JP6705700B2 - Polyolefin resin composition, method for producing the same, and method for producing a molded article - Google Patents

Description

The present invention relates to a polyolefin-based resin composition and a molded product, more specifically, a polyolefin-based resin composition and a molded product molded from the same.

BACKGROUND ART Heretofore, it has been proposed to mold a molded product from a molding material in which sustained-release particles having antibiotic activity are blended with a polyolefin (see, for example, Patent Document 1).

International Publication No. 2015/030213

However, the molded product is required to have excellent impact resistance depending on the application and purpose. However, the molded article described in Patent Document 1 has a problem that the above-mentioned requirements cannot be sufficiently satisfied.

An object of the present invention is to provide a molded product having excellent impact resistance and a polyolefin resin composition for molding the molded product.

That is, the present invention is
[1] A polymer produced from a polyolefin resin, particles containing an antibiotic active compound containing a first functional group, and a monomer component containing a polymerizable hydrocarbon monomer, the first functional group being: A polyolefin-based resin composition comprising a reactive dispersion stabilizer containing a second functional group capable of reacting,
[2] The antibiotic-active compound-containing particle contains a core and a shell that coats the core, the shell being formed by interfacial polymerization of an active hydrogen group-containing component and a polyisocyanate component. 1 functional group is an active hydrogen group in the active hydrogen group-containing component, or a group derived from an isocyanate group in the polyisocyanate component, in the interfacial polymerization, the equivalent ratio of the active hydrogen group to the isocyanate group, The polyolefin-based resin composition according to the above [1], which is greater than 1.00 or less than 1.00.
[3] In the interfacial polymerization, the equivalent ratio is 1.20 or more, the polyolefin resin composition according to the above [2].
[4] A molded product characterized by being molded from the polyolefin resin composition according to the above [1] to [3].

The molded article of the present invention obtained by molding the polyolefin resin composition of the present invention has excellent impact resistance.

FIG. 1 shows a schematic cross-sectional view of first particles, which is an example of particles containing an antibiotic compound. FIG. 2 shows a schematic cross-sectional view of second particles which are an example of particles containing an antibiotic compound. FIG. 3 shows a schematic cross-sectional view of third particles, which is an example of particles containing an antibiotic compound. FIG. 4 is a graph showing the relationship between the equivalent ratio and the Izod impact strength in the interfacial polymerization of Examples 1 to 6.

1. Polyolefin resin composition The polyolefin resin composition of the present invention contains a polyolefin resin, particles containing an antibiotic compound, and a reactive dispersion stabilizer. Hereinafter, each component will be described in detail.

2. Polyolefin Resin A polyolefin resin is a thermoplastic resin produced from a monomer component containing an olefin, and includes, for example, an olefin homopolymer, an olefin copolymer, and a copolymer of olefin and a hydrocarbon monomer other than olefin. Examples thereof include a combination, a copolymer of an olefin and a non-hydrocarbon-based monomer, and the like.

Examples of the olefin homopolymer include polyethylene (PE) such as high-density polyethylene (HDPE), medium-density polyethylene, and low-density polyethylene (LDPE), for example, polypropylene (PP).

Examples of the olefin copolymer include an ethylene-propylene block copolymer, an ethylene-propylene random copolymer, an ethylene-butene copolymer, a propylene-butene copolymer, and the like.

Examples of copolymers of olefins and hydrocarbon monomers other than olefins include ethylene-styrene copolymers, hydrogenated styrene-butadiene copolymers (SEBS, styrene-ethylene-butylene copolymers), styrene. -A hydrogenated product of isoprene copolymer (SEPS, styrene-ethylene-propylene copolymer), ethylene-propylene-diene copolymer (EPDM) and the like can be mentioned.

Examples of copolymers of olefins and non-hydrocarbon monomers include ethylene-(meth)acrylic acid ester copolymers such as ethylene-methyl methacrylate copolymers and ethylene-vinyl acetate copolymers (EVA). Ethylene-vinyl ester copolymer, ethylene-vinyl chloride copolymer, chlorinated polyethylene, chlorinated polypropylene, ethylene-vinyl acetate-vinyl chloride copolymer and other ethylene-chlorinated monomer copolymers.

The polyolefin resin is preferably an olefin homopolymer or an ethylene-vinyl acetate copolymer, more preferably polyethylene or polypropylene, and particularly preferably high density polyethylene. Examples of polyethylene and polypropylene include those produced by high-temperature high-pressure polymerization, for example, coordination polymerization with a Ziegler catalyst or Ziegler-Natta catalyst, for example, coordination polymerization with a metallocene catalyst such as Kaminsky catalyst.

The melt mass flow rate of the polyolefin-based resin measured according to JIS-K 7210 is, for example, 0.04 g/10 min or more, preferably 0.10 g/10 min or more, and for example, 1.00 g/10 min or less, It is preferably 0.20 g/10 min or less.

As the polyolefin-based resin, a commercially available product can be used, and specifically, Hi-Zex series (produced by Prime Polymer Co., Ltd.) and the like are used.

The blending ratio of the polyolefin-based resin is, for example, 80 mass% or more, preferably 90 mass% or more, and for example, 99.9 mass% or less, preferably 99. It is 0 mass% or less.

3. Particles Containing Antibiotic Active Compound The particles containing an antibiotic active compound are phase-separated with respect to the polyolefin resin when the reactive dispersion stabilizer described below is not contained in the polyolefin resin composition, and the antibiotic activity compound is contained in the antibiotic active compound. Since the affinity between the compound-containing particles and the polyolefin resin is low, it has the property of reducing the impact resistance of the polyolefin resin composition.

The particles containing the antibiotic compound contain the first functional group.

3-1. First Functional Group The first functional group is an active hydrogen group in the active hydrogen group-containing component described below or an active hydrogen group derived from the isocyanate group in the polyisocyanate component. Specifically, examples of the first functional group include an amino group and a hydroxyl group. Preferred is an amino group. When the amino group is an active hydrogen group in the active hydrogen group-containing component, it is an amino group contained in the active hydrogen group-containing component, and an active hydrogen group derived from the isocyanate group contained in the polyisocyanate component. If it is, the resulting carbamic acid (-NH-COOH) by reacting the isocyanate groups with water, further, by a carbon dioxide (CO ₂₎ is desorbed, an amino group which is generated.

3-2. Antibiotic Active Compound Further, the particles containing an antibiotic active compound contain an antibiotic active compound. Examples of the antibiotic compound include a first antibiotic compound that is substantially insoluble in the polymerizable vinyl monomer and is substantially hydrophobic. Included are second antibiotic active compounds that are substantially compatible (soluble or soluble) and substantially hydrophobic. Furthermore, examples of the antibiotic compound include capsaicins and/or extracts.

The first antibiotic compound is an insecticide, insecticide, fungicide, which has antibiotic activity such as insecticidal, insecticidal, bactericidal, antibacterial, antiseptic, herbicidal, antialgal, antifungal, inducement, repellent, and rodenticidal. It is selected from antibacterial agents, antiseptics, herbicides, algae agents, fungicides, attractants, repellents and rodenticides. The first antibiotic compound has, for example, extremely low solubility in a polymerizable vinyl monomer at room temperature (20 to 30° C., more specifically 25° C.), and specifically, the solubility at room temperature is, for example, 0.1 parts by mass/(use) polymerizable vinyl monomer (mixture) 100 parts by volume (1 g/L) or less, preferably 0.05 parts by mass/(use) polymerizable vinyl monomer (mixture) 100 parts by volume (0.5 g/L) or less. Further, the antibiotic compound is substantially hydrophobic, and specifically has, for example, extremely low solubility in water at room temperature (20 to 30° C., more specifically 25° C.), Specifically, for example, the solubility at room temperature is 1.5 parts by mass/100 parts by volume of water (15 g/L) or less, preferably 0.5 parts by mass/100 parts by volume of water (5 g/L) or less, and more preferably Is 0.1 part by mass/100 parts by volume of water (1 g/L) or less. Examples of the first antibiotic active compound include neonicotinoid insecticides such as clothianidin and imidacloprid, insect growth regulators, and insecticides such as acaricides.

