resin molded articles, the repeating units contained in the polymer (A1) include repeating units derived from α-olefin monomers having 2 to 4 carbon atoms. Units are preferred. Note that the various copolymers described above may be one or both of a random copolymer and a block copolymer.
As the copolymer as the above-mentioned polymer (A1), a chlorinated polyolefin obtained by chlorinating a polyolefin can also be used. In order to improve the solubility of the olefin polymer (A1) in a solvent, the degree of chlorination of the chlorinated polyolefin when the polyolefin is chlorinated is preferably 5% by weight or more based on the total mass of the polyolefin, More preferably 10% by weight or more. Further, it is preferably 40% by weight or less, more preferably 30% by weight or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 40% by weight, more preferably 10 to 30% by weight.

Examples of the polymer (A1) include polyethylene, polypropylene, ethylene-butene copolymer, ethylene-propylene copolymer, propylene-butene copolymer, propylene-hexene copolymer, chlorinated polyethylene, chlorinated polypropylene, Chlorinated ethylene-propylene copolymer, chlorinated propylene-butene copolymer, ethylene-vinyl acetate copolymer, hydrogenated product of styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer Examples include hydrogenated polymers (SEPS).

In terms of good compatibility with the propylene resin, examples of the polymer (A1) include propylene homopolymers, copolymers of propylene and other olefin monomers (M), and chlorinated versions thereof. Preferred are propylene homopolymers, ethylene-propylene copolymers, propylene-butene copolymers, chlorinated polypropylene, chlorinated ethylene-propylene copolymers, and chlorinated propylene-butene copolymers, More preferred are propylene homopolymers, ethylene-propylene copolymers, propylene-butene copolymers, and ethylene-propylene-butene copolymers that do not contain chlorine.

The polymer (A1) may be used alone or in combination of two or more.

As the polymer (A1), a propylene-based polymer having a repeating unit derived from propylene is preferred. When the polymer (A1) has repeating units derived from propylene, its compatibility with the polypropylene resin tends to increase. The proportion of repeating units derived from propylene to all repeating units of the propylene polymer is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more. Moreover, 100 mol% or less is preferable. For example, it is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%. If it is within the above range, it has sufficient compatibility with the polypropylene resin, and the higher the proportion of repeating units derived from propylene, the more the compatibility with the polypropylene resin tends to increase, and the appearance of the molded product improves. , the adhesion of the paint film when applied is improved.

In the polyolefin resin powder of the present invention, the weight average molecular weight Mw of the polymer (A1) can be measured by GPC (Gel Permeation Chromatography) and converted using the calibration curve of each polyolefin to determine the weight average molecular weight Mw. The weight average molecular weight Mw of the polymer (A1) is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 50,000 or more, and particularly preferably 100,000 or more. Moreover, 500,000 or less is preferable, and 300,000 or less is more preferable. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 5,000 to 500,000, more preferably 10,000 to 500,000, even more preferably 50,000 to 300,000, and particularly preferably 100,000 to 300,000. Within the above range, the greater the weight average molecular weight Mw, the more rigid the resin molded article tends to be. Further, within the above range, the smaller the weight average molecular weight Mw, the higher the compatibility with the olefin resin tends to be.
The polyolefin resin powder of the present invention preferably has a weight average molecular weight Mw of 50,000 or more, more preferably 100,000 or more, as measured from a sample dried at 40° C. for 6 hours under reduced pressure of 5 mmHg or less. Further, it is preferably 500,000 or less, more preferably 300,000 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 50,000 to 500,000, more preferably 100,000 to 300,000. If it is within the above range, the molded product will have sufficient rigidity, and the impact resistance and scratch resistance of the molded product will increase. Furthermore, the greater the weight average molecular weight Mw, the higher the rigidity of the molded article tends to be. In addition, within the above range, there is sufficient compatibility with the olefin resin, the appearance of the molded article is improved, and the adhesion of the paint film when applied is improved. The smaller the weight average molecular weight Mw, the higher the compatibility with the olefin resin.

The weight average molecular weight Mw can be measured by GPC using a conventionally known method using a commercially available GPC device, for example, using orthodichlorobenzene as a solvent.

The melting point Tm of the polymer (A1) is preferably 120°C or lower, more preferably 100°C or lower, and even more preferably 90°C or lower. Further, the temperature is preferably 50°C or higher. For example, the temperature is preferably 50 to 120°C, more preferably 50 to 100°C, even more preferably 50 to 90°C. If it is within the above range, the molded product will have sufficient rigidity, and the impact resistance and scratch resistance of the molded product will increase. Furthermore, the higher the melting point Tm, the higher the rigidity of the molded article tends to be. In addition, within the above range, there is sufficient compatibility with the olefin resin, the appearance of the molded article is improved, and the adhesion of the paint film when applied is improved. Furthermore, the lower the melting point Tm, the higher the compatibility with the olefin resin.

The method for producing the polymer (A1) is not particularly limited. Examples of methods for producing the polymer (A1) include radical polymerization, cationic polymerization, anionic polymerization, and coordination polymerization, each of which may be a living polymerization method.

When producing the polymer (A1) by coordination polymerization, examples include a method of polymerization using a Ziegler-Natta catalyst and a method of polymerizing using a single site catalyst. Polymerization using a single-site catalyst is preferred because the molecular weight distribution and stereoregularity distribution can be sharpened by the design of the ligand.

As the single site catalyst used in the method of polymerization using a single site catalyst, for example, a metallocene catalyst or a Brookhart type catalyst can be used. As the metallocene catalyst, an appropriate catalyst may be selected depending on the stereoregularity of the polyolefin to be polymerized, such as a C1 symmetric type, a C2 symmetric type, a C2V symmetric type, a CS symmetric type, etc.

As a method for producing the polymer (A1), any polymerization method such as solution polymerization, slurry polymerization, bulk polymerization, gas phase polymerization, etc. can be used. Examples of solvents for producing the polymer (A1) by solution polymerization and slurry polymerization include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, and octane; cyclohexane and methylcyclohexane. alicyclic hydrocarbons such as; halogenated hydrocarbons, esters, ketones, and ethers. In terms of easily dissolving the polymer (A1), aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferred, and toluene, xylene, heptane, and cyclohexane are more preferred. These may be used alone or in combination of two or more.
The molecular structure of the polymer (A1) may be linear or branched.

[Modified olefin polymer having reactive group (A2)]
As the polymer (A2), for example, a copolymer (A2a) obtained by copolymerizing an olefin and a radically polymerizable unsaturated compound having a reactive group during polymerization (hereinafter referred to as "modified polymer (A2a)") ), a graft polymer (A2b) in which a radically polymerizable unsaturated compound having a reactive group is graft-polymerized onto a polymer having a repeating unit derived from an olefinic monomer (hereinafter referred to as a "modified graft polymer ( A2b)") may be mentioned.

