JP5727870B2 - Polyolefin resin modifier - Google Patents

Description

  The present invention relates to a polyolefin resin modifier that imparts excellent wettability to a polyolefin resin substrate. More specifically, the present invention relates to a polyolefin resin modifier that imparts excellent wettability to a polyolefin resin substrate without impairing mechanical strength. Here and below, wettability means affinity for water and is evaluated by wet tension described later.

Polyolefin resins are excellent in moldability, rigidity, heat resistance, chemical resistance, electrical insulation, and the like, and are inexpensive, so they are widely used as films, fibers, and other shaped articles of various shapes. On the other hand, a polyolefin resin is a so-called nonpolar and extremely inert polymer substance having no polar group in the molecule. In addition, since it has high crystallinity and extremely low solubility in solvents, there are problems such as adhesion and paintability, and poor wettability with water and water repellent, so that water-based paint cannot be applied. It was.
Conventionally, as a method for improving wettability, a surface of a thermoplastic resin base material, for example, a polyolefin resin molded product, is subjected to corona treatment or plasma treatment (for example, see Patent Document 1), and a surfactant is added to the polyolefin resin composition. A method of adding and making this into a molded product (for example, see Patent Document 2) is known.

JP 2000-319426 A JP 2004-169014 A

However, the method of subjecting the surface of the molded product to corona treatment or plasma treatment has a problem that wettability decreases with the passage of time after treatment. In addition, in the method of adding a surfactant to a polyolefin resin composition and making this into a molded product, the mechanical strength inherent to the original molded product of the polyolefin resin substrate can be obtained by adding an amount sufficient to exert a modification effect. (Tensile modulus, impact resistance, etc., the same shall apply hereinafter) are impaired, and the surfactant may bleed out of the molded product, and improvements have been eagerly desired.
An object of the present invention is to provide a polyolefin resin modifier that imparts excellent wettability to water to a polyolefin resin substrate without impairing mechanical strength.

  The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides a polyolefin (A) having a number average molecular weight of 800 to 50,000, an unsaturated dicarboxylic acid (anhydride) (B), and a styrene or styrene derivative (C) in the presence of a radical initiator (E). Is a polyolefin resin modifier (K) obtained by copolymerizing

The modifier for polyolefin resin of the present invention and a molded product obtained by molding a polyolefin resin composition containing the modifier have the following effects.
(1) The modifier imparts excellent wettability to water to the polyolefin resin substrate without impairing the original mechanical strength.
(2) The molded article has excellent wettability with water and is excellent in its sustainability.

In the presence of the radical initiator (E), the polyolefin resin modifier (K) of the present invention is a polyolefin (A) having a number average molecular weight of 800 to 50,000, an unsaturated dicarboxylic acid (anhydride) (B). And styrene or a styrene derivative (C).
[Polyolefin (A)]
The polyolefin (A) in the present invention includes one or two or more (co) polymers of olefins, and one or more of olefins and one or more of other monomers. A polymer is included.
Examples of the olefin include alkenes having 2 to 30 carbon atoms (hereinafter abbreviated as C) such as ethylene, propylene, 1- and 2-butene, and isobutene, and C5-30 α-olefins (1-hexene, 1-hexene, Decene, 1-dodecene, etc.); Other monomers include C4-30 unsaturated monomers having copolymerizability with olefins such as styrene and vinyl acetate.

Specific examples of (A) include ethylene unit-containing (propylene unit-free) (co) polymers such as high, medium, and low density polyethylene, and ethylene and C4-30 unsaturated monomers [butene (1 -Butene, etc.), copolymers with C5-30 α-olefins (1-hexene, 1-dodecene, etc.), vinyl acetate, etc. [weight ratio is the moldability of the polyolefin resin composition and the terminal end of (A). From the viewpoint of the amount of heavy bonds, preferably 30/70 to 99/1, more preferably 50/50 to 95/5), etc .; propylene unit-containing (ethylene unit-free) (co) polymers such as polypropylene, propylene and C4 Copolymer with -30 unsaturated monomers (same as above) (weight ratio is the same as above); ethylene / propylene copolymer (weight ratio is the moldability of polyolefin resin substrate and end of (A)) From the viewpoint of the amount of double bonds, preferably 0.5 / 99.5 to 30/70, more preferably 2/98 to 20/80); (co) polymers of C4 or higher olefins such as polybutene are included. .
Among these, polyethylene, polyprolene, ethylene / propylene copolymer, propylene / C4 are preferable from the viewpoint of copolymerization with an unsaturated dicarboxylic acid (anhydride) (B), styrene or a styrene derivative (C) described later. -30 unsaturated monomer copolymers, more preferably ethylene / propylene copolymers, and propylene / C4-30 unsaturated monomer copolymers.

  Number average molecular weight of (A) [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method described later. same as below. ] Is 800 to 50,000, preferably 1,000 to 45,000. If the Mn is less than 800, the mechanical strength of the molded article of the composition containing the polyolefin resin modifier (K) based on the (A) in the polyolefin resin deteriorates, and if it exceeds 50,000 (K) Productivity and wettability of the product deteriorate.