The second antibiotic compound is a bactericidal agent, antibacterial agent, antiseptic agent, algae agent having antibacterial activity such as bactericidal, antibacterial, antiseptic, algae, antifungal, insecticidal, inducement, repellent, and rodenticidal. , Fungicides, herbicides, insecticides, attractants, repellents and rodenticides. Examples of the second antibiotic active compound include iodine compounds such as IPBC, triazole compounds such as flucirazole, and isothiazoline compounds such as OIT, Cl-MIT and DCOIT. Agents, for example, pyrethroid compounds such as cyfluthrin, and termiticides (anticides) such as neonicotinoid compounds such as acetamiprid. The water solubility of the second antibiotic active compound is selected from the same range as that of the first antibiotic active compound.

Examples of capsaicins include capsaicin (N-[(4-hydroxy-3-methoxyphenyl)methyl]-8-methyl-6-nonenamide) and capsaicin derivatives. Examples of the capsaicin derivative include nonyl acid vanillyl amide, decyl acid vanillyl amide, nordihydrocapsaicin, dihydrocapsaicin, homodihydrocapsaicin, homocapsaicin and the like. These can be used alone or in combination. As the capsaicin, preferably, capsaicin and nonic acid vanillyl amide are mentioned. The capsaicins can be obtained, for example, by chemical synthesis, or can be obtained, for example, by purifying an extract (described later) containing the capsaicins. The capsaicins obtained by purifying the extract containing capsaicins are preferably a mixture containing capsaicin as a main component and a capsaicin derivative as a subcomponent. Regarding the solubility of capsaicins in water at room temperature (25°C), the solubility at room temperature (25°C) is, for example, 1.00 g/water 1 L or less, preferably 0.50 g/water 1 L or less.

The extract is an extract containing capsaicins, for example, an extract (capsicum extract) extracted from the fruit of Capsicum, specifically, extracted from the seed coat and/or pericarp of Capsicum with a solvent. Then, an extract (capsicum extract) obtained by distilling off the solvent thereafter can be mentioned.

Examples of the genus Capsicum include capsicum, boot jolokia, habanero and the like.

The extract contains contaminants in addition to capsaicins, for example.

Contaminants are impurities that are mixed in the extract (impurities that accompany capsaicins), and specifically include substances that are insoluble or sparingly soluble in water. For example, pigments such as carotene, such as lipids. Is mentioned.

The content ratio of capsaicins in the extract is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, less than 50% by mass, and further 40% by mass or less. The content ratio of contaminants in the extract is, for example, more than 50% by mass, further 60% by mass or more, and, for example, 90% by mass or less, preferably 80% by mass or less.

3-3. Morphology of Antibiotics-Active Compound-Containing Particles Antibiotics-active compound-containing particles include core-shell particles including a core and a shell coating the core. Examples of such core-shell particles include a core containing the above-mentioned first antibiotic compound and the first polymer and a second polymer, as described in WO 2015/030213 and the like. And a sustained-release particle (first particle) comprising a shell coating a core, such as the second antibiotic active compound and the first antibiotic as described in WO 2012/124599 and the like. Examples of the sustained-release particles (second particles) include a core containing a polymer and a shell made of a second polymer and covering the core. Furthermore, as the particles containing an antibiotic compound, a core containing the first polymer and the above-mentioned capsaicin and/or the above-mentioned extract containing capsaicin and extracted from the fruit of Capsicum genus. , A particle comprising a second polymer and having a shell coating the core (third particle).

On the other hand, in the present invention, the antibiotic-active compound-containing particles include, for example, a core substance comprising the above-mentioned second antibiotic-active compound and a solvent, as described in JP 2001-247409 A, and the like. It does not include microcapsules provided with an encapsulating membrane, and further does not include antibiotic-active compound-free particles or antibiotic-active compound-free particles consisting of only a polymer.

As the particles containing an antibiotic compound, preferably sustained release particles, more preferably sustained release particles described in WO 2015/030213, more specifically, first particles, capsaicins. A third particle having a core containing a and a shell made of a second polymer and covering the core is included.

3-4. First Particles Specifically, the first particles are formed as spherical particles, as shown in FIG. The first particle 1 includes a core 4 and a shell 5 that covers the core 4.

The core 4 has a matrix 2 and domains 3 dispersed in the matrix 2. The matrix 2 is composed of a first polymer produced from a polymerizable vinyl monomer. Domain 3 consists of an antibiotic active compound. The matrix 2 and the domain 3 are incompatible with each other and form a phase-separated structure or a two-phase structure that separates from each other.

The shell 5 is formed on the surface of the core 4, more specifically, the surface of the matrix 2. The shell 5 is composed of a second polymer produced from a hydrophobic shell forming component and a hydrophilic shell forming component described later. The shell 5 and the core 4 form a core-shell structure.

The method for producing such first particles 1 is, for example, a first antibiotic that is hydrophobic and substantially insoluble in a hydrophobic polymerizable vinyl monomer in the absence of a solvent. An oil phase component preparing step of preparing an oil phase component containing a hydrophobic slurry by dispersing an active compound in a hydrophobic polymerizable vinyl monomer, an oil phase component is dispersed in water to prepare an aqueous dispersion liquid. A water dispersion step and a polymerization step of producing a first polymer by suspension-polymerizing a polymerizable vinyl monomer are provided. Further, in this method, in the oil phase component preparation step, the first antibiotic active compound is dispersed in the polymerizable vinyl monomer to prepare a hydrophobic slurry, and then the hydrophobic slurry and the hydrophobic shell-forming component are combined. Blend to prepare an oil phase component including a hydrophobic slurry and a hydrophobic shell forming component. In addition, in the polymerization step, a hydrophilic shell-forming component is blended to interfacially polymerize the hydrophobic shell-forming component and the hydrophilic shell-forming component.

Hereinafter, the first antibiotic active compound, the polymerizable vinyl monomer, the hydrophobic shell-forming component and the hydrophilic shell-forming component will be sequentially described.

(First antibiotic compound)
Examples of the first antibiotic active compound include the antibiotic active compounds described in WO 2015/030213.

(Polymerizable vinyl monomer)
Examples of the polymerizable vinyl monomer include (meth)acrylic acid ester-based monomers, aromatic vinyl monomers, vinyl ester-based monomers, maleic acid ester-based monomers, vinyl halides, vinylidene halides, nitrogen-containing vinyl monomers, and crosslinkable monomers. And so on. Preferred are (meth)acrylic acid ester-based monomers such as isobutyl (meth)acrylate and crosslinkable monomers such as ethylene glycol dimethacrylate. The polymerizable vinyl monomers can be used alone or in combination.

(Hydrophobic shell-forming component and hydrophilic shell-forming component)
The hydrophobic shell-forming component and the hydrophilic shell-forming component are shell-forming components for forming a shell, and are two reaction components different from each other. The hydrophobic shell-forming component and the hydrophilic shell-forming component are interfacially polymerized (reacted) by polyaddition or polycondensation (condensation polymerization) or the like to produce a second polymer.