The modified polymer (A2a) is obtained by copolymerizing an olefin and a radically polymerizable unsaturated compound having a reactive group, and is a copolymer in which the radically polymerizable unsaturated compound having a reactive group is introduced into the main chain. It is a polymer. Examples of the reactive group include carboxyl group and its anhydride, amino group, epoxy group, isocyanate group, sulfonyl group, and hydroxyl group. The radically polymerizable unsaturated compounds having a reactive group may be used alone or in combination of two or more.
In view of the excellent reactivity of the reactive group, the reactive group in the radically polymerizable unsaturated compound having a reactive group is preferably a carboxyl group or its anhydride. Examples of the modified polymer (A2a) include α-olefins such as ethylene, propylene, butene, and carboxyl groups such as (meth)acrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, and anhydrides thereof. Examples include copolymers of radically polymerizable unsaturated compounds having α,β-unsaturated carboxylic acids or anhydrides thereof, such as radically polymerizable unsaturated compounds having the above-mentioned properties, or anhydrides thereof. Examples of the modified polymer (A2a) include ethylene-acrylic acid copolymer and ethylene-acrylic acid ester-maleic anhydride copolymer. These may be used alone or in combination of two or more.
The modified polymer (A2a) can be produced in the same manner as described for the polymer (A1).

The modified graft polymer (A2b) can be obtained by graft polymerizing a radically polymerizable unsaturated compound having a reactive group onto a polymer having repeating units derived from an olefinic monomer. As the reactive group, those similar to those listed for the modified polymer (A2a) can be used.
The radically polymerizable unsaturated compounds having a reactive group may be used alone or in combination of two or more.
In view of the excellent reactivity of the reactive group, the reactive group in the radically polymerizable unsaturated compound having a reactive group is preferably a carboxyl group or its anhydride. For example, a radically polymerizable unsaturated compound having a carboxyl group, such as (meth)acrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, or anhydride thereof, or anhydride thereof is grafted onto a polyolefin such as polyethylene or polypropylene. Examples include polymerized polymers.
The polyolefin resin powder of the present invention uses a radically polymerizable unsaturated compound having a carboxyl group or its anhydride as a modified polymer (A2a) and/or a modified graft polymer (A2b), preferably as a modified graft polymer (A2b). Containing 2% by weight or more of an acid-modified polyolefin copolymerized and/or graft-polymerized improves the modification rate of a compound having a repeating unit derived from alkylene oxide, which will be described later, and improves the content of the acid-modified polyolefin copolymerized and/or graft-polymerized. This is preferable because it improves the paintability and adhesion. The content of acid-modified polyolefin contained in the polyolefin resin powder is more preferably 10% by weight or more, further preferably 30% by weight or more, and particularly preferably 50% by weight or more.

The polymer (A1) can be used as the polymer having a repeating unit derived from an olefin monomer that can be used in the modified graft polymer (A2b).
Examples of the modified graft polymer (A2b) include maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-modified propylene-butene copolymer, acrylic acid-modified polypropylene, and acrylic acid-modified ethylene-propylene. Examples include propylene copolymers, acrylic acid-modified propylene-butene copolymers, and chlorinated products thereof. These may be used alone or in combination of two or more.

The modified graft polymer (A2b) can be produced using radical polymerization. The radical polymerization initiator used in the production using radical polymerization can be appropriately selected from common radical polymerization initiators, and examples thereof include organic peroxides and azonitrile. These may be used alone or in combination of two or more.
Examples of organic peroxides include peroxyketals such as di(t-butylperoxy)cyclohexane; hydroperoxides such as cumene hydroperoxide; dialkyl peroxides such as di(t-butyl)peroxide; Examples include diacyl peroxides such as benzoyl peroxide; and peroxy esters such as t-butylperoxyisopropyl monocarbonate.
Examples of azonitrile include azobisbutyronitrile and azobisisopropylnitrile.
As the radical polymerization initiator, benzoyl peroxide and t-butylperoxyisopropyl monocarbonate are preferred because they have a strong hydrogen abstracting power and are excellent in grafting reactions.

When producing the modified graft polymer (A2b) by radical polymerization, the ratio (mole ratio) of the radical polymerization initiator to all repeating units contained in the modified graft polymer (A2b) is: radical polymerization initiator: modified graft polymer. The total number of repeating units contained in the aggregate (A2b) is preferably 1:100 to 2:1, more preferably 1:20 to 1:1. Within the above range, bonding between the produced modified graft polymers can be suppressed.
The reaction temperature when producing the modified graft polymer (A2b) by radical polymerization is preferably 50°C or higher, more preferably 80 to 200°C. If it is within the above range, the grafting reaction will proceed sufficiently due to the hydrogen abstracting force of the radical polymerization initiator. The reaction time is usually about 2 to 20 hours.

The method for producing the modified graft polymer (A2b) is not particularly limited, but includes, for example, a method of dissolving it in a solvent and reacting, a method of reacting by melting and stirring without a solvent, a method of reacting by heating and kneading with an extruder. There are several methods.
As a solvent in the case of manufacturing by dissolving in a solvent, the solvents exemplified for polymer (A1) can be similarly used.

The content of reactive groups in the polymer (A2) is preferably 0.01 mmol/g or more, more preferably 0.02 mmol/g or more, even more preferably 0.05 mmol/g or more per 1 g of the polymer (A2). . Moreover, it is preferably 1 mmol/g or less, more preferably 0.5 mmol/g or less, and even more preferably 0.3 mmol/g or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.01 to 1 mmol/g, more preferably 0.02 to 0.5 mmol/g, even more preferably 0.05 to 0.3 mmol/g. If it is within the above range, the hydrophilicity of the polymer (A2) increases, so that the molded product has sufficient paintability and adhesion, and the higher the content of reactive groups, the better the paintability of the molded product. There is a tendency for the adhesion to improve. In addition, within the above range, the polymer (A2) and the olefin resin have sufficient compatibility, and the lower the content of the reactive group, the more compatible the polymer (A2) and the olefin resin are. Solubility tends to increase.

When the polyolefin resin powder of the present invention contains a polymer (A2), the content of the polymer (A2) is preferably 2% by weight or more, more preferably 10% by weight or more, even more preferably 30% by weight or more, and 50% by weight or more. Particularly preferably % by weight or more. Further, it is preferably 99% by weight or less, more preferably 90% by weight or less, and even more preferably 80% by weight or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 2 to 99% by weight, more preferably 10 to 99% by weight, even more preferably 30 to 90% by weight, and particularly preferably 50 to 80% by weight. If it is within the above range, the particle size of the polyolefin resin powder can be easily controlled, and the coating properties and adhesion of the coating material when used in a molded article are likely to be improved.