The measurement conditions of Mn by the GPC method in the present invention are as follows.
Equipment: High temperature gel permeation chromatography
["Alliance GPC V2000", manufactured by Waters Corporation]
Solvent: Orthodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm, MIXED-B 2 in series [polymer laboratory
Product]
Column temperature: 135 ° C

(A) preferably has an unsaturated bond (double bond) at the molecular end from the viewpoint of polymerizability with the below-mentioned unsaturated dicarboxylic acid (anhydride) (B), styrene or styrene derivative (C).
The number of unsaturated bonds (double bonds) at the molecular terminals per 1,000 carbon atoms in (A) is the copolymerizability of (A) with (B) and (C) and the productivity of (K). From this viewpoint, the number is preferably 0.1 to 20, more preferably 0.3 to 18, and particularly preferably 0.5 to 15. Here, the number of unsaturated bonds can be calculated from the integrated value of the double bond-derived peak at 4.5 to 6.0 ppm in the spectrum obtained from ¹ H-NMR (nuclear magnetic resonance) spectroscopy.

  The production method of (A) includes polymerization methods (for example, those described in JP-A-59-206409) and degradation methods [thermal, chemical and mechanical degradation methods, etc. Examples of the formation method (hereinafter sometimes referred to as thermal degradation method) include those described in JP-B No. 43-9368, JP-B No. 44-29742, and JP-B No. 6-70094].

  The polymerization method includes a method of (co) polymerizing one or more of the olefins, and a method of copolymerizing one or more of the olefins and one or more of the other monomers. It is.

  In the degradation method, a polyolefin (A0) having a high molecular weight [preferably Mn 30,000 to 400,000, more preferably 50,000 to 200,000] obtained by the polymerization method is thermally, chemically or mechanically used. The method of degrading is included.

Among the degradation methods, in the thermal degradation method, the polyolefin (A0) is continuously introduced for 0.5 to 10 hours at 300 to 450 ° C. in the absence of an organic peroxide under nitrogen aeration. And (2) a method of continuously thermally degrading at 180 to 300 ° C. for 0.5 to 10 hours in the presence of an organic peroxide.
Among these, it is preferable from the viewpoint of copolymerization with (A) and (B) and (C) to be obtained that those having a larger number of unsaturated bonds (double bonds) at the molecular terminals are easily obtained ( This is the method 1).

  Among these production methods (A), those having a larger number of unsaturated bonds (double bonds) at the molecular ends are easily obtained, and copolymerization of (A), (B), and (C) is easy. From the viewpoint of being present, a degradation method is preferred, and a thermal degradation method is more preferred.

[Unsaturated dicarboxylic acid (anhydride) (B)]
The unsaturated dicarboxylic acid (anhydride) (B) in the present invention is a dicarboxylic acid (anhydride) having one polymerizable unsaturated group. In the present invention, the unsaturated dicarboxylic acid (anhydride) represents an unsaturated dicarboxylic acid or an unsaturated dicarboxylic acid anhydride.
The (B) includes C4-30, such as aliphatic (C4-24, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and their anhydrides), and alicyclic ones ( C8-24, for example, cyclohexanedicarboxylic acid, cycloheptenedicarboxylic acid). (B) may be used alone or in combination of two or more.
Of these, unsaturated dicarboxylic acid anhydride is preferred from the viewpoint of copolymerization with (A) and styrene or styrene derivative (C) described later, and maleic anhydride is more preferred.

[Styrene or styrene derivative (C)]
In the present invention, styrene or a styrene derivative (C) includes styrene, C9-26 alkylstyrene (α-methylstyrene, o-, m- and p-methyl, -ethyl, -propyl and -butylstyrene, o- and p-phenylstyrene, mesityl styrene, 2,4-, 2,5- and 3,5-dimethylstyrene, etc.); C9-26 alkoxystyrenes (o-, m- and p-methoxystyrene, etc.); C8- 26 halogenated styrenes (o-, m- and p-chlorostyrene, o-, m- and p-bromostyrene, o-, m- and p-fluorostyrene, o-methyl-p-fluorostyrene, etc.); Examples thereof include silylated styrene (such as trimethylsilylstyrene) and carboxyl group-containing styrene (such as vinyl benzoic acid). (C) may be used alone or in combination of two or more.
Of these, styrene and alkylstyrene are preferable from the viewpoint of copolymerizability with (A) and (B), and styrene is more preferable.

  The content of each component based on the total weight of (A), (B), and (C) is as follows. (A) is a viewpoint for improving the productivity of the modifier (K) of the present invention and improving the wettability of the polyolefin resin substrate. From 30 to 98%, more preferably from 40 to 90%; (B) is preferably from 0.03 to 40%, more preferably from the viewpoint of improving the wettability of the composition and the productivity of (K). 5 to 35%; (C) is preferably 0.6 to 65%, more preferably 1 to 50% from the viewpoint of improving the mechanical strength and wettability of the polyolefin resin substrate.