The hydrophobic shell-forming component is, for example, substantially hydrophobic and specifically has a very low solubility in water at room temperature, and more specifically, for example, a solubility at room temperature of 1 part by mass/water. 100 parts by volume (10 g/L) or less, preferably 0.5 parts by weight/water 100 parts by volume (5 g/L) or less, more preferably 0.1 parts by weight/water 100 parts by volume (1 g/L) or less. Is. The hydrophobic shell-forming component is an oil-soluble compound that forms a shell by polyaddition or polycondensation with the hydrophilic shell-forming component, and examples thereof include polyisocyanates, for example, polycarboxylic acid chlorides such as terephthalic acid dichloride, and the like. , Benzenesulfonyl dichloride and other polysulfonic acid chlorides. Preferably, polyisocyanate (polyisocyanate component) is used.

Examples of the polyisocyanate include aromatic polyisocyanates (aromatic diisocyanates) such as diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), and polymeric MDI, and aliphatic polyisocyanates (fatty acid) such as hexamethylene diisocyanate (HDI). Alicyclic polyisocyanates (alicyclic diisocyanates) such as isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, for example, xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate And other araliphatic polyisocyanates (araliphatic diisocyanates). Examples thereof include multimers of the above polyisocyanates, and specific examples include dimers, trimers (isocyanurate group-containing polyisocyanates, cyclic trimers), pentamers, heptamers, and the like. Furthermore, modified polyisocyanates (excluding multimers) described above are also exemplified, and examples thereof include polyol-modified polyisocyanates such as trimethylolpropane IPDI adducts, buret reaction adducts of polyisocyanates, and allophanate reaction adducts. Be done. Preferred are polyisocyanate trimers, specifically, IPDI trimers.

The hydrophilic shell-forming component is a water-soluble compound existing in the aqueous phase before the interfacial polymerization and is an active hydrogen group-containing component. The active hydrogen group-containing component is a component (compound) having an active hydrogen group such as an amino group and a hydroxyl group, and specific examples thereof include polyamine, polyol and water. Preferred are polyamines and polyols, and more preferred are polyamines.

Examples of the polyamine include diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, diaminotoluene, phenylenediamine, piperazine, and trivalent diamines such as diethylenetriamine (DETA), triethylenetetramine, tetraethylene, pentaminepentaethylenehexamine. The above polyamines and the like can be mentioned. Preferred are trivalent or higher polyamines, and more preferred are diethylenetriamine.

Examples of the polyol include ethylene glycol, propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedimethanol, polyethylene glycol and polypropylene glycol. Diols such as glycerol, triols such as trimethylolpropane, and tetraols such as pentaerythritol.

The hydrophilic shell-forming components can be used alone or in combination.

Then, the above-mentioned oil phase component preparation step, water dispersion step and polymerization step are sequentially carried out to produce sustained release particles.

In particular, in the oil phase component preparation step, preferably, the hydrophobic shell-forming component is mixed with the hydrophobic slurry together with a polymerization initiator such as an oil-soluble organic peroxide or an oil-soluble azo compound. Thus, the oil phase component containing the polymerization initiator, the hydrophobic shell forming component and the hydrophobic slurry is prepared.

In the polymerization step, the polymerizable vinyl monomer is suspension-polymerized, the hydrophilic shell-forming component is blended, and the hydrophobic shell-forming component and the hydrophilic shell-forming component are interfacially polymerized to coat the first polymer. Then, a shell made of the second polymer is formed.

The mixing ratio of the hydrophilic shell forming component (active hydrogen group-containing component) is such that the active hydrogen group of the hydrophilic shell forming component (specifically, an amino group when the hydrophilic shell forming component is a polyamine) is The equivalent ratio of the hydrophobic shell-forming component (polyisocyanate component) to the isocyanate group (active hydrogen group/isocyanate group, more specifically, amino group/isocyanate group) is not particularly limited and exceeds 1.00, for example. Or the ratio is less than 1.00.

If the above equivalent ratio exceeds 1.00, when the hydrophilic shell-forming component (active hydrogen group-containing component) and the hydrophobic shell-forming component (polyisocyanate component) undergo interfacial polymerization, active hydrogen groups are left over. Can exist as the first functional group in the particles containing the antibiotic compound, and can react with the second functional group of the reactive dispersion stabilizer, thereby improving the impact resistance of the polyolefin resin composition. You can

On the other hand, when the above-mentioned equivalent ratio is less than 1.00, when the hydrophilic shell-forming component (active hydrogen group-containing component) and the hydrophobic shell-forming component (polyisocyanate component) undergo interfacial polymerization, isocyanate groups are left over, Subsequently, resulting carbamate (-NH-COOH) by reacting such isocyanate groups with water, further, carbon dioxide (CO ₂₎ is desorbed, generates an amino group (-NH _2), it It can be present as the first functional group in the particles containing the antibiotic compound. Then, the first functional group can react with the second functional group, and as a result, the impact resistance of the polyolefin resin composition can be improved.

Further, the equivalent ratio of the active hydrogen group to the isocyanate group (active hydrogen group/isocyanate group) exceeds 1.00 from the viewpoint of avoiding hydrolysis of the isocyanate group and reduction in mass yield of the second polymer. Preferably. The equivalent ratio of the active hydrogen group to the isocyanate group (active hydrogen group/isocyanate group) is, for example, 1.20 or more, preferably 1.25 or more, preferably 1.50 or more, more preferably 1.75 or more. Is. When the equivalent ratio is at least the above lower limit, a sufficient amount of the first functional group can be present (contained) in the particles containing the antibiotic compound, and the impact resistance of the molded article molded from the polyolefin resin composition can be improved. The property can be further improved.

The equivalent ratio of the active hydrogen group to the isocyanate group (active hydrogen group/isocyanate group) is, for example, 5.0 or less, preferably 4.0 or less, and more preferably 3.0 or less. When the equivalent ratio is not more than the above upper limit, the first functional group of the hydrophilic shell-forming component (active hydrogen group-containing component) is consumed in the formation of the second polymer, and the free active hydrogen group-containing component is prevented from remaining. be able to. In particular, when the active hydrogen group-containing component is a polyamine, first, the primary amino group at least at one end of the polyamine molecule reacts with the isocyanate group to become a part of the second polymer, which is safe. It is possible to suppress the residual of free polyamine having a problem in the property.

On the other hand, when the equivalent ratio of the active hydrogen group to the isocyanate group (active hydrogen group/isocyanate group) is less than 1.00, for example, 0.90 or less, 0.75 or less, or, for example, 0.50 or more. Is. When the equivalent ratio is not more than the above upper limit, a sufficient amount of the first functional group can be present in the particles, and the impact resistance of the molded product can be further improved. When the equivalent ratio is at least the above lower limit, the hydrolysis amount of the isocyanate group is small, and a sufficient shell thickness can be secured.

The amount of the first functional group (specifically, an amino group) on the surface of the particles containing an antibiotic compound is determined as follows, ignoring the side reaction between isocyanate and water and considering the amount of the isocyanate group remaining unreacted. Given by the formula.