A resin dispersion can also be used as the olefin polymer (A). As the resin dispersion of the olefin polymer (A), for example, Aptlock manufactured by Mitsubishi Chemical Co., Ltd., Auroren and Superclone manufactured by Nippon Paper Industries, Hardlene manufactured by Toyobo Co., Ltd., and Arrowbase manufactured by Unitika Co., Ltd. are used, for example. You can also do that.

The polyolefin resin powder of the present invention contains a polyolefin resin (polyolefin polymer) modified with a compound having repeating units derived from alkylene oxide. The compound having a repeating unit derived from alkylene oxide is preferably a compound having a polyoxyalkylene structure.
The compound having a repeating unit derived from alkylene oxide is preferably a compound having one or more types of repeating units derived from ethylene oxide and propylene oxide. When the compound having a repeating unit derived from alkylene oxide is a compound having one or more types of repeating units derived from ethylene oxide and propylene oxide, the paintability and adhesion of the molded article tend to be good.
A compound having a repeating unit derived from alkylene oxide is, for example, a repeating unit derived from ethylene oxide, a repeating unit derived from propylene oxide, a repeating unit derived from butylene oxide, and a repeating unit derived from tetramethylene oxide, either alone or in combination of two or more. Has a structure.

The weight average molecular weight of a compound having a repeating unit derived from alkylene oxide can be measured using GPC. The weight average molecular weight Mw of the compound having a repeating unit derived from alkylene oxide measured by GPC using a polystyrene calibration curve is preferably 200 or more, more preferably 300 or more, and even more preferably 500 or more. Further, it is preferably 100,000 or less, more preferably 10,000 or less, and even more preferably 5,000 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 200 to 100,000, more preferably 300 to 10,000, even more preferably 500 to 5,000. When the weight average molecular weight Mw is at least the above lower limit, the paintability and adhesiveness of the molded article are likely to be improved. When the weight average molecular weight Mw is below the above upper limit, the compatibility with the olefin resin tends to improve.
GPC measurement is performed by a conventionally known method using, for example, a commercially available device using tetrahydrofuran as a solvent.

The polyolefin resin powder of the present invention preferably contains an olefin polymer (A) modified with a compound having a repeating unit derived from alkylene oxide.
The polyolefin resin powder of the present invention preferably contains an olefin polymer (A) modified with a compound having repeating units derived from alkylene oxide, and a compound having repeating units derived from alkylene oxide. The polyolefin resin powder of the present invention may further contain an olefin polymer (A) that is not modified with a compound having repeating units derived from alkylene oxide.
In the polyolefin resin powder of the present invention, by using an olefin polymer (A) modified with a compound having repeating units derived from alkylene oxide, it is possible to use a polyolefin resin powder containing a compound having repeating units derived from alkylene oxide. When formed into a molded article, the dispersibility of the compound having a repeating unit derived from alkylene oxide contained in the polyolefin resin powder is improved, and the paintability and adhesiveness are improved.

Examples of methods for modifying polyolefin resins (polyolefin polymers), particularly olefin polymers (A), with compounds having repeating units derived from alkylene oxide include, for example,
(1) A method of reacting the reactive group of the olefin polymer (A2) with a compound having a repeating unit derived from an alkylene oxide having a functional group that can react;
(2) A method of grafting a compound having a repeating unit derived from an alkylene oxide having a radically polymerizable group in the presence of the olefin polymer (A) using a radical polymerization initiator capable of abstracting hydrogen;
(3) A method of copolymerizing a compound having a repeating unit derived from an alkylene oxide having a radically polymerizable group during the polymerization of the olefin polymer (A),
(4) A method of ring-opening polymerization of a cyclic alkylene oxide during polymerization of the olefin polymer (A),
can be mentioned.
From the viewpoint of simplicity of synthesis and ease of reaction control, (1) a method of reacting the reactive group of the olefin polymer (A2) with a compound having a repeating unit derived from an alkylene oxide having a functional group capable of reacting with the reactive group of the olefin polymer (A2); is preferred.
In the compound having a repeating unit derived from alkylene oxide which has a functional group capable of reacting with the reactive group of the olefin polymer (A), the functional group capable of reacting with the reactive group of the olefin polymer (A) includes olefin-based Depending on the type of reactive group in the polymer (A), examples thereof include a carboxylic acid group, a dicarboxylic acid anhydride group, a dicarboxylic acid monoester group, a hydroxyl group, an amino group, an epoxy group, and an isocyanate group, with an amino group being preferred. Amino groups are preferred because they are highly reactive with various reactive groups such as carboxylic acid groups, carboxylic anhydride groups, glycidyl groups, and isocyanate groups, so that they can easily be bonded to polyolefins and hydrophilic polymers. The amino group may be primary, secondary, or tertiary, with primary amino groups being preferred.
In a compound having a repeating unit derived from an alkylene oxide that has a functional group that can react with the reactive group of the olefin polymer (A), the functional group that can react with the reactive group of the olefin polymer (A) is within the molecule. It is sufficient if there is one or more, but it is preferable to have only one. If the number of such functional groups is only one, a three-dimensional network structure is formed when bonding with the olefin polymer (A), and gelation can be suppressed. However, even if it has a plurality of such functional groups, it suffices as long as it has only one highly reactive functional group. For example, a preferred example is a hydrophilic polymer having multiple hydroxyl groups and one amino group that is more reactive than the hydroxyl group. Here, reactivity means reactivity with the reactive group of the olefin polymer (A).
Examples of the compound having a repeating unit derived from an alkylene oxide having a primary amino group include Jeffamine M series, D series, and ED series manufactured by Huntsman, which are polyalkylene oxides having a primary amino group.
Examples of the linking group formed by reacting the reactive group of the olefin polymer (A) with the functional group of a compound having a repeating unit derived from alkylene oxide include an amide bond, an ester bond, a carbonate bond, Examples include urethane bonds and ether bonds, with amide bonds being preferred.

In the polyolefin resin powder of the present invention, as the compound having a repeating unit derived from alkylene oxide, in addition to the above-mentioned compounds, a compound that does not react with the olefin polymer (A) may be used. Examples of compounds having repeating units derived from alkylene oxide that do not react with the olefin polymer (A) include surfactants having repeating units derived from alkylene oxide.

In the polyolefin resin powder of the present invention, the content of the polyolefin resin modified with a compound having repeating units derived from alkylene oxide, particularly the olefin polymer (A) modified with a compound having repeating units derived from alkylene oxide, is as follows: The content is preferably 40% by weight or more, more preferably 55% by weight or more, and even more preferably 65% by weight or more. Further, it is preferably 99% by weight or less, more preferably 98% by weight or less, even more preferably 95% by weight or less, and particularly preferably 90% by weight or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 40 to 99% by weight, more preferably 40 to 98% by weight, even more preferably 55 to 95% by weight, and particularly preferably 65 to 90% by weight. If it is within the above range, the particle size of the polyolefin resin powder can be easily controlled, and the coating properties and adhesion of the coating material when used in a molded article are likely to be improved.