In order to further improve the wettability of the polyolefin resin substrate, in addition to the (A), (B), and (C), the copolymer component constituting the polyolefin resin modifier (K) of the present invention. If necessary, a C6-36 α-olefin (D) can be further added to the copolymerization component.
(D) includes C6-36 α-olefin, maintenance of mechanical strength of the polyolefin resin base material to be modified, and excellent wettability of the modifier (K) of the present invention to water on the base material. From the viewpoint of imparting, C8-30 linear α-olefins and branched α-olefins are preferably included.
In (D), examples of the linear α-olefin include 1-hexene, 1-octene, 1-nonene, 1-decene, and a mixture of two or more thereof.
Examples of the α-olefin having a branched chain include propylene trimer, propylene tetramer, and a mixture of two or more thereof.
Of these (D), from the viewpoint of copolymerization with (A), (B), and (C), a linear α-olefin is preferable, and 1-decene is more preferable.

  The content of (D) is usually 65% or less based on the total weight of (A), (B), and (C), preferably from the viewpoint of improving the wettability of the polyolefin resin substrate and mechanical strength. 6 to 60%, more preferably 1 to 50%.

[Radical initiator (E)]
In the present invention, (A), (B), (C) and (D) added as necessary [in the following, (A), (B), (C), etc. may be referred to. ] Is copolymerized in the presence of the radical initiator (E).
Examples of (E) include azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.), peroxides [monofunctional (having one peroxide group in the molecule) (benzoyl peroxide, di- t-butyl peroxide, lauroyl peroxide, dicumyl peroxide, etc.) and polyfunctional (having two or more peroxide groups in the molecule) [2,2-bis (4,4-di-t-butylperoxy Cyclohexyl) propane, di-t-butylperoxyhexahydroterephthalate, diallylperoxydicarbonate, etc.]] and the like.
Among these, from the viewpoint of the copolymerizability of the copolymer components such as (A), (B) and (C), a peroxide is preferable, a monofunctional peroxide is more preferable, and a difunctional peroxide is particularly preferable. t-butyl peroxide, lauroyl peroxide, dicumyl peroxide.

  The amount of (E) used is preferably 0.05 to 10% based on the total weight of copolymer components such as (A), (B) and (C), from the viewpoint of reactivity and side reaction suppression, and more preferably Preferably it is 0.2 to 5%, Most preferably, it is 0.5 to 3%.

[Modifier for polyolefin resin (K)]
In the presence of the radical initiator (E), the polyolefin resin modifier (K) of the present invention is a polyolefin (A) having an Mn of 800 to 50,000, an unsaturated dicarboxylic acid (anhydride) (B), styrene or It is a modifier for a polyolefin resin obtained by copolymerizing a styrene derivative (C) and, if necessary, a C6-36 α-olefin (D).

Specific manufacturing methods (K) include the following methods [1] and [2].
[1] (A), (B), (C) and, if necessary, (D) with an appropriate organic solvent [C3-18, such as aliphatic hydrocarbon (hexane, heptane, octane, dodecane, etc.), aromatic hydrocarbon (Benzene, toluene, xylene, etc.), halogenated hydrocarbons (di-, tri-, and tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone, di-t-butyl ketone, etc.), ethers (ethyl-n-propyl) Ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)], and if necessary, dissolve (E) [or (E) in an appropriate organic solvent (same as above). Solution], a method of adding a chain transfer agent (t) and a polymerization inhibitor (f), which will be described later, and stirring while heating (solution method) Preferred are aromatic hydrocarbons from the viewpoint of solubility, more preferred are toluene, xylene).;
[2] (A), (B), (C) and, if necessary, (D), (E), (t), (f) are mixed in advance and melted using an extruder, Banbury mixer, kneader, etc. Kneading method (melting method).

  The reaction temperature in the solution method may be a temperature at which (A) is dissolved in an organic solvent, and is preferably 50 to 220 from the viewpoint of copolymerization and productivity of (A), (B), (C) and the like. ° C, more preferably 110 to 210 ° C, particularly preferably 120 to 180 ° C.

  Further, the reaction temperature in the melting method may be any temperature at which (A) melts, and preferably from the viewpoints of copolymerizability such as (A), (B), (C) and the decomposition temperature of the reaction product. It is 120-260 degreeC, More preferably, it is 130-240 degreeC.

Examples of the chain transfer agent (t) include hydrocarbons [C6-24, such as aromatic hydrocarbons (toluene, xylene, ethylbenzene, isopropylbenzene, etc.), unsaturated aliphatic hydrocarbons (1-butene, 2-butene, 1- and 2-pentene, 1-hexene, etc.]]; halogenated hydrocarbons (C1-24, such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane); alcohols (C1-24, such as methanol, ethanol, 1-propanol, 2 -Butanol, allyl alcohol); thiols (C1-24, eg ethylthiol, propiothiol, 1- and 2-butylthiol, 1-octylthiol); ketones (C3-24, eg acetone, methyl ethyl ketone); aldehydes (C2 -18, for example 2-methyl-2-propyla Dehydr, 1- and 2-butyraldehyde, 1-pentylaldehyde); Phenol (C6-36, eg phenol, o-, m- and p-cresol); Amine (C3-24, eg diethylmethylamine, triethylamine, diphenylamine) ); Disulfides (C2-24, such as diethyl disulfide, di-1-propyl disulfide).
The amount of (t) used is usually 30% or less based on the total weight of copolymer components such as (A), (B), and (C), and copolymers such as (A), (B), and (C). From the viewpoint of productivity and productivity, it is preferably 0.1 to 20%.