Amino group amount (mol) = | Charged isocyanate amount (mol)- Charged amino group (mol) |
However, actually, the equivalent ratio of the active hydrogen group to the isocyanate group (active hydrogen group/isocyanate group) may be 1.00. In that case, when the hydrophobic shell-forming component and the hydrophilic shell-forming component are polyisocyanate and polyamine, respectively, the finally remaining amino group (remaining at the interface between the first particles 1 and the polyolefin resin) The theoretical amount of (amino group) is 0. However, before the interfacial polymerization of the hydrophobic shell-forming component (polyisocyanate) and the hydrophilic shell-forming component (polyamine) is started by blending the hydrophilic shell-forming component (polyamine), the inside of the first polymer and the A part of the hydrophobic shell-forming component (polyisocyanate) present on the surface of the/or the surface is hydrolyzed by a trace amount of water in the oil phase to generate an amino group. Therefore, even after the hydrophilic shell-forming component (polyamine) is blended and the hydrophobic shell-forming component (polyisocyanate) and the hydrophilic shell-forming component (polyamine) are interfacially polymerized, the particles 1 still have excess amino groups (first group). 1 functional group). That is, the amount of residual amino groups at the interface between the first particles 1 and the polyolefin resin actually has a value (a positive number) that exceeds 0, not 0.

3-5. Second particles As shown in FIG. 2, the sustained-release particles (second particles) described in WO 2012/124599 are homogeneous particles composed of a second antibiotic compound and a first polymer. A core 4 having a phase and a shell 5 covering the core 4 and made of a second polymer are provided. In the production of the sustained-release particles (specifically, interfacial polymerization), the equivalent ratio of the active hydrogen group of the hydrophilic shell forming component to the isocyanate group of the hydrophobic shell forming component (polyisocyanate component) (active hydrogen (Group/isocyanate group) is the same as the above range.

3-6. Third Particles The third particles dissolve capsaicins and/or an extract containing capsaicins with a hydrophobic polymerizable vinyl monomer in the absence of a solvent, and blend a hydrophobic shell forming component. Thus, a hydrophobic solution is prepared, and then the hydrophobic solution is dispersed in water to prepare an aqueous dispersion, and then a polymerizable vinyl monomer is radically polymerized in the presence of an oil-soluble polymerization initiator, A shell made of a second polymer that coats the core by forming a core made of a first polymer, blending a hydrophilic shell forming component, and interfacially polymerizing a hydrophobic shell forming component and a hydrophilic shell forming component. It is obtained by forming.

Examples of the polymerizable vinyl monomer, the hydrophobic shell-forming component, the hydrophilic shell-forming component, the oil-soluble polymerization initiator, and other additives used during the polymerization include those described in WO 2012/124599. Can be mentioned. As shown in FIG. 3, the third particles have a phase-separated structure in which capsaicins form microdomains 3 in the matrix 2 of the first polymer in the core 4 after completion of the polymerization. Therefore, the core 4 of the third particle having a phase-separated structure is distinguished from the core 4 of the second particle having a homogeneous phase in which the antibiotic compound is compatible with the first polymer.

3-7. Physical Properties and Mixing Ratio of Antibiotic Active Compound-Containing Particles The average particle size of the antibiotic active compound-containing particles is not particularly limited, and is, for example, 0.5 μm or more, preferably 1 μm or more, more preferably 2 μm or more. Further, for example, it is 20 mm or less, preferably 10 mm or less, and more preferably 5 mm or less. The average particle size is calculated as the median size.

The particles containing the antibiotic compound are dried as a suspension and formulated as a powder.

The content ratio of the particles containing the antibiotic compound is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and for example, 20.0% by mass with respect to the polyolefin resin composition. Hereafter, it is preferably 10.0 mass% or less. Further, the compounding ratio of the particles containing the antibiotic compound is, for example, 0.1 part by mass or more, preferably 0.2 part by mass or more, and, for example, 20. It is 0 part by mass or less, preferably 10.0 parts by mass or less.

If the blending ratio of the antibiotic-active compound-containing particles is at least the above lower limit, it is possible to sufficiently impart the function of the antibiotic-active compound-containing particles (specifically, antibiotic activity etc.) to the polyolefin resin composition. it can. When the compounding ratio of the particles containing the antibiotic compound is not more than the above upper limit, it is possible to prevent the impact resistance of the polyolefin resin composition from being excessively lowered.

4. Reactive Dispersion Stabilizer The reactive dispersion stabilizer is delocalized (dispersed) at the interface between the polyolefin-based resin and the particles containing the antibiotic compound, and reduces the free energy at the interface to reduce the free energy. It is an additive (or modifier) that stabilizes the phase-separated structure between the particles containing the antibacterial active compound. Further, the reactive dispersion stabilizer has an amphipathic chemical structure. Specifically, the reactive dispersion stabilizer has a polymer portion that is compatible with the polyolefin resin and a reactive portion that reacts with the antibiotic-active compound-containing particles.

The reactive dispersion stabilizer consists of a polymer containing a second functional group (reactive moiety).

Examples of the second functional group include reactive groups such as an acid anhydride group (an acid anhydride ring), an epoxy group (epoxy ring), a carboxyl group, a carboxylate group, a hydroxyl group, an amino group, a double bond and a triple bond. Be done. An acid anhydride group, an epoxy group, a carboxyl group and a carboxylate group are preferable, and an acid anhydride group and an epoxy group are more preferable.

The polymer is produced from a monomer component containing a polymerizable hydrocarbon monomer. Examples of the hydrocarbon-based monomer include olefins such as ethylene, propylene, butene, pentene, hexene, and octene; aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, and vinylnaphthalene; for example, butadiene and isoprene. And conjugated dienes such as cyclopentadiene. Further, the monomer component is, for example, an acid anhydride group-containing monomer containing an acid anhydride group, an epoxy group-containing monomer containing an epoxy group, a carboxyl group-containing monomer containing a carboxyl group, a carboxylate containing a carboxylate group. A second functional group-containing vinyl monomer, such as a group-containing monomer is included. Further, the monomer component is, for example, a (meth)acrylic acid ester-based monomer such as methyl methacrylate, a vinyl ester-based monomer such as vinyl acetate, a nitrogen-containing vinyl monomer such as (meth)acrylonitrile, vinyl chloride, vinyl fluoride, or the like. A vinyl halide monomer or the like can also be contained.

The polymer is, for example, a copolymer, and specifically, a random copolymer, a block copolymer, a graft copolymer, a copolymer obtained by combining these, and the like. The graft copolymer is one in which one or more molecules of the monomer are chemically bonded as a side chain of the polymer main chain, and is represented by main chain polymer-g-side chain monomer or side chain oligomer or side chain polymer. Does not specify the molecular weight of.

The reactive dispersion stabilizer is not particularly limited, and examples thereof include acid anhydride group-containing polymer, epoxy group-containing polymer, carboxyl group-containing polymer, and carboxylate group-containing polymer. Further, examples of the reactive dispersion stabilizer include polyolefin having an acid value, for example, an acrylic graft polymer grafted with a second functional group.

Examples of the acid anhydride group-containing polymer include maleic anhydride grafted polypropylene (PP-g-MAH), maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride grafted ethylene-vinyl acetate copolymer (EVA). -G-MAH), maleic anhydride grafted ethylene-acrylic acid ester copolymer (E·Ac-g-MAH), maleic anhydride grafted ethylene-propylene rubber (EPR-g-MAH), maleic anhydride grafted ethylene- Propylene-diene rubber, maleic anhydride-grafted polyolefin polymer such as (EPDM-g-MAH), for example, maleic anhydride-grafted polystyrene (PS-g-MAH), maleic anhydride-grafted styrene-butadiene-styrene copolymer (SBS). -G-MAH), maleic anhydride-grafted styrene-ethylene-butene copolymer (SEBS-g-MAH), and other maleic anhydride-grafted polystyrene-based polymers, for example, styrene-maleic anhydride copolymer, styrene-acrylic acid -Maleic anhydride copolymer, acrylic acid ester-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, ethylene-(meth)acrylic acid ester-maleic anhydride copolymer, α-olefin-maleic anhydride Styrene-acrylonitrile graft copolymerization of a copolymer of a monomer containing a hydrocarbon monomer and a maleic anhydride, such as an acid copolymer and a maleic anhydride-terminated polypropylene, for example, ethylene-ethyl acrylate-maleic anhydride copolymer. Polymer, styrene-based polymer graft copolymer to copolymer of ethylene-ethyl acrylate-maleic anhydride copolymer, styrene-methyl methacrylate graft copolymer, etc., monomer containing hydrocarbon monomer and maleic anhydride Is mentioned.