In the polyolefin resin composition and polyolefin resin molded article containing the polyolefin resin powder of the present invention, a polyolefin resin modified with a compound having a repeating unit derived from an alkylene oxide, particularly a compound having a repeating unit derived from an alkylene oxide. The content of the olefin polymer (A) is preferably 0.1% by weight or more, more preferably 1% by weight or more, even more preferably 3% by weight or more, even more preferably 10% by weight or more, and even more preferably 30% by weight or more. Particularly preferred. Further, it is preferably 99% by weight or less, more preferably 98% by weight or less, even more preferably 95% by weight or less, and particularly preferably 90% by weight or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.1 to 99% by weight, more preferably 1 to 99% by weight, even more preferably 3 to 98% by weight, even more preferably 10 to 95% by weight, and particularly preferably 30 to 90% by weight. If it is above the lower limit, the paintability and adhesiveness of the coating material when formed into a molded article are likely to be improved. If it is less than the above upper limit, the rigidity and appearance of the molded article are likely to be improved.

When the polyolefin resin powder of the present invention contains a compound having repeating units derived from alkylene oxide, the content of the compound having repeating units derived from alkylene oxide in the polyolefin resin powder is preferably 1% by weight or more, and preferably 2% by weight. The content is more preferably 5% by weight or more, even more preferably 10% by weight or more. Further, it is preferably 60% by weight or less, more preferably 45% by weight or less, and even more preferably 35% by weight or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 60% by weight, more preferably 2 to 60% by weight, even more preferably 5 to 45% by weight, and particularly preferably 10 to 35% by weight. If it is within the above range, the coating properties and adhesion of the coating material when used on a molded article are likely to be improved.

When the polyolefin resin composition and polyolefin resin molded article containing the polyolefin resin powder of the present invention contain a compound having a repeating unit derived from alkylene oxide, the polyolefin resin composition and polyolefin resin molded article contain a repeating unit derived from alkylene oxide. The content of the compound is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, even more preferably 1% by weight or more, and particularly preferably 3% by weight or more. Further, it is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and particularly preferably 10% by weight or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.1 to 50% by weight or more, more preferably 0.5 to 30% by weight or more, even more preferably 1 to 20% by weight or more, and particularly preferably 3 to 10% by weight or more. If it is above the lower limit, the paintability and adhesiveness of the coating material when formed into a molded article are likely to be improved. If it is less than the above upper limit, the rigidity and appearance of the molded article are likely to be improved.

In the polyolefin resin powder of the present invention, a polyolefin resin modified with a compound having repeating units derived from alkylene oxide, particularly an olefin polymer (A) modified with a compound having repeating units derived from alkylene oxide and an alkylene oxide derived [polyolefin resin modified with a compound having repeating units derived from alkylene oxide]/[compound having repeating units derived from alkylene oxide] or [repeating units derived from alkylene oxide] The weight ratio expressed by olefin polymer (A) modified with a compound having a compound having a repeating unit derived from an alkylene oxide] is preferably from 99/1 to 1/99, and preferably from 99/1 to 50 /50 is more preferable, and 99/2 to 70/30 is even more preferable.

The polyolefin resin powder of the present invention includes:
- Suspension polymer particles containing a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide, particularly an olefin polymer (A) modified with a compound having a repeating unit derived from alkylene oxide,
- A powder obtained by pulverizing a lump containing a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide, particularly an olefin polymer (A) modified with a compound having a repeating unit derived from alkylene oxide,
・Heat-melt and pelletize a polyolefin resin modified with a compound having repeating units derived from alkylene oxide, particularly a resin composition containing an olefin polymer (A) modified with a compound having repeating units derived from alkylene oxide. what you did,
- Filtration and/or a dispersion of a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide, particularly a dispersion of a resin containing an olefin polymer (A) modified with a compound having a repeating unit derived from alkylene oxide. dry powder,
- A polyolefin resin modified with a compound having repeating units derived from alkylene oxide, particularly a resin containing an olefin polymer (A) modified with a compound having repeating units derived from alkylene oxide, is dissolved in a solvent or heated and melted. , a powder precipitated in a poor solvent and then filtered and/or dried;
can be mentioned.
As a method for drying a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide, particularly a dispersion of a resin containing an olefin polymer (A) modified with a compound having a repeating unit derived from alkylene oxide, Examples include a method of precipitating in a poor solvent, filtration and/or drying, and a spray drying method.
From the viewpoint of easy particle size control and improved strength and appearance when used in a molded article, a method that yields a dried powder state is preferable, and a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide, Particularly preferred is a method in which a dispersion of a resin containing an olefin polymer (A) modified with a compound having repeating units derived from alkylene oxide is dried by spray drying to form a powder.

[Polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide, particularly a dispersion of a resin containing an olefin polymer (A) modified with a compound having a repeating unit derived from alkylene oxide]
A dispersion of a polyolefin resin modified with a compound having repeating units derived from alkylene oxide, particularly a resin containing an olefin polymer (A) modified with a compound having repeating units derived from alkylene oxide, is prepared by dispersing resin particles in a solvent. has a dispersed aspect. The solvent used for dispersion may be either water or an organic solvent, or a combination of two or more thereof, but preferably 90% by weight or more of the total solvent used is water.
A polyolefin resin modified with a compound having repeating units derived from alkylene oxide, particularly an olefin polymer (A) modified with a compound having repeating units derived from alkylene oxide, and a compound having repeating units derived from alkylene oxide. As a method for producing a resin dispersion containing, for example,
- A method of dispersing the polyolefin resin, especially the olefin polymer (A) in water by incorporating a surfactant into the polyolefin resin, especially the olefin polymer (A),
- A method of dispersing in water a polyolefin resin, especially a graft copolymer in which a hydrophilic polymer is grafted to an olefin polymer (A);
- When the reactive group of the polymer (A2) is an acidic group such as a carboxyl group, its anhydride, or a sulfonyl group, by neutralizing these acidic groups with a basic compound, the polymer (A2) ) in water,
can be mentioned.

Used in producing a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide, particularly a resin dispersion containing an olefin polymer (A) modified with a compound having a repeating unit derived from alkylene oxide. Hydrophilic polymer means a polymer in which the insoluble content is 1% by weight or less when dissolved in water at 25° C. at a concentration of 10% by weight. The hydrophilic polymer can be used without any particular limitation as long as it does not significantly impair the effects of the present invention, and for example, synthetic polymers, semi-synthetic polymers, and natural polymers can be used. From the viewpoint of excellent mechanical stability of the resin dispersion, the number average molecular weight Mn of the hydrophilic polymer is preferably 300 or more. Further, from the viewpoint of excellent mechanical stability of the resin dispersion, it is preferable to use a compound having the above-mentioned alkylene oxide-derived repeating unit as the hydrophilic polymer.