Examples of the polymerization inhibitor (f) include catechol (C6-36, for example, 2-methyl-2-propylcatechol), quinone (C6-24, for example, p-benzoquinone), hydrazine (C2-36, for example, 1, 3, 5-triphenylhydrazine), nitro compounds (C3-24, such as nitrobenzene), stabilized radicals [C5-36, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2,6,6 -Tetramethyl-1-piperidinyl oxide (TEMPO)].
The amount of (f) used is usually 5% or less based on the total weight of copolymer components such as (A), (B), (C), productivity, (A), (B), (C), etc. From the viewpoint of the stability of the copolymer component and the reactivity of (A), (B), (C) and the like, it is preferably 0.01 to 0.5%.

  The Mn of the modifier (K) is preferably from 1,500 to 70,000, more preferably from 2,000 to 70, from the viewpoint of mechanical properties and moldability of a molded product (hereinafter sometimes referred to simply as a molded product) described later. 60,000, particularly preferably 2,500 to 50,000.

  The acid value of (K) is preferably from 0.5 to 200 mgKOH / g (only numerical values are shown below), from the viewpoint of the wettability of the molded product and the compatibility between (K) and the polyolefin resin (F) described later. Preferably it is 1-180. The acid value here is a value measured according to JIS K0070.

  The modifier (K) of the present invention is used as a modifier for the polyolefin resin (F) described later.

[Polyolefin resin composition]
The polyolefin resin composition of the present invention comprises the modifier (K) and the polyolefin resin (F).
(F) includes a polymerization method exemplified as the production method of (A), or a degradation (thermal, chemical and mechanical degradation) method of a high molecular weight polyolefin (preferably Mn 80,000 to 400,000). For example, an ethylene unit-containing (propylene unit-free) (co) polymer, a propylene unit-containing (ethylene-unit-free) (co) polymer, an ethylene / propylene copolymer, and (Co) polymers of C4 or higher olefins are included.

  As a combination of (F) and (K), the case where the structural unit of (F) and the structural unit of the polyolefin (A) constituting (K) are the same or similar is the case of (F) and (K) It is preferable from the viewpoint of compatibility. For example, when (F) is a propylene unit-containing (ethylene unit-free) (co) polymer, (A) constituting (K) is also a propylene unit-containing (ethylene unit-free) (co) polymer. Some cases are preferred.

  Mn in (F) is preferably 10,000 to 500,000, more preferably 20,000 to 400,000, from the viewpoint of mechanical properties of the polyolefin resin substrate and compatibility with (K).

The polyolefin resin composition of the present invention can further contain various additives (G) as necessary within a range not inhibiting the effects of the present invention.
(G) includes colorant (G1), flame retardant (G2), filler (G3), lubricant (G4), antistatic agent (G5), dispersant (G6), antioxidant (G7), and ultraviolet light. The 1 type (s) or 2 or more types chosen from the group which consists of an absorber (G8) are mentioned.

Examples of the colorant (G1) include pigments and dyes.
Examples of the pigment include inorganic pigments (alumina white, graphite and the like); organic pigments (azo lake type and the like).

  Examples of the dye include azo series and anthraquinone series.

  Examples of the flame retardant (G2) include organic flame retardants [nitrogen-containing compounds [salts such as urea compounds and guanidine compounds], sulfur-containing compounds [sulfuric esters, sulfamic acids, and their salts, esters, amides, etc.], silicon-containing compounds Compound [polyorganosiloxane etc.], phosphorus-containing [phosphate ester etc.]]; inorganic flame retardant [antimony trioxide, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, etc.] and the like.

  Fillers (G3) include carbonates (magnesium carbonate, calcium carbonate, etc.), sulfates (aluminum sulfate, etc.), sulfites (calcium sulfite, etc.), metal sulfides (molybdenum disulfide, etc.), silicates (aluminum silicate) Etc.), diatomaceous earth, silica powder, talc, silica, zeolite, and mixtures thereof.

  Examples of the lubricant (G4) include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide).

Antistatic agents (G5) include nonionic, cationic, anionic and amphoteric surfactants described below and in US Pat. Nos. 3,929,678 and 4,331,447. .
(1) Nonionic surfactant Alkylene oxide (hereinafter abbreviated as AO) addition type nonionics, for example, active hydrogen atom-containing compound having a hydrophobic group (C8-24 or more) [saturated and unsaturated, higher alcohol (C8-18), higher aliphatic amines (C8-24) and higher fatty acids (C8-24) etc.] (poly) oxyalkylene derivatives (higher fatty acid mono- and di-esters of AO adducts and polyalkylene glycols) A (poly) oxyalkylene derivative of a higher fatty acid (C8-24) ester of a polyhydric alcohol (C3-60) (Tween type nonionics, etc.); a (poly) oxyalkylene derivative of a (alkanol) amide of a higher fatty acid (above) A (poly) oxyalkylene of a polyhydric alcohol (above) alkyl (C3-60) ether Derivatives; and polyoxypropylene polyols [polyoxypropylene derivatives of polyhydric alcohols and polyamines (C2-10) (pluronic and tetronic nonionics)]; polyhydric alcohols (above) type nonionics (for example of polyhydric alcohols) Fatty acid esters, polyhydric alcohol alkyl (C3-60) ethers, and fatty acid alkanolamides); and amine oxide type nonionics [eg (hydroxy) alkyl (C10-18) di (hydroxy) alkyl (C1-3) amine oxide ].