Examples of the epoxy group-containing polymer include glycidyl methacrylate graft polystyrene (PS-g-GMA), glycidyl methacrylate graft styrene-methyl methacrylate copolymer (MS-g-GMA), glycidyl methacrylate graft styrene-acrylonitrile copolymer (AS). -G-GMA) or other epoxy group-containing vinyl monomer grafted styrene-based polymer, for example, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-glycidyl methacrylate-methyl acrylate copolymer, A copolymer of a monomer containing a hydrocarbon-based monomer and an epoxy group-containing vinyl monomer, such as an ethylene-glycidyl methacrylate-ethyl acrylate copolymer, for example, a polystyrene graft copolymer (to an ethylene-glycidyl methacrylate copolymer ( E.GMA-g-PS), a styrene-methyl methacrylate graft copolymer to an ethylene-glycidyl methacrylate copolymer (E-GMA-g-MS), a styrene-acrylonitrile graft copolymer to an ethylene-glycidyl methacrylate copolymer Styrene-based polymer graft copolymer to copolymer of monomer containing hydrocarbon monomer and vinyl monomer containing epoxy group, such as polymer (E.GMA-g-AS), to ethylene-glycidyl methacrylate copolymer Examples thereof include (meth)acrylic acid ester-based polymer graft copolymer (E.GMA-g-Ac).

Examples of the carboxyl group-containing polymer include carboxyl group-containing vinyl monomer-grafted polyolefin-based polymers such as acrylic acid graft polypropylene (PP-g-AA) and acrylic acid graft ethylene-vinyl acetate copolymer (EVA-g-AA). Examples thereof include vinyl monomer-carboxyl group-containing vinyl monomer copolymers such as ethylene-methacrylic acid copolymer, styrene-methacrylic acid copolymer, and styrene-acrylic acid copolymer.

Examples of the carboxylate group-containing polymer include a carboxylate group-containing vinyl monomer copolymer such as ethylene-methacrylate copolymer (ionomer).

These reactive dispersion stabilizers are produced, for example, by melt-kneading a polyolefin-based polymer, an organic peroxide and a vinyl monomer containing a second functional group, and grafting the vinyl monomer containing a second functional group onto the polyolefin. be able to. These reactive dispersion stabilizers are obtained by copolymerizing, for example, an olefin with a vinyl monomer having a second functional group by thermal polymerization at high temperature and high pressure, or coordination polymerization using a Ziegler catalyst or a metallocene catalyst. Can be manufactured.

A commercially available product can be used as the reactive dispersion stabilizer. For example, when an acid anhydride group-containing polymer is given as an example, maleic anhydride graft polypropylene (PP-g-MAH) is used as DuPont's Fusabond 5000 series, Toyobo's Toyotac series, Kayaku Akzo's Kaya Bridley's, Addivant. Polybond 3000 series manufactured by the same company, and maleic anhydride-grafted polyethylene (PE-g-MAH) include Fusabond 2200 series manufactured by DuPont. Maleic anhydride-grafted ethylene-vinyl acetate copolymer (EVA-g). -MAH) include DuPont's Fusabond 3000 series, 3800 series, and the like, and maleic anhydride-grafted ethylene-acrylic ester copolymer (EAc-g-MAH) includes DuPont's Fusabond 5000 series. Examples of the maleic anhydride-grafted ethylene-propylene-diene rubber (EPDM-g-MAH) include Royal Tuff 400 series manufactured by Addivant, and examples of the ethylene-maleic anhydride copolymer include Fusabond M603 manufactured by DuPont. Examples of ethylene-(meth)acrylic acid ester-maleic anhydride copolymers include Arkema's Rotada MAH series, Bondine series, Nippon Polyethylene's Lexpearl ET, and the like. α-olefin-maleic anhydride copolymer As coalesced, Mitsubishi Chemical Co., Ltd. Diakarna and the like, maleic anhydride terminal polypropylene, such as Sanyo Kasei Co., Ltd. Umex series, and the like, ethylene-ethyl acrylate-maleic anhydride copolymer styrene-acrylonitrile Examples of the graft copolymer include MODIPER A8400 manufactured by NOF CORPORATION.

Moreover, when exemplifying a commercially available product of an epoxy group-containing polymer, specifically, as an ethylene-glycidyl methacrylate copolymer, for example, Arkema company Rotada AX8840, Sumitomo Chemical Co., Ltd. Bondfast 2C, E, CG5001 and the like can be mentioned. Examples of the ethylene-glycidyl methacrylate-vinyl acetate copolymer include Sumitomo Chemical Co., Ltd. Bondfast 2B and 7B. As the ethylene-glycidyl methacrylate-methyl acrylate copolymer, Arkema Rotader AX8900, Sumitomo Chemical BondFirst 7L, 7M, and the like. As a polystyrene graft copolymer (E.GMA-g-PS) to an ethylene-glycidyl methacrylate copolymer, MODIPER A4100 manufactured by NOF CORPORATION can be mentioned, and an ethylene-glycidyl methacrylate copolymer. Examples of (meth)acrylic acid ester-based polymer graft copolymers (E.GMA-g-Ac) include NOF CORPORATION MODIPER A4300 (methyl methacrylate-butyl acrylate copolymer) and ethylene- Examples of the styrene-acrylonitrile graft copolymer (E.GMA-g-AS) on the glycidyl methacrylate copolymer include NOF Corp. MODIPER A4400.

Furthermore, when exemplifying a commercial product of a carboxyl group-containing polymer, specifically, as an acrylic acid-grafted polypropylene (PP-g-AA), for example, Polybond 1000 series manufactured by Adivant Co. may be mentioned, and acrylic acid-grafted ethylene-acetic acid. Examples of the vinyl copolymer (EVA-g-AA) include Fusabond 3100 series manufactured by DuPont, and examples of the ethylene-methacrylic acid copolymer include Nuclel series manufactured by DuPont.

Examples of commercially available carboxylate-group-containing polymers include ethylene-methacrylate copolymers such as DuPont's Surlyn series and Mitsui DuPont Polychemical's High Milan series.

Examples of polyethylene having an acid value include Optiwell 100 series and 300 series manufactured by Honeywell Co., Ltd., and acrylic resin having a second functional group grafted thereto includes Reseda manufactured by Toagosei Co., Ltd. Examples of the reactive dispersion stabilizer in which the second functional group is introduced into polyolefin include MODIC manufactured by Mitsubishi Chemical Co., and ADMER manufactured by Mitsui Chemicals.