In the polyolefin resin powder of the present invention, a polyolefin resin modified with a compound having a repeating unit derived from an alkylene oxide, particularly a resin dispersion containing an olefin polymer (A) modified with a compound having a repeating unit derived from an alkylene oxide. Examples of basic compounds used in producing the compound include inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonia; triethylamine, diethylamine, ethanolamine, dimethylethanolamine, and 2-methyl-2-amino-propanol. , triethanolamine, morpholine, pyridine, and other organic bases. The neutralization rate with the basic compound is not particularly limited as long as dispersibility in water can be obtained, but it is preferably 1 to 100 mol%, more preferably 50 to 100 mol%, based on the acidic group. If it is within the above range, sufficient dispersibility in water can be easily obtained by neutralization, and the higher the neutralization rate, the better the dispersibility in water.

It is preferable that the weight percentage of the polyolefin resin powder of the present invention that passes through a sieve with a diameter of 75 mm and an opening of 5.6 mm is 90% or more. In particular, when 10 g of the polyolefin resin powder is placed on a sieve with a diameter of 75 mm and an opening of 5.6 mm, and the powder is shaken 20 times with an amplitude of 200 mm and a shaking speed of 1 time/second from side to side, the weight that passes through the sieve is It is preferable that the ratio is 90% or more and 100% or less. If the weight ratio passing through a sieve with a diameter of 75 mm and an opening of 5.6 mm is 90% or more, the paintability and adhesion properties when used in molded objects will improve, and the polyolefin resin powder can be used by dissolving it in a solvent. In some cases, it can be dissolved in a solvent in a short time.

The average particle diameter of the polyolefin resin powder of the present invention is preferably larger than 1 μm, more preferably 3.5 μm or more, even more preferably 5 μm or more, and even more preferably 8 μm or more. Further, the thickness is preferably 5 mm or less, more preferably 1 mm or less, even more preferably 700 μm or less, even more preferably 100 μm or less, and particularly preferably 30 μm or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably larger than 1 μm and 5.6 mm or less, more preferably larger than 1 μm and 1 mm or less, even more preferably 3.5 to 700 μm, even more preferably 5 to 100 μm, and particularly preferably 8 to 30 μm. If the average particle diameter is below the above upper limit, the coating properties and adhesion properties when used in a molded article are likely to be improved. If it is more than the lower limit, the handleability when used in a molded article is likely to be improved. Moreover, if the average particle diameter is below the above-mentioned upper limit, when the polyolefin resin powder is used after being dissolved in a solvent, it can be dissolved in the solvent in a short time.
The average particle diameter can be measured by, for example, a dynamic light scattering method, a laser Doppler method, or an image-based particle size distribution measurement method. The average particle diameter in the present invention means the volume average particle diameter that accounts for 50% of the cumulative particle size distribution in the volume-based particle size distribution.

The polyolefin resin powder of the present invention may contain resins other than the above-mentioned polyolefin resin (polyolefin polymer) as long as the paintability and adhesiveness of the molded article are not impaired. Examples of resins other than the aforementioned polyolefin resins (polyolefin polymers) include olefin resins other than the aforementioned polyolefin resins (polyolefin polymers), acrylic resins, urethane resins, polyester resins, polycarbonate resins, polystyrene resins, vinyl acetate resins, Examples include vinyl chloride resin, vinylidene chloride resin, styrene-butadiene resin, butadiene resin, poly(meth)acrylonitrile resin, (meth)acrylamide resin, nylon resin, phenol resin, silicone resin, and epoxy resin.

A polyolefin resin powder containing a resin other than the above-mentioned polyolefin resin (polyolefin polymer) can be produced, for example, by coexisting a resin other than the above-mentioned polyolefin resin (polyolefin polymer) with the olefin polymer (A) by the following method. can do.
- A method of polymerizing a radically polymerizable monomer in a dispersion of an olefin polymer (A).
- A method in which the olefin polymer (A) and the radically polymerizable monomer are dissolved and polymerized after being dispersed.
- A method in which the olefin polymer (A) and a resin other than the above-mentioned polyolefin resin (polyolefin polymer) are melt-kneaded or dissolved using a solvent.
From the viewpoint of paintability and adhesiveness of the molded article, a method in which a radically polymerizable monomer is polymerized in a dispersion of the olefin polymer (A) is preferred.

The polyolefin resin powder of the present invention includes, for example, elastomers, plasticizers, solvents, crosslinking agents, lubricants, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, dyes, and pigments. It can contain colorants such as, and modifying resins.

The polyolefin resin powder of the present invention may contain volatile components, and when the polyolefin resin powder of the present invention contains volatile components, the amount of volatile components is preferably 10% by weight or less, more preferably 5% by weight or less. , 3% by weight or less is more preferable, and it is particularly preferable that no volatile components are included. If the amount of volatile components is within the above range, the appearance when used in a molded article is likely to be improved.
The amount of volatile components means a value calculated from the remaining weight when no weight loss is observed for 60 seconds when 1.0 g of a sample is heated at a temperature of 180° C. using an infrared moisture meter.

[Resin composition (D)]
The resin composition of the present invention (hereinafter sometimes referred to as "resin composition (D)") contains the polyolefin resin powder of the present invention.The content of the polyolefin resin powder in the resin composition (D) is The amount is preferably 0.1 to 70% by weight, more preferably 1 to 50% by weight, and even more preferably 2 to 30% by weight.Within the above range, the molded product has sufficient paintability and adhesion. In addition, the higher the content, the better the paintability and adhesion when formed into a molded object.In addition, within the above range, when formed into a molded object, the content will have sufficient rigidity. The lower the amount, the easier it is to increase the rigidity when formed into a molded product.
In the resin composition (D), the polyolefin resin powder may be dissolved or dispersed. In the resin composition (D), the polyolefin resin powder may or may not have a powder form.

Components other than the polyolefin resin powder contained in the resin composition (D) are not particularly limited, but the same components as the aforementioned polyolefin resin powder may be used. It is preferable to include an olefin resin in addition to the polyolefin resin powder of the present invention in terms of compatibility with the polyolefin resin powder, weight reduction of members made using the resin composition (D), and cost. As the olefin resin contained other than the polyolefin resin powder of the present invention, the same ones as the olefin polymer (A) can be used. That is, the resin composition (D) may contain an olefin resin other than the polyolefin resin powder of the present invention and the polyolefin resin powder of the present invention, or may contain two or more types of polyolefin resin powders of the present invention. You can stay there. Further, the resin composition (D) may contain an olefin resin other than the polyolefin resin powder of the present invention and two or more types of the polyolefin resin powder of the present invention. The content of the olefin resin other than the polyolefin resin powder of the present invention in the resin composition (D) is preferably 30 to 99.9% by weight, more preferably 50 to 99.0% by weight, and more preferably 70 to 98% by weight. is more preferred, and 80 to 95% by weight is particularly preferred. If it is within the above range, it will have sufficient rigidity when formed into a molded object, and the higher the content, the easier the rigidity will be when formed into a molded object. In addition, within the above range, the molded product has sufficient paintability and adhesiveness, and the lower the content, the better the paintability and adhesiveness of the molded product.