(2) Cationic surfactants Quaternary ammonium salt-type cationix [tetraalkyl ammonium salt (C11-100) alkyl (C8-18) trimethylammonium salt and dialkyl (C8-18) dimethylammonium salt etc.]; trialkyl Benzylammonium salt (C17-80) (lauryldimethylbenzylammonium salt etc.); alkyl (C8-60) pyridinium salt (cetylpyridinium salt etc.); (poly) oxyalkylene (C2-4) trialkylammonium salt (C12-100) ) (Polyoxyethylene lauryl dimethyl ammonium salt, etc.); and acyl (C8-18) aminoalkyl (C2-4) or acyl (C8-18) oxyalkyl (C2-4) tri [(hydroxy) alkyl (C1-4 ]] Ammoni Um salts (sapamine type quaternary ammonium salts) [these salts include, for example, halides (chlorides, bromides, etc.), alkyl sulfates (methosulphate, etc.) and organic acids (below); and amine salt types Cationics: 1-3 primary amines [for example, higher aliphatic amines (C12-60), polyoxyalkylene derivatives of aliphatic amines (methylamine, diethylamine, etc.) [ethylene oxide (hereinafter abbreviated as EO) adducts, etc.], and acyl Aminoalkyl or acyloxyalkyl (above) di (hydroxy) alkyl (above) amine (such as stearoyloxyethyl dihydroxyethylamine, stearamide ethyl diethylamine)], inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc.) salt and organic Acid (C2-22) salt.

(3) Anionic surfactant Higher fatty acid (above) salt (such as sodium laurate), ether carboxylic acid [carboxymethylated product of EO (1-10 mol) adduct, etc.], and salts thereof; sulfate salt ( Alkyl and alkyl ether sulfates, etc.), sulfated oils, sulfated fatty acid esters and sulfated olefins; sulfonates [alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfosuccinic acid dialkyl ester types, α-olefins (C12-18) Sulfonates, N-acyl-N-methyl taurine (Igepon T type, etc.)], and phosphate ester salts (alkyl, alkyl ethers, alkylphenyl ether phosphates, etc.).

(4) Amphoteric surfactant:
Carboxylic acid (salt) type amphoterics [amino acid type amphoterics (such as laurylaminopropionic acid (salt)) and betaine type amphoterics (such as alkyldimethylbetaine and alkyldihydroxyethylbetaine)]; sulfuric acid Ester (salt) type amphoterics [sulfuric ester (salt) of laurylamine, hydroxyethyl imidazoline sulfate ester (salt), etc.]; sulfonic acid (salt) type amphoterics [pentadecyl sulfotaurine, imidazoline sulfonic acid ( Salt) etc.], and phosphate ester (salt) type amphoterics etc. [phosphate ester (salt) etc. of glycerol lauryl ester].

  Salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); Ammonium salts; and amine salts and quaternary ammonium salts.

  Examples of the dispersant (G6) include polymers having Mn of 1,000 to 20,000, such as vinyl resin {polyolefin (polyethylene, polypropylene, etc.), modified polyolefin [polyethylene oxide (polyethylene oxide oxidized with ozone, etc., carboxyl group, carbonyl group and And / or those having a hydroxyl group introduced therein), and vinyl resins other than the above polyolefins (polyhalogenated vinyl [polyvinyl chloride, polyvinyl bromide, etc.], polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly (meta ) Acrylic acid, poly (meth) acrylic acid ester [poly (meth) methyl acrylate etc.] and styrene resin [polystyrene, acrylonitrile / styrene (AS) resin etc.] etc .; polyester resin [polyethylene terephthalate etc.], polyamid Examples include resins [6,6-nylon, 12-nylon, etc.], polyether resins [polyethersulfone, etc.], polycarbonate resins [polycondensates of bisphenol A and phosgene, etc.], and block copolymers thereof. .

  Antioxidants (G7) include hindered phenol compounds [pt-amylphenol-formaldehyde resin, nordihydroguaiaretic acid (NDGA), 2,6-di-tert-butyl-4-methylphenol (BHT). ), 2-t-butyl-4-methylphenol (BHA), 6-t-butyl-2,4, -methylphenol (24M6B), 2,6-di-t-butylphenol (26B) and the like];

  Sulfur-containing compounds [N, N'-diphenylthiourea, dimyristylthiodipropionate, etc.];

  Phosphorus-containing compound [2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, dioctadecyl-4-hydroxy-3,5-di- t-butylbenzylphosphonate and the like] and the like.

  Examples of the ultraviolet absorber (G8) include salicylate compounds [phenyl salicylate and the like]; benzophenone compounds [2,4-dihydroxyzenzophenone and the like]; benzotriazole compounds [2- (2′-hydroxy-5′-methylphenyl). ) -Benzotriazole and the like].