The blending ratio of the reactive dispersion stabilizer is, for example, 0.10% by mass or more, preferably 0.20% by mass or more, and for example, 10% by mass or less, based on the polyolefin resin composition. It is preferably 5.0% by mass or less. The mixing ratio of the reactive dispersion stabilizer is, for example, 5.0 parts by mass or more, preferably 10 parts by mass or more, and, for example, 250 parts by mass with respect to 100 parts by mass of the antibiotic active compound-containing particles. It is not more than 100 parts by mass, preferably not more than 100 parts by mass. Furthermore, the mixing ratio of the reactive dispersion stabilizer is, for example, 0.10 parts by mass or more, preferably 0.50 parts by mass or more, relative to 100 parts by mass of the polyolefin resin, and, for example, It is 10 parts by mass or less, preferably 5.0 parts by mass or less.

When the blending ratio of the reactive dispersion stabilizer is at least the above lower limit, the impact resistance of the polyolefin resin composition can be sufficiently improved. When the blending ratio of the reactive dispersion stabilizer is not more than the above upper limit, it is possible to obtain the effect of improving the impact resistance according to the blending ratio and suppress the cost increase.

The mixing ratio of the reactive dispersion stabilizer is such that the equivalent ratio (second functional group/first functional group) of the second functional group in the reactive dispersion stabilizer to the first functional group in the particles containing an antibiotic compound is. Is adjusted to, for example, 0.1 or more, preferably 0.5 or more, and for example, 10 or less, preferably 5 or less.

The polyolefin-based resin composition is a colorant, an antioxidant, and an ultraviolet absorber in addition to the above-mentioned polyolefin-based resin, antibiotic-active compound-containing particles and a reactive dispersion stabilizer as long as the effects of the present invention are not impaired. Additives (additives other than reactive dispersion stabilizer) such as agents, flame retardants, plasticizers, antistatic agents, lubricants, anti-eyes agents, impact modifiers, fillers, etc. it can.

5. Preparation of Polyolefin Resin Composition and Molding of Molded Body To obtain this polyolefin resin composition, first, a polyolefin resin, particles containing an antibiotic compound and a reactive dispersion stabilizer (further blended as necessary) The additives described above are blended and they are melt-kneaded to prepare a kneaded product.

To prepare the kneaded product, for example, specifically, a single-screw extruder, a twin-screw extruder, a heating kneader, a Banbury mixer, a heating roll and the like are used, and preferably a twin-screw extruder is used. The kneaded material is a molding material for molding a molded body, and specifically, once cooled, it is prepared as a pellet-shaped molding material. On the other hand, the kneaded product can be continuously used as it is in the molten state (melt kneaded product) without being taken out as a solid molding material, which will be described later.

After that, a pellet or a melt-kneaded product is molded into a molded body.

As the molding method, for example, injection molding, extrusion molding, inflation molding, pultrusion molding, compression molding and the like are adopted.

As a result, a molded product molded from the polyolefin resin composition is obtained.

Such a molded product is used for various purposes, for example, a building material, for example, an electric wire cable material, and a covering material for the electric wire cable, for example, a buried pipe of the electric wire cable, a conduit of gas, and the buried pipe thereof. It is also used as a covering material for pipes and conduits, for example, textiles such as clothes and mosquito nets.

6. Effect And, in the above-mentioned polyolefin resin composition, the reactive dispersion stabilizer is a polymer of a monomer component containing a polymerizable hydrocarbon monomer, so that the affinity with the polyolefin resin can be improved. At the same time, the second functional group can react with the first functional group. Therefore, the free energy of the interface between the polyolefin resin and the particles containing the antibiotic compound can be reduced.

As a result, the molded product molded from the polyolefin-based resin composition has excellent impact resistance.

Furthermore, the antibiotic-active compound-containing particle contains a core and a shell that coats the core, the shell is formed by interfacial polymerization of an active hydrogen group-containing component and a polyisocyanate component, and the first functional group is It is derived from the active hydrogen group in the active hydrogen group-containing component or the isocyanate group in the polyisocyanate, and in the interfacial polymerization, if the equivalent ratio of the active hydrogen group to the isocyanate group exceeds 1.00, the excess active hydrogen group is , Present in the shell of the particles containing the antibiotic compound as the first functional group. Alternatively, in the interfacial polymerization, when the equivalent ratio of the active hydrogen group to the isocyanate group is less than 1.00, the excess isocyanate group reacts with water to form carbamic acid, and carbon dioxide gas is desorbed to form an amino group. The resulting amino groups are present in the shell of the particles containing the antibiotic compound as the first functional group. Then, the first functional group can surely react with the second functional group during melt-kneading. Therefore, the affinity between the particles containing the antibiotic compound and the reactive dispersion stabilizer can be improved.

Further, when the above-mentioned equivalent ratio is 1.20 or more, a sufficient amount of the first functional group (amino group) can be present (contained) in the antibiotic-active compound-containing particles, and the polyolefin resin composition It is possible to further improve the impact resistance of the molded product molded from.

Further, a molded product molded from the polyolefin-based resin composition has excellent impact resistance in a wide temperature range, and includes, for example, low temperature (specifically, -30 to 0° C.) and normal temperature (specifically, 20 to 20). Excellent impact resistance at 25°C.

Then, the above-mentioned molded article is used for impact resistance, preferably for impact resistance over a wide temperature range, specifically, for buried pipes of electric cables in cold regions, gas. It is suitable for use as a conduit.

Hereinafter, the present invention will be described more specifically by showing Preparation Examples, Examples and Comparative Examples. The present invention is not limited to these. Further, specific numerical values such as a mixing ratio (content ratio), physical property values, and parameters used in the following description are described in the above “Mode for carrying out the invention”, and a corresponding mixing ratio ( Substitute the upper limit value (value defined as "below" or "less than") or the lower limit value (value defined as "greater than or equal to" "exceeding") such as content ratio), physical property value, parameter etc. be able to. Further, in the following description, "part" and "%" are based on mass unless otherwise specified.

1. Details of Components and Devices Components and devices used in each preparation example, each example and each comparative example are described below.
-Clothianidin: Antibiotic active compound (neonicotinoid insecticide), molecular weight 250, melting point 177°C, solubility in water: 0.33 g/L, manufactured by Sumitomo Chemical Co., Ltd.- VNA: Nonylic acid vanillylamide (N- Vanillyl nonanamide), molecular weight 293, melting point 54°C, solubility in water: almost insoluble, Tokyo Chemical Industry's EGDMA: ethylene glycol dimethacrylate, crosslinkable monomer, trade name "light ester EG", insoluble in water , Kyoeisha Chemical Co., Ltd.-i-BMA: isobutyl methacrylate, (meth)acrylic acid ester-based monomer, water solubility: 0.6 g/L, Nippon Shokubai Co., Ltd.-MMA: methyl methacrylate, trade name "light ester" M”, solubility in water 16 g/L (25° C.), Kyoeisha Chemical Co., Ltd., DISPERBYK-164: trade name, functional group-modified copolymer for pigment dispersion (tertiary amine-containing polyester-modified polyurethane polymer, molecular weight 10,000) To 50000) in butyl acetate, solid content concentration 60%, manufactured by Big Chemie T-1890: trade name "VESTANAT T 1890/100", isophorone diisocyanate cyclic trimer (IPDI trimer), polyisocyanate component (isocyanate concentration 17. 3%), solubility in water: 0.02 g/L, manufactured by Evonik Industries, Inc., Parloyl L: trade name, dilauroyl peroxide, oil-soluble polymerization initiator, manufactured by NOF Corporation, DETA: diethylenetriamine, molecular weight 103, Active hydrogen group-containing component, Wako first-class reagent, Wako Pure Chemical Industries, Ltd., Pronone 208: trade name, polyoxyethylene polyoxypropylene block copolymer, nonionic surfactant, NOF Corporation, PVA-217: trade name " Kuraray Poval 217", partially saponified polyvinyl alcohol, dispersant, Kuraray's Demol NL: trade name, 41% aqueous solution of β-naphthalenesulfonic acid formaldehyde condensate sodium salt, Kao's HiZex 6300M: high density polyethylene, melt Mass flow rate: 0.11 g/10 min, manufactured by Prime Polymer Co., Rotada AX8840: reactive dispersion stabilizer, ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate content: 8% by mass), manufactured by Arkema, twin-screw extruder: KZW15-30MG, Technovel Co., injection molding machine: NEX110, Nissei Plastic Industry Co., Ltd., Izod impact tester: Ueshima Seisakusho Co., Ltd.