[Polyolefin resin molded body]
One embodiment of the polyolefin resin molded article of the present invention is an injection molded article containing a polyolefin resin modified with a compound having a surface water contact angle of 100° or less and having a repeating unit derived from alkylene oxide. Another embodiment of the polyolefin resin molded article of the present invention includes the polyolefin resin powder of the present invention. Further, still another embodiment of the polyolefin resin molded article of the present invention is obtained by preferably injection molding the polyolefin resin powder of the present invention, and may be formed from the resin composition (D).
This allows the water contact angle on the surface of the molded product to be 100° or less, resulting in good paintability and adhesion. That is, the polyolefin resin molded article of the present invention contains a polyolefin modified with a compound having a repeating unit derived from alkylene oxide, and the water contact angle on the surface of the molded article is 100° or less. The water contact angle on the surface of the molded product is preferably 40° or more. Further, the angle is preferably less than 97°, more preferably 90° or less, and even more preferably 85° or less. For example, the angle is preferably 40° or more and 100° or less, more preferably 40° or more and less than 97°, even more preferably 40° or more and 90° or less, and particularly preferably 40° or more and 85° or less. Within the above range, paintability and adhesiveness will be good.

The polyolefin resin modified with a compound having a repeating unit derived from an alkylene oxide and contained in the polyolefin resin molded article of the present invention may be a polyolefin resin powder containing a polyolefin resin modified with a compound having a repeating unit derived from an alkylene oxide. Preferably, the polyolefin resin powder of the present invention is more preferable. A polyolefin resin powder containing a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide, in particular, by using the polyolefin resin powder of the present invention, a polyolefin resin molded article modified with a compound having a repeating unit derived from an alkylene oxide The dispersibility of the polyolefin resin thus obtained is improved, and the coating and adhesion properties of the molded article are improved.
In the polyolefin resin molded article, the polyolefin resin powder may or may not have a powder form. That is, the polyolefin resin molded article of the present invention may be produced using the polyolefin resin powder of the present invention, or may be produced by injection molding using the polyolefin resin powder of the present invention.

The polyolefin resin molded article of the present invention may contain a compound having a repeating unit derived from the above-mentioned alkylene oxide, and when the polyolefin resin molded article of the present invention contains a compound having a repeating unit derived from an alkylene oxide, The content of the compound having a repeating unit derived from alkylene oxide in the polyolefin resin molded article is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and even more preferably 3 to 18% by weight. Particularly preferred is 4 to 15% by weight. When it is at least the above lower limit, the water contact angle of the molded article can be lowered, and the paintability and adhesiveness are likely to be improved. If it is below the above upper limit, the rigidity of the molded article tends to increase.

The polyolefin resin molded article of the present invention preferably contains an acid-modified polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide. By including the acid-modified polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide, the compatibility with the olefin resin becomes good, and the molded article has good paintability and adhesion. Examples of the acid-modified polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide include polyolefin polymers modified with an acid among the olefin polymers (A).

The content of the polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide in the polyolefin resin molded article is preferably 1 to 70% by weight, more preferably 5 to 50% by weight, and even more preferably 20 to 50% by weight. . When it is at least the above lower limit, the water contact angle of the molded article is likely to be lowered, and the coating properties and adhesion properties are likely to be improved. If it is below the above upper limit, the rigidity of the molded article tends to increase.

The polyolefin resin molded article of the present invention can also contain components other than a compound having a repeating unit derived from alkylene oxide and a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide. Examples of the components that the polyolefin resin molded article may contain include the same components that the resin composition (D) may contain.

Injection molding is preferred as the method for molding the polyolefin resin molded article of the present invention. That is, the method for producing a polyolefin resin molded article of the present invention preferably includes injection molding of a compound containing polyolefin resin powder.

The polyolefin resin powder and polyolefin resin composition of the present invention can be used, for example, in paints, powder coatings, adhesives, resin modifiers, films, and molded bodies.
The polyolefin resin molded article of the present invention can be used, for example, in members used for automobile interiors and exteriors, food and medical containers, parts for furniture and electrical appliances, toys, and civil engineering and construction materials.

Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples, but the present invention is not limited thereto. Note that "parts" in the examples represent "parts by mass." Each measurement and evaluation was performed by the method shown below.

[Grafting rate of acid-modified polyolefin resin]
200 mg of the polymer and 4,800 mg of chloroform were placed in a 10 mL sample bottle and heated at 50° C. for 30 minutes to completely dissolve, thereby obtaining a polymer solution. Chloroform was placed in a liquid cell made of NaCl and having an optical path length of 0.5 mm to serve as a background. The obtained polymer solution was placed in a liquid cell, and an infrared absorption spectrum was measured using FT-IR460plus manufactured by JASCO Corporation with 32 integrations. The grafting rate of maleic anhydride was calculated using a calibration curve prepared by measuring a solution in which maleic anhydride was dissolved in chloroform. Then, from the area of the carbonyl group absorption peak (maximum peak near 1780 cm ^-1 , 1750 to 1813 cm ^-1 ), the content of the acid component in the polymer is calculated based on a separately prepared calibration curve, and this is calculated based on the grafting ratio. (% by weight).

[Measurement of contact angle]
The static contact angle of the surface of a molded article obtained using polyolefin resin powder as a raw material was measured with 1 μL of water using an automatic contact angle meter DM500 manufactured by Kyowa Kaimen Kagaku Co., Ltd. using a liquid drop method. The results are listed in Table 2.
[Measurement of melting point]
A polyolefin resin powder dried at 40°C for 6 hours under reduced pressure of 5 mmHg or less was used as a sample, and the temperature was raised from 0°C to 180°C at a rate of 2°C/min using a differential scanning calorimeter (EXSTAR6000, manufactured by Seiko Instruments). The peak top temperature of the crystal melting peak when the temperature was measured was defined as the melting point.

[Weight percentage of polyolefin resin powder that passes through a sieve with a diameter of 75 mm and an opening of 5.6 mm]
Attach a saucer to the bottom of a sieve with a diameter of 75 mm and an opening of 5.6 mm, weigh out 10 g of the obtained polyolefin resin powder, place it on the sieve, attach a lid to the top of the sieve, hold it with both hands, and shake it from side to side with an amplitude of 200 mm. After shaking 20 times at a shaking speed of 1 time/second, the weight of the polyolefin resin powder that fell into the saucer is taken as the weight that passed through the sieve, and the weight of the polyolefin resin powder that passed through the sieve with a diameter of 75 mm and opening of 5.6 mm per 10 g. The weight ratio was calculated.