The total content of (G) in the polyolefin resin composition is usually 20% or less based on the total weight of the composition, preferably 0.05 to 10 from the viewpoint of functional expression of each (G) and an industrial viewpoint. %, More preferably 0.1 to 5%.
The amount of each additive used based on the total weight of the composition is as follows: (G1) is usually 5% or less, preferably 0.1 to 3%; (G2) is usually 8% or less, preferably 1 to 3%; (G3) is usually 5% or less, preferably 0.1 to 1%; (G4) is usually 8% or less, preferably 1 to 5%; (G5) is usually 8% or less, preferably 1 to 3%; (E6) is usually 1% or less, preferably 0.1 to 0.5%; (G7) is usually 2% or less, preferably 0.05 to 0.5%; (G8) is usually 2% or less, preferably Is 0.05 to 0.5%.

  When the additive is the same and overlaps between (G1) to (G8) above, it is not used regardless of the effect as the other additive in an amount in which each additive exhibits the corresponding effect, Considering that the effects as other additives can be obtained at the same time, the amount used is adjusted according to the purpose of use.

As a production method of the polyolefin resin composition of the present invention,
(1) A method (collective method) in which (F), (K) and, if necessary, (G) are collectively mixed to obtain a polyolefin resin composition;
(2) A masterbatch polyolefin resin composition containing a high concentration of (K) is prepared by mixing a part of (F), the total amount of (K), and if necessary, a part or all of (G). Then, a method (masterbatch method) is included in which the remaining (F) and, if necessary, the remaining (G) are added and mixed to obtain a polyolefin resin composition.
The method (2) is preferable from the viewpoint of the mixing efficiency of (K).

  The weight ratio of (K) and (F) in the polyolefin resin composition of the present invention is preferably 10/90 to 40/60, more preferably 15/85, from the viewpoint of wettability and mechanical properties of the molded product described later. 35/65, particularly preferably 20/80 to 30/70.

As a specific mixing method in the manufacturing method of the polyolefin resin composition,
(I) For each component to be mixed, for example, a powder mixer [“Henschel Mixer” [trade name “Henschel Mixer FM150L / B”, manufactured by Mitsui Mining Co., Ltd.], “Nauter Mixer” [trade name “Nauter Mixer” DBX3000RX "manufactured by Hosokawa Micron Co., Ltd.]," Banbury mixer "[trade name" MIXTRON BB-16MIXER "manufactured by Kobe Steel Co., Ltd.], etc.] A single-screw kneader, a twin-screw kneader, etc.)] and the like, usually at 120-220 ° C. for 0.5-30 minutes;
(Ii) A method of directly kneading the components to be mixed under the same conditions using the same melt-kneading apparatus as described above without mixing powders in advance.
Among these methods, the method (i) is preferable from the viewpoint of mixing efficiency.

[Molding]
The molded product of the present invention is formed by molding the polyolefin resin composition.
Examples of molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), etc., depending on the purpose. Molding, multilayer molding, foam molding and the like can be performed by any method that incorporates means. Examples of the form of the molded product include a plate shape, a sheet shape, a film, and a fiber (including a nonwoven fabric).

The molded article of the present invention has excellent mechanical strength and good paintability and printability, and a molded article can be obtained by coating and / or printing the molded article.
Examples of the method for coating the molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating.
Examples of the paint include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.

Further, as a method for further printing after coating the molded product or the molded product, any printing method generally used for plastic printing can be used. For example, gravure printing, flexographic printing, Examples include printing, screen printing, pad printing, dry offset printing, and offset printing.
As the printing ink, those usually used for printing plastics, for example, gravure ink, flexographic ink, screen ink, pad ink, dry offset ink and offset ink can be used.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means “part by weight” and “%” other than mol% means “% by weight”.

Production Example 1
Polyolefin (P1) [trade name “Sun Allomer PZA20A”, manufactured by Sun Allomer Co., Ltd., Mn 100,000, hereinafter the same, with 98 mol% of propylene and 2 mol% of ethylene as structural units. ] 100 parts were charged in a nitrogen atmosphere, heated and melted with a mantle heater while nitrogen was passed through the gas phase, and heat-degraded at 360 ° C. for 80 minutes with stirring, to obtain a polyolefin thermal degradation product (A-1 ) (A-1) had 10.8 molecular terminal double bonds per 1,000 carbon atoms, and Mn was 2,000.

Production Example 2
In Production Example 1, a polyolefin thermal degradation product (A-2) was obtained in the same manner as in Production Example 1 except that the thermal degradation time was changed from 80 minutes to 100 minutes. In (A-2), the number of molecular terminal double bonds per 1,000 carbon atoms was 18, and Mn was 1,200.

Production Example 3
In Production Example 1, a polyolefin thermal degradation product (A-3) was obtained in the same manner as in Production Example 1 except that the thermal degradation time was changed from 80 minutes to 20 minutes. In (A-3), the number of molecular terminal double bonds per 1,000 carbon atoms was 0.3, and Mn was 45,000.

Production Example 4
In Production Example 1, instead of 100 parts of polyolefin (P1), polyolefin (P2) having 80 mol% of propylene and 20 mol% of 1-butene as structural units [trade name “Tuffmer XM-5080”, Mitsui Chemicals, Inc. Manufactured, Mn 90,000, and so on. ] Except having used 100 parts, it carried out similarly to manufacture example 1, and obtained the polyolefin thermal degradation product (A-4). In (A-4), the number of molecular terminal double bonds per 1,000 carbon atoms was 10.8, and Mn was 2,000.