2. Preparation of Particles Containing Antibiotic Active Compound Preparation Example 1
(Oil phase component preparation process)
90 g of EGDMA, 90 g of i-BMA, 20 g of DISPERBYK-164 and 100 g of clothianidin were placed in a glass bottle, and zirconia beads (diameter 1.0 mm) were placed in 1/3 volume of the glass bottle to obtain a paint conditioner (paint). A shaker, trade name "THECLASSIC Model 1400", manufactured by Red Devil) was wet-milled for 2 hours to obtain a slurry (hydrophobic slurry, hereinafter referred to as clothianidin slurry) containing 33.3% of clothianidin. The average particle size of clothianidin in the clothianidin slurry was 1.38 μm as a result of measurement with a concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).

A 200-mL beaker (1) was charged with 50 g of clothianidin slurry, 17.5 g of i-BMA, 17.5 g of EGDMA, 15 g of T-1890, and 0.5 g of perloyl L, and stirred at room temperature to give i-BMA, EGDMA, T-1890 and Perloyl L were dissolved in clothianidin slurry. This prepared an oil phase component containing i-BMA, EGDMA, T-1890, perloyl L and clothianidin slurry.

(Water dispersion process)
Separately, in a 500 mL beaker (2), 245.36 g of ion-exchanged water, 40 g of a 10% aqueous solution of PVA-217, 1 g of a 1% aqueous solution of pronone 208, and 0.24 g of demol NL were charged, and the mixture was stirred at room temperature to homogeneity. An aqueous solution was obtained.

Then, the oil phase component was added to a 500 mL beaker (2), and T. K. The oil phase component was dispersed in the aqueous solution by stirring with a homomixer MARK 2.5 type (manufactured by Primix Co., Ltd.) at a rotation speed of 4000 rpm for 6 minutes to prepare a suspension (aqueous dispersion).

Then, the suspension (aqueous dispersion) was transferred to a 500 mL 4-neck Kolben equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, and stirred under a nitrogen stream.

(Polymerization process including interfacial polymerization)
Then, 12.9 g of a 10 mass% aqueous solution of DETA was added to the suspension at room temperature to initiate interfacial polymerization. Then, the temperature of the suspension was raised to 70° C. to start suspension polymerization. The suspension polymerization was carried out at 70° C. for 30 minutes and then at 80° C. for 5 hours.

Then, the suspension after the reaction was cooled to 30° C. or lower to obtain a suspension (suspension agent) of sustained-release particles in which clothianidin was dispersed in a matrix and the matrix was coated with polyurea.

The median diameter of the sustained-release particles in the suspension was measured by a laser diffraction scattering type particle size distribution measuring device LA-920 (manufactured by Horiba Ltd.). The results are shown in Table 1.

Then, the suspension was dehydrated by centrifugation, dried at 40° C. for 24 hours, and sifted with a 80-mesh sieve to obtain a dry powder (powder) of sustained-release particles.

Preparation Examples 2-6
A suspension of sustained-release particles coated with polyurea and containing clothianidin was obtained in the same manner as in Preparation Example 1, except that the concentration and blending amount of the aqueous solution of DETA were changed as described in Table 1. Table 1 shows the measurement results of the median diameter.

Then, the suspension was dehydrated by centrifugation, dried at 40° C. for 24 hours, and sifted with a 80-mesh sieve to obtain a dry powder (powder) of sustained-release particles.

Preparation Example 7
(Oil phase component preparation process)
A 200 mL beaker was charged with 17.0 g of VNA, 64.6 g of MMA, 3.4 g of EGDMA, 15.0 g of T-1890 and 0.5 g of perloyl L and stirred at room temperature to prepare a uniform hydrophobic solution.

(Water dispersion process)
Separately, in a 500 mL beaker, ion-exchanged water, 40.0 g of a 10% aqueous solution of PVA-217, 1.0 g of a 1% aqueous solution of pronone 208, and 0.24 g of demole NL were charged, and a uniform aqueous solution was obtained by stirring at room temperature. Obtained.

Then, a hydrophobic aqueous solution was added to the aqueous solution in a 500 mL beaker, and T. K. The hydrophobic aqueous solution was dispersed in the aqueous solution by stirring for 5 minutes at a rotation speed of 2000 rpm with a homomixer MARK 2.5 type (manufactured by PRIMIX Corporation) to prepare an aqueous dispersion.

Then, the aqueous dispersion was transferred to a 500 mL 4-neck Kolben equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introducing tube, and stirred under a nitrogen stream.

(Polymerization process including interfacial polymerization)
Then, the temperature of the suspension was raised to 70° C. to start suspension polymerization. After reacting at 70° C. for 3 hours, 15.9 g of a 20 mass% aqueous solution of DETA was added to initiate interfacial polymerization. Then, the reaction was performed at 70° C. for 2 hours.

By cooling the suspension after the reaction to 30° C. or lower, VNA was dispersed in the matrix to obtain a suspension (suspension agent) of sustained-release particles in which the matrix was covered with polyurea.

The median diameter of the sustained-release particles in the suspension was measured by a laser diffraction scattering type particle size distribution measuring device LA-920 (manufactured by Horiba Ltd.). The results are shown in Table 1.

Then, the suspension was dehydrated by centrifugation, dried at 40° C. for 24 hours, and sifted with a 80-mesh sieve to obtain a dry powder (powder) of sustained-release particles.

Comparative Preparation Example 1
Into a 200 mL beaker (1), 50 g of clothianidin slurry prepared in Preparation Example 1 was charged with 5.0 g of i-BMA, 45.0 g of EGDMA, and 0.5 g of perloyl L, and the mixture was stirred at room temperature to give i- BMA, EGDMA, and Perloyl L were dissolved in clothianidin slurry. This prepared an oil phase component containing i-BMA, EGDMA, Perloyl L and clothianidin slurry.

Separately, a 500 mL beaker (2) was charged with 258.26 g of ion-exchanged water, 40 g of a 10% aqueous solution of PVA-217, and 1 g of a 1% aqueous solution of pronone 208, and the mixture was stirred at room temperature to obtain a uniform aqueous solution.

Then, the oil phase component was added to a 500 mL beaker (2), and T. K. A homomixer MARK 2.5 type (manufactured by PRIMIX Corporation) was stirred at a rotation speed of 5000 rpm for 5 minutes to disperse the oil phase component to prepare a suspension (aqueous dispersion liquid).

Then, the suspension (aqueous dispersion) was transferred to a 500 mL 4-neck Korben equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introducing tube, and heated under stirring under a nitrogen stream to carry out suspension polymerization. Carried out.

Suspension polymerization was carried out continuously when the temperature reached 55° C., and after that, the temperature was raised to 70±1° C. for 5 hours including the heating time, and 80±1° C. for 2 hours.