[Measurement of average particle diameter of polyolefin resin powder]
The obtained polyolefin resin powder was measured using a laser diffraction/scattering particle size distribution analyzer LA-960 (manufactured by Horiba, Ltd.) to determine the cumulative 50% in the volume-based particle size distribution when the refractive index was 1.47-0.000i. % particle size was measured.

[Solvent solubility of polyolefin resin powder]
Put a stirring bar and 90 g of toluene into a 200 mL mayonnaise bottle, and while stirring at 300 rpm using a stirrer, measure and add 10 g of polyolefin resin powder, cover with a lid, stir while heating at 40 ° C, and dissolve. The time it took to do so was measured.

[Paint adhesion test]
(Creation of water-based paint)
51 parts by mass of DAOTAN VTW1225/40WA (urethane emulsion, non-volatile content 40%) manufactured by Allnex as a base resin, and Aptlock BW-5635 manufactured by Mitsubishi Chemical Corporation (average particle diameter 120 nm, non-volatile content 30%, weight average molecular weight 21) as an adhesive. 27 parts by mass), 19 parts by mass of WT-9004 white (titanium oxide aqueous dispersion, nonvolatile content 65%) manufactured by Nippon Pigment Co., Ltd. as a pigment, 3 parts by mass of TEGOWETKL-245 manufactured by EVONIK as a wetting agent, and a homodisper stirrer. (Polytron PT-3100) and stirred at 700 rpm for 5 minutes. After stirring, the mixture was allowed to stand at room temperature for one day, and the filtrate was filtered through a 300-mesh filter medium to obtain a water-based paint.

(Cross-cut paint film adhesion test)
The surface of a molded product obtained using polyolefin resin powder as a raw material was wiped with isopropyl alcohol, the resulting water-based paint was spray applied to a dry film thickness of 10 μm, and after being set at room temperature for 10 minutes, it was placed in a drying oven. A test piece was obtained by drying at 80° C. for 30 minutes to form a coating film.

Next, make a cross cut on the coated surface of the test piece with a cutter knife so as to reach the molded body, stick cellophane adhesive tape so that the end of the tape is in the center, and apply cellophane adhesive tape in the vertical direction of the test piece. The state of the coating film after peeling off was visually confirmed and evaluated using the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
A: No peeling B: Partial peeling C: Severe peeling

[Production Example 1: Production of acid-modified polyolefin resin]
"Tafmer (registered trademark) (in terms of polypropylene), 200 kg of molecular weight distribution [Mw/Mn] 2.2) and 5 kg of maleic anhydride were dry blended using a super mixer. Thereafter, using a twin-screw extruder ("TEX54αII" manufactured by Japan Steel Works, Ltd.), t-butylperoxyisopropyl monocarbonate (NOF While feeding "Perbutyl I" (manufactured by Komatsu Co., Ltd.) midway through a liquid addition pump, the mixture was kneaded under the conditions of a cylinder temperature of 200°C in the kneading section, a screw rotation speed of 125 rpm, and a discharge rate of 80 kg/hour to form pellets modified with maleic anhydride. A propylene-butene copolymer was obtained. The maleic anhydride group content (grafting ratio) of the maleic anhydride-modified propylene-butene copolymer obtained was 1% by weight. Further, the weight average molecular weight (polystyrene equivalent) [Mw] was 160,000, and the number average molecular weight [Mn] was 80,000.

[Production Example 2: Production of a dispersion containing an acid-modified polyolefin resin and a compound having a repeating unit derived from alkylene oxide]
The inside of a glass flask equipped with a reflux condenser, a thermometer, and a stirrer was replaced with nitrogen gas, and 50 g of the maleic anhydride-modified propylene-butene copolymer obtained in Production Example 1 and "Tafmer (registered trademark) 7070'' was dissolved in 120 g of toluene, 1.0 g of maleic anhydride, and 0.5 g of t-butylperoxyisopropyl monocarbonate (``Perbutyl I'' manufactured by NOF Corporation) were added and reacted at 110°C for 7 hours. Ta. The temperature of the resulting reaction solution was lowered to 70°C, and 30 g of methoxypoly(oxyethylene/oxypropylene)-2-propylamine "Jeffamine M-1000: manufactured by Huntsman" dissolved in 50 g of 2-propanol (100 weight polyolefin resin) was added. (equivalent to 30 parts by weight of a compound having a repeating unit derived from alkylene oxide) and reacted at 70° C. for 1 hour. The temperature of the resulting reaction solution was maintained at 45°C, heated and stirred, and while 300 g of water was added dropwise, the degree of vacuum in the system was lowered and toluene and 2-propanol were distilled off under reduced pressure until the polymer concentration was 30% by weight. A milky white aqueous resin dispersion was obtained. The dispersed particle diameter (50% particle diameter D50) of the obtained aqueous resin dispersion was 110 nm.
Methoxypoly(oxyethylene/oxypropylene)-2-propylamine used in Production Example 2 is a compound with repeating units derived from alkylene oxide, and is insoluble when dissolved in water at 25°C at a concentration of 10% by weight. The aqueous resin dispersion obtained in Production Example 2 contains a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide.

[Example 1: Production of polyolefin resin powder (P-1)]
The aqueous resin dispersion obtained in Production Example 2 was spray-dried using a two-fluid nozzle method using a TR160 type spray dryer manufactured by Pris Co., Ltd. at a spray pressure of 0.3 MPa, a hot air temperature of 60°C, and a coating amount of 0.7 kg/hr. A polyolefin resin powder (P-1) having an average particle diameter of 19 μm, a volatile content of 1.2%, a weight average molecular weight of 200,000, and a melting point of 70° C. was obtained. The weight percentage of the resin powder (P-1) obtained in Example 1 passing through a 5 mm sieve was 100%, and the time required for dissolution in the solvent solubility test was 20 minutes.

[Production Example 3: Production of a dispersion containing an acid-modified polyolefin resin and a compound having a repeating unit derived from alkylene oxide]
The inside of a glass flask equipped with a reflux condenser, a thermometer, and a stirrer was replaced with nitrogen gas, and 100 g of the maleic anhydride-modified propylene-butene copolymer obtained in Production Example 1 was dissolved in 100 g of toluene. 1.2 g of acid and 0.4 g of t-butyl peroxyisopropyl monocarbonate ("Perbutyl I" manufactured by NOF Corporation) were added and reacted at 110° C. for 7 hours. The temperature of the resulting reaction solution was lowered to 70°C, 10g of isopropanol was added, and the mixture was stirred for 1 hour, and then 600g of 70°C warm water was added and stirred. After stirring for 30 minutes, the mixture was allowed to stand and was separated into two phases: a toluene solution phase in the upper part and a warm water phase in the lower part.The warm water phase was extracted from the bottom extraction valve. 50 g of toluene was added to the toluene solution phase remaining in the flask, and 15 g (polyolefin A solution prepared by dissolving a compound (corresponding to 15 parts by weight of a compound having repeating units derived from alkylene oxide) in 200 g of isopropanol and 50 g of water was added dropwise over 1 hour to 100 parts by weight of the resin. After the completion of the dropwise addition, after stirring for 1 hour, 1.0 g of a 90% aqueous solution of 2-amino-2-methyl-1-propanol (AMP90) was added, and while keeping the internal temperature at 50 ° C., 270 g of water was added dropwise. The degree of vacuum in the system was lowered and toluene and 2-propanol were distilled off under reduced pressure until the polymer concentration reached 30% by weight to obtain a milky white aqueous resin dispersion. The dispersed particle diameter (50% particle diameter D50) of the obtained aqueous resin dispersion was 100 nm.
The aqueous resin dispersion obtained in Production Example 3 contains a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide.