Comparative production example 1
In Production Example 1, a polyolefin thermal degradation product (ratio A-1) was obtained in the same manner as in Production Example 1 except that the thermal degradation time was changed from 80 minutes to 120 minutes. In (Ratio A-1), the number of molecular terminal double bonds per 1,000 carbon atoms was 36, and Mn was 600.

Comparative production example 2
In Production Example 1, a polyolefin thermal degradation product (ratio A-2) was obtained in the same manner as in Production Example 1 except that the thermal degradation time was changed from 80 minutes to 10 minutes. In (Ratio A-2), the number of molecular terminal double bonds per 1,000 carbon atoms was 0.05, and Mn was 65,000.

Example 1
A reaction vessel was charged with 100 parts of (A-1), 30 parts of maleic anhydride, 17.3 parts of styrene (C-1), and 100 parts of xylene. After purging with nitrogen, the temperature was raised to 130 ° C. under nitrogen flow. And uniformly dissolved. A solution prepared by dissolving 0.5 parts of dicumyl peroxide [trade name “Park Mill D”, manufactured by NOF Corporation] in 10 parts of xylene was added dropwise over 10 minutes, and stirring was continued for 3 hours under reflux of xylene. It was. Thereafter, xylene and unreacted maleic anhydride were distilled off under reduced pressure (1.5 kPa, the same applies hereinafter) to obtain a polyolefin resin modifier (K-1). (K-1) had an acid value of 110 and Mn of 7,000.

Example 2
In Example 1, instead of (A-1) 100 parts, maleic anhydride 30 parts, (C-1) 17.3 parts, (A-2) 100 parts, maleic anhydride 82 parts, (C-1 ) A polyolefin resin modifier (K-2) was obtained in the same manner as in Example 1 except that 57.6 parts were used. (K-2) had an acid value of 196 and Mn of 9,000.

Example 3
In Example 1, instead of 100 parts of (A-1), 30 parts of maleic anhydride, and 17.3 parts of (C-1), 100 parts of (A-3), 1 part of maleic anhydride, (C-1 ) A polyolefin resin modifier (K-3) was obtained in the same manner as in Example 1 except that 2 parts were used. (K-3) had an acid value of 6 and Mn of 45,000.

Example 4
In Example 1, it replaced with 100 parts of (A-1), and performed similarly to Example 1 except having used 100 parts of (A-4), and obtained modifier (K-4) for polyolefin resins. It was. (K-4) had an acid value of 110 and Mn of 7,000.

Example 5
In Example 1, in place of 17.3 parts of (C-1), except that 19.6 parts of p-methylstyrene (C-2) was used, the modification for polyolefin resin was performed. Agent (K-5) was obtained. (K-5) had an acid value of 105 and Mn of 7,100.

Example 6
In Example 1, instead of 30 parts of maleic anhydride and 17.3 parts of (C-1), 82 parts of maleic anhydride and 0.9 parts of (C-1) were used, and 1-decene [trade name " Linearlen 10 ”, manufactured by Idemitsu Kosan Co., Ltd., and so on. ] (D-1) Except having used 57.6 parts, it carried out similarly to Example 1 and obtained the modifier for polyolefin resins (K-6). (K-6) had an acid value of 196 and Mn of 10,000.

Example 7
In Example 1, instead of 30 parts of maleic anhydride and 17.3 parts of (C-1), 24 parts of maleic anhydride and 18.5 parts of (C-1) were used, and (D-1) 0 Except having used 9 parts, it carried out similarly to Example 1 and obtained the modifier for polyolefin resins (K-7). (K-7) had an acid value of 95 and Mn of 5,000.

Example 8
In Example 1, instead of 30 parts of maleic anhydride and 17.3 parts of (C-1), 24 parts of maleic anhydride and 18.5 parts of (C-1) were used, and 1-hexene [trade name] Except for using 0.5 parts of “Linearene 6”, manufactured by Idemitsu Kosan Co., Ltd.] (D-2), the same procedure as in Example 1 was performed to obtain a polyolefin resin modifier (K-8). . (K-8) had an acid value of 95 and Mn of 5,000.

Example 9
In Example 1, instead of 30 parts of maleic anhydride and 17.3 parts of (C-1), 17.6 parts of acrylic acid [trade name “acrylic acid” manufactured by Nippon Shokubai Co., Ltd.], (C-1 ) 18.5 parts, and 1-octadecene [trade name “Linearene 18”, Idemitsu Kosan Co., Ltd., C18 α-olefin] (D-3) 2.7 parts, In the same manner as in Example 1, a polyolefin resin modifier (K-9) was obtained. (K-9) had an acid value of 95 and Mn of 5,000.

Comparative Example 1
In Example 1, instead of 30 parts of maleic anhydride and 17.3 parts of (C-1), Example 1 was used except that 11 parts of maleic anhydride was used and (C-1) was not used. In the same manner as above, a polyolefin resin modifier (ratio K-1) was obtained. (Ratio K-1) had an acid value of 50 and Mn of 2,500.