Thereafter, the suspension after the reaction was cooled to 30° C. or lower to obtain a suspension of sustained-release particles containing clothianidin. Table 1 shows the measurement results of the median diameter.

Then, the suspension was dehydrated by centrifugation, dried at 40° C. for 24 hours, and sieved with an 80-mesh sieve to obtain a dry powder of sustained-release particles.

Example 1
A homogeneous dry blended product was prepared by mixing 98.00 parts by mass of Hi-Zex 6300M, 1.30 parts by mass of the first particles of Preparation Example 1, and 0.70 part by mass of Rotada AX8840. Subsequently, the dry blended product was supplied to a twin-screw extruder KZW15-30M by a screw feeder, melt-kneaded (melt-blended), and then passed through a cooling water tank and a pelletizer to obtain pellets. The set temperature of the cylinder and the die of the twin-screw extruder was 200°C, and the screw rotation speed was 470 rpm.

Examples 2-7 and Comparative Examples 1-8
Pellets were obtained by treating under the same conditions as in Example 1 except that the formulation shown in Table 2 was changed.

(Impact resistance test)
(Measurement of Izod impact strength)
The notched Izod impact test pieces were molded from the pellets of each example and each comparative example using an injection molding machine. The set temperature of the cylinder and the die during injection molding was 200°C, and the set temperature of the mold was 30°C. The notched Izod impact test piece is a test piece according to JIS K7110, and specifically has a length of 100 mm, a width of 10 mm, a thickness of 4 mm, and a notch residual width of 8 mm.

Then, the Izod impact test piece with each notch was measured for Izod impact strength at 20° C. and −25° C. according to JIS K7110 using an Izod impact tester. The results are shown in Table 2.

Discussion The following points can be seen from the results of the impact resistance test described above.

1) Izod impact strength of each of Examples 1 to 6 containing polyethylene, an amino group-containing particle containing an antibiotic compound, and a reactive dispersion stabilizer is the same as that of polyethylene or an amino group-free antibiotic activity. It is higher than the Izod impact strength of compound-containing particles (Comparative Preparation Example 1) and Comparative Example 5 containing a reactive stabilizer. (Effect of the first functional group)
2) Comparing Example 1 with Comparative Example 1, the Izod impact strength at 20° C. is significantly improved by blending (adding) the reactive dispersion stabilizer to the polyolefin resin and the sustained release particles. To do. This is because the comparison between Example 2 and Comparative Example 2, the comparison between Example 5 and Comparative Example 3, the comparison between Example 6 and Comparative Example 4, and the comparison between Example 7 and Comparative Example 8. The same is true (effect of reactive dispersion stabilizer).

3) Compared with Example 3 in which the amount of amino groups was 0, Examples 1, 2, 4 to 6 in which the amount of amino groups on the surface of the sustained-release particles exceeded 0, Izod impact strength at 20° C., and , -25° C. Izod impact strength is high (effect of the first functional group).

4) That is, as can be seen from FIG. 4, when the equivalent ratio of the amino group to the isocyanate group (amino group/isocyanate group) in the preparation in the interfacial polymerization at the time of producing the particles containing the antibiotic compound exceeds 1.00. Examples 4 to 6 and Examples 1 and 2, which are less than 1.00, have an Izod impact strength of 20° C. as compared with Example 3 in which the equivalent ratio (amino group/isocyanate group) is 1.00. Also, the Izod impact strength at -25°C is high (effect of the amount of the first functional group).

5) Further, as can be seen from Examples 1, 2, 4 to 6 in FIG. 4, as the equivalence ratio deviates from 1, the Izod impact strength at 20° C. and the Izod impact strength at −25° C. are both higher. (Effect of the amount of the first functional group).

6) Specifically, among Examples 4 to 6 in which the equivalent ratio (amino group/isocyanate group) exceeds 1.00, as Example 4 progresses to Example 6, that is, the equivalent ratio deviates from 1. That is, the larger the absolute value of the value obtained by subtracting 1 from the equivalent ratio (amino group/isocyanate group) (|(equivalent ratio)-1|), the greater the Izod impact strength at 20°C and the Izod at -25°C. High impact strength.

Further, among Examples 1 and 2 in which the equivalent ratio (amino group/isocyanate group) is less than 1.00, Example 1 has an equivalent ratio smaller than 1, that is, the equivalent ratio (amino Group/isocyanate group) minus 1 is large in absolute value (|(equivalent ratio)-1|) (synonymous with "residual amino group amount at interface" in Table 1), Izod impact strength at 20°C, and , -25° C. Izod impact strength is high (effect of the amount of the first functional group).

7) Examples 4 and 5 in which the equivalence ratio (amino group/isocyanate group) exceeds 1.00 and Examples 1 and 2 in which the equivalence ratio (amino group/isocyanate group) is less than 1.00, 20 Compare Izod impact strengths at ℃ and -25 ℃. Then, when the same value of |(equivalent ratio)-1| (that is, when estimating the same value of |(equivalent ratio)-1|), the equivalent ratio (amino group/isocyanate group) is 1 If it exceeds 0.000 (examples similar to Examples 4 and 5), the equivalent ratio (amino group/isocyanate group) is less than 1.00 (examples similar to Examples 1 and 2). In comparison, the Izod impact strength at 20° C. and −25° C. tends to be high (dominance of amino group/isocyanate group>1).

8) The Izod impact strength of Comparative Example 6 containing polyethylene and particles containing an antibiotic group not containing an amino group (Comparative Preparation Example 1) was higher than that of Comparative Example 7 consisting of polyethylene only. Low (impact resistance lowering effect of particles containing an antibiotic compound).

9) Polyethylene, particles containing an amino group-free antibiotic active compound (Comparative Preparation Example 1), and Comparative Example 5 containing a reactive dispersion stabilizer are those in which the epoxy group of the reactive dispersion stabilizer is an antibiotic. Since it does not react with the surface of the active compound-containing particles, its Izod impact strength is equivalent to that of Comparative Example 6 containing polyethylene and an amino group-free antibiotic active compound-containing particle (Comparative Preparation Example 1). (Control of the effect of the first functional group).

The polyolefin resin composition is used as a molding material for a molded body. Such a molded article is, for example, a building material, for example, an electric wire cable material, and a covering material for the electric wire cable, for example, a buried pipe of the electric wire cable, a conduit such as gas, and a covering material for the buried pipe or conduit, For example, it is used as textile products such as clothes and mosquito nets.

1 Sustained release particles (an example of particles containing an antibiotic compound)
4 core 5 shell

Claims (4)

Polyolefin resin,
Antibiotic active compound-containing particles containing a first functional group,
A polymer produced from a monomer component containing a polymerizable hydrocarbon monomer, which contains a reactive dispersion stabilizer containing a second functional group capable of reacting with the first functional group. A polyolefin-based resin composition comprising: A method for producing the polyolefin resin composition according to claim 1, wherein
The antibiotic active compound-containing particles contain a core and a shell coating the core,
The shell is formed by interfacial polymerization of an active hydrogen group-containing component and a polyisocyanate component,
The first functional group is an active hydrogen group in the active hydrogen group-containing component, or a group derived from an isocyanate group in the polyisocyanate component,
In the interfacial polymerization, the equivalent ratio of the active hydrogen groups to the isocyanate groups is more than 1.00 or less than 1.00, the method for producing a polyolefin resin composition. The said equivalence ratio is 1.20 or more in the said interfacial polymerization, The manufacturing method of the polyolefin resin composition of Claim 2 characterized by the above-mentioned. Characterized by forming a polyolefin resin composition according to claim 1, process for producing a molded article.

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