[Example 2: Production of polyolefin resin powder (P-2)]
The aqueous resin dispersion obtained in Production Example 3 was spread on a Teflon-treated bat, dried in a drying oven at 40°C for 24 hours while appropriately stirring with a stirring bar, and then dried under reduced pressure at 40°C for 8 hours. The obtained solid resin was crushed in a mortar, further crushed in a crusher (manufactured by Osaka Chemical Co., Ltd., OML-2), and dried under reduced pressure at 40°C for 8 hours to obtain an average particle size of 606 μm and a volatile content of 1.8%. A polyolefin resin powder (P-2) having a weight average molecular weight of 160,000 and a melting point of 70°C was obtained. The weight percentage of the resin powder (P-2) obtained in Example 2 that passed through a 5.6 mm sieve was 100%, and the time required for dissolution in the solvent solubility test was 15 minutes.

[Example 3: Production of polyolefin resin powder (P-3)]
The aqueous resin dispersion obtained in Production Example 2 was spread on a Teflon-treated bat, dried in a drying oven at 40°C for 24 hours while appropriately stirring with a stirring rod, and then dried under reduced pressure at 40°C for 8 hours. The obtained solid resin was crushed in a mortar, passed through a 5 mm sieve, and the polyolefin resin powder remaining on the sieve was further dried under reduced pressure at 40°C for 8 hours to obtain a volatile content of 1.9%, a weight average molecular weight of 200,000, and a melting point of 70. ℃ polyolefin resin powder (P-3) was obtained. The weight percentage of the resin powder (P-3) obtained in Example 3 passing through a 5.6 mm sieve was 0%, and the time required for dissolution in the solvent solubility test was 60 minutes.

[Example 4: Production of molded body containing polyolefin resin powder]
As the base resin, 90 parts by mass of Wintec WMG03 (random polypropylene) manufactured by Nippon Polypropylene Co., Ltd. and 10 parts by mass of the polyolefin resin powder (P-1) obtained in Example 1 were dry blended in a super mixer. , using a twin-screw extruder KZW15 manufactured by Technovel Co., Ltd. at a cylinder temperature of 180°C and a screw rotation speed of 125 rpm, and using an injection molding machine SE18 manufactured by Sumitomo Heavy Industries, Ltd. at a cylinder temperature of 180°C and a mold temperature of 40°C. A molded article of 80 mm x 40 mm x 2 mm was obtained at ℃.

[Examples 5 to 6: Production of molded body containing polyolefin resin powder]
A molded body was produced in the same manner as in Example 1, except that the parts by mass of the base resin Wintec WMG03 and the parts by mass of the polyolefin resin powder described in Example 4 were changed to the proportions shown in Table 1.

[Example 7: Production of molded body containing polyolefin resin powder]
Example except that the parts by mass of the base resin Wintec WMG03 and the type and parts by mass of the polyolefin resin powder described in Example 4 were changed to those listed in Table 2, and the cylinder temperature was changed to 200°C and the mold temperature was changed to 80°C. A molded body was created in the same manner as in 4.

[Comparative Example 1: Production of a molded body containing no polyolefin resin powder]
A molded body was produced in the same manner as in Example 4, except that 100 parts by mass of Wintec WMG03, the base resin described in Example 4, was used and the polyolefin resin powder was not used.

The results of Examples 1 to 3 are shown in Table 1, and the results of Examples 4 to 7 and Comparative Example 1 are shown in Table 2.

The polyolefin resin powders of Examples 1 to 3, which are the polyolefin resin powders of the present invention, were able to be dissolved in a solvent.
Further, the molded bodies of Examples 4 to 7 containing the polyolefin resin powder of the present invention had good coating film adhesion.
On the other hand, the molded article of Comparative Example 1 which did not contain the polyolefin resin powder of the present invention had poor coating film adhesion.

Claims (13)

1. A polyolefin resin powder containing a polyolefin resin modified with a compound having repeating units derived from alkylene oxide.
2. When 10 g of polyolefin resin powder is placed on a sieve with a diameter of 75 mm and an opening of 5.6 mm and shaken 20 times at an amplitude of 200 mm and a shaking speed of 1 time/sec from side to side, the weight percentage passing through the sieve is 90. % or more and 100% or less.
3. The polyolefin according to claim 1 or 2, wherein the compound having a repeating unit derived from alkylene oxide is a compound having one or more repeating units selected from the group consisting of a repeating unit derived from ethylene oxide and a repeating unit derived from propylene oxide. resin powder.
4. The polyolefin resin powder according to claim 1 or 2, wherein the average particle diameter is greater than 1.0 μm and less than 5.6 mm.
5. The polyolefin resin powder according to claim 1 or 2, wherein the content of volatile components is 10% by weight or less.
6. The polyolefin resin powder according to claim 1 or 2, which has a melting point of 120° C. or less when measured using a sample of polyolefin resin powder dried at 40° C. for 6 hours under reduced pressure of 5 mmHg or less.
7. The polyolefin resin powder according to claim 1 or 2, which has a weight average molecular weight of 50,000 or more when measured using a sample of polyolefin resin powder dried at 40° C. for 6 hours under reduced pressure of 5 mmHg or less.
8. A resin composition comprising the polyolefin resin powder according to claim 1 or 2.
9. The resin composition according to claim 8, further comprising another olefin resin in addition to the polyolefin resin powder according to claim 1 or 2.
10. The resin composition according to claim 9, wherein the content of the polyolefin resin powder according to claim 1 or 2 is 0.1 to 70% by weight.
11. A polyolefin resin molded article that is an injection molded article containing a polyolefin resin modified with a compound having a repeating unit derived from alkylene oxide and having a surface water contact angle of 100° or less.
12. A polyolefin resin molded article comprising the polyolefin resin powder according to claim 1 or 2.
13. A method for producing a polyolefin resin molded article, comprising injection molding of a compound containing the polyolefin resin powder according to claim 1 or 2.