Comparative Example 2
In Example 1, instead of (A-1) 100 parts, maleic anhydride 30 parts, (C-1) 17.3 parts, (Ratio A-1) 100 parts, maleic anhydride 40 parts, (C- 1) Except having used 55 parts, it carried out similarly to Example 1 and obtained the modifier for polyolefin resins (ratio K-2). (Ratio K-2) had an acid value of 117 and Mn of 1,000.

Comparative Example 3
In Example 1, instead of 100 parts of (A-1), 30 parts of maleic anhydride, and 17.3 parts of (C-1), 100 parts of (ratio A-2), 5.5 parts of maleic anhydride, ( C-1) Except having used 5.5 parts, it carried out similarly to Example 1 and obtained the modifier for polyolefin resins (ratio K-3). (Ratio K-3) had an acid value of 28 and Mn of 67,000.

Examples 10-20, Comparative Examples 4-12
(K-1) to (K-9), (Ratio K-1) to (Ratio K-3), (A-1) and the following commercially available products according to the composition (parts) shown in Table 1, respectively. After blending for 3 minutes with a Henschel mixer, a polyolefin resin composition was obtained by melt-kneading in a twin screw extruder with a vent at 180 ° C., 100 rpm, and a residence time of 5 minutes.
(Ratio K-4): Commercially available low molecular weight modifier [aliphatic ester nonionic surfactant, trade name “
Chemistat 1100 ", Sanyo Chemical Industries, Ltd.]
(F-1): Commercially available polypropylene [trade name “Sun Allomer PL500A”, Sun Allo
[Mer Co., Ltd.]
(F-2): Commercially available polyethylene [trade name “Novatech HJ362N”, Nippon Polyethylene
Len Co., Ltd., Mn 350,000]
(F-3): Commercially available ethylene / propylene copolymer [trade name “Sun Allomer PB522”
A ", manufactured by Sun Allomer Co., Ltd., Mn 300,000]

Each resin composition was molded at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. using an injection molding machine [trade name “PS40E5ASE”, Nissei Plastic Industry Co., Ltd.], and a predetermined test piece was prepared. Evaluation was made according to the method. The results are shown in Table 1.

<Evaluation method>
1. Impact resistance (Unit: J / m)
Izod impact values were measured according to ASTM D256.
2. Tensile modulus (unit: MPa)
The measurement was performed according to JIS K7161.
3. Wettability (Unit: mN / m)
The wetting tension was measured in accordance with JIS K6768 using a test liquid mixture [ethylene glycol monoethyl ether / formamide = 100/0 to 0/100 (volume ratio)].
It shows that the wettability with respect to water is so favorable that wetting tension is large.
4). Persistence of wettability (unit: mN / m)
Circulating thermostat whose specimen was adjusted to 50 ° C. [trade name “DN410H”, manufactured by Yamato Scientific Co., Ltd.]
After standing for 30 days, the above 3. The wetting tension was measured in the same manner as above.

  From the results shown in Table 1, the polyolefin resin composition of the present invention is excellent in moldability, and the molded product formed by molding the composition has mechanical strength, wettability to water and sustainability of the wettability as compared with the comparative product. It turns out that all are excellent.

  The modifier for polyolefin resin of the present invention is excellent in imparting wettability to water without lowering the mechanical strength of a molded product, and is a molding formed by molding a polyolefin resin composition containing the modifier The product has an excellent balance between wettability and mechanical strength, and also has excellent sustainability of the wettability, so it can be used for electrical and electronic equipment, packaging materials, transport materials, household materials, building materials, etc. Can be applied in the field. In addition, since the molded product contains a modifier having a carboxyl group, it has excellent scavenging ability for ammonium ions, metal ions, etc., so it can be used in applications where the performance is expected (such as battery separators). It can be applied to a wide range of fields, such as being applicable, and is extremely useful.

Claims (9)

In the presence of the radical initiator (E), a polyolefin (A) having a number average molecular weight of 800 to 50,000, an unsaturated dicarboxylic acid (anhydride) (B) , styrene or a styrene derivative (C) and 6 to 36 carbon atoms. The modifier for polyolefin resins (K) obtained by copolymerizing the α-olefin (D ). 2. (A) has from 0.1 to 20 unsaturated bonds per 1,000 carbon atoms at the molecular ends. The modifier described. The modifier according to claim 1 or 2 , wherein (A) is obtained by thermally degrading a polyolefin having a number average molecular weight of 30,000 to 400,000. The content based on the total weight of (A), (B) and (C) is 30 to 98% for (A), 0.03 to 40% for (B), and 0.6 to 65% for (C). The modifier according to any one of claims 1 to 3 . The modifier according to any one of claims 1 to 4 , wherein the content of (D) based on the total weight of (A), (B) and (C) is 65% or less. A polyolefin resin composition comprising the modifier (K) according to any one of claims 1 to 5 and a polyolefin resin (F). The composition according to claim 6 , wherein the weight ratio of (K) to (F) is from 10/90 to 40/60. A molded article formed by molding the composition according to claim 6 or 7 . A molded article obtained by coating and / or printing the molded article according to claim 8 .