JP2018199760A - Modified polyolefin - Google Patents

Abstract

To provide a modified polyolefin imparting excellent adhesiveness with a fibrous substance such as a carbon fiber and a glass fiber to a polyolefin resin, and a fibrous substance-containing polyolefin resin composition capable of obtaining a molded product having mechanical strength such as excellent tensile strength and flexure elasticity.SOLUTION: A modified polyolefin (X) that is a radical reactant between a polyolefin (A) having 1 to 20 double bonds per 1000 carbon atoms and a monomer component (B) containing an epoxy group-containing vinyl monomer (b1), the radical reactant has a structure in which the (A) and (B) are copolymerized and/or a structure in which the (B) is grafted to the (A).SELECTED DRAWING: None

Description

  The present invention relates to a modified polyolefin and a polyolefin resin composition comprising the modified polyolefin, a polyolefin resin and a fibrous substance.

  Fiber-reinforced composite materials using polyolefin resin as a matrix are excellent in mechanical strength and heat-resistant dimensional stability, etc., and are widely used in automotive parts, electrical parts, and various industrial parts. Studies have been conducted on improving the adhesion between the matrix resin and the fibrous material.

As a method for improving the adhesion between the polyolefin resin and the fibrous material, a method using a polyolefin modified with an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof is a glass fiber (see, for example, Patent Documents 1 and 2). ) And carbon fibers (see, for example, Patent Documents 3 and 4).
However, in applications requiring high strength such as structural members, the above technique is not sufficient, and further improvement in mechanical strength is required.

JP-A-48-56739 Japanese Patent Publication No.49-15467 JP 2003-277525 A JP 2005-213478 A

  An object of the present invention is to obtain a modified polyolefin that imparts excellent adhesion to a fibrous material such as carbon fiber and glass fiber to a polyolefin resin, and a molded product having excellent mechanical strength such as tensile strength and flexural modulus. Another object of the present invention is to provide a polyolefin resin composition containing a fibrous substance.

As a result of intensive studies to solve the above problems, the present inventor has reached the present invention. That is, the present invention is a radical reaction product of a polyolefin component (A) having 1 to 20 double bonds per 1,000 carbon atoms and a monomer component (B) containing an epoxy group-containing vinyl monomer (b1). A modified polyolefin (X) having a structure in which (A) and (B) are copolymerized and / or a structure in which (B) is grafted to (A);
A polyolefin resin composition (Y) comprising the modified polyolefin (X), a polyolefin resin (D) and a fibrous substance (E); a molded article formed by molding the polyolefin resin composition (Y); A molded article obtained by painting and / or printing a product.

The modified polyolefin (X) of the present invention has the following effects.
(1) The modified polyolefin of the present invention is excellent in the effect of improving the adhesion between the polyolefin resin and the fibrous material.
(2) The molded article of the polyolefin resin composition containing the modified polyolefin, polyolefin resin, and fibrous substance of the present invention is excellent in mechanical strength (tensile strength, flexural modulus, etc.).

  The modified polyolefin (X) of the present invention comprises a monomer component (B) containing a polyolefin (A) having 1 to 20 double bonds per 1,000 carbon atoms and an epoxy group-containing vinyl monomer (b1). And (A) and (B) are copolymerized and / or (A) is grafted onto (A).

[Polyolefin (A)]
In the polyolefin (A) having 1 to 20 double bonds per 1,000 carbon atoms in the present invention, the following polyolefin (A0) may be referred to as a thermal degradation method (hereinafter referred to as a thermal degradation method). The production method described in JP-B No. 43-9368, JP-B No. 44-29742, and JP-B No. 6-70094 is preferred.

As the thermal degradation method, the polyolefin (A0) is (1) a thermal degradation method in the absence of an organic peroxide, preferably at 300 to 450 ° C. for 0.5 to 10 hours, and (2) an organic peroxide. In the presence of a product [for example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane], a method of thermally degrading at 180 to 300 ° C. for 0.5 to 10 hours is preferable.
Among these, the method (1) in which a compound having a larger number of double bonds in the molecular terminal and / or molecular chain is more preferable from the viewpoint of the modification property of the resulting modified polyolefin (X).

  As the polyolefin (A0) in the present invention, one or two or more (co) polymers of olefins and one or more of olefins and one or two or more of other monomers are co-weighted. Coalescence is mentioned. Examples of the olefin include alkenes having 2 to 30 carbon atoms (hereinafter sometimes abbreviated as C) such as ethylene, propylene, 1- or 2-butene and isobutene, and C5-30 α-olefins (1-hexene, 1-decene, 1-dodecene, etc.); other monomers include C4-30 unsaturated monomers having copolymerizability with olefins, such as vinyl acetate.

Specific examples of (A0) include ethylene unit-containing (propylene unit-free) (co) polymers such as high, medium or low density polyethylene and ethylene and C4-30 unsaturated monomers [butene (1-butene Etc.), a copolymer with a C5-30 α-olefin (such as 1-hexene and 1-dodecene) and vinyl acetate, etc. [weight ratio is the moldability of the polyolefin resin composition and the molecular end of (A) and / or Or from the viewpoint of the amount of double bonds in the molecular chain, preferably 30:70 to 99: 1, more preferably 50:50 to 95: 5], etc .; propylene unit-containing (ethylene unit-free) (co) polymer, For example, a copolymer of polypropylene, propylene and a C4-30 unsaturated monomer (same as above) (weight ratio is the same as above); ethylene / propylene copolymer (weight ratio is polyolefin resin composition) From the viewpoint of moldability and the amount of double bonds in the molecular ends and / or molecular chains of (A), 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.
Among these, polyethylene, polypropylene, ethylene / propylene copolymer and propylene / C4-30 unsaturated monomer copolymer are preferable from an industrial viewpoint, and polyethylene, ethylene / propylene copolymer are more preferable. And an unsaturated monomer copolymer of propylene / C4-30. In addition, (A0) may be used individually by 1 type, or may use 2 or more types together.

  The number average molecular weight (hereinafter abbreviated as Mn) of (A0) is preferably 100,000 to 2,000,000, more preferably from the viewpoint of the mechanical strength of the molded article and the productivity of polyolefin (A) described later. Is 150,000 to 1,500,000, particularly preferably 200,000 to 1,000,000.

Mn in the present invention is measured by the gel permeation chromatography (GPC) method under the following conditions.
Apparatus: High-temperature gel permeation chromatograph
["Alliance GPC V2000", manufactured by Waters Corporation]
Detector: Refractive index detector Solvent: Orthodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm, MIXED-B 2 in series
[Made by Polymer Laboratories, Inc.]
Column temperature: 135 ° C

(A) preferably has a double bond in the molecular terminal and / or molecular chain from the viewpoint of reactivity with the monomer component (B).
The number of double bonds per 1,000 carbon atoms (also referred to as 1,000 carbon atoms) in (A) is 1 to 20, preferably 3.0 to 20 from the viewpoint of reactivity with (B). The number is more preferably 3.2 to 18, and particularly preferably 3.5 to 15.
The number of double bonds in the present invention can be determined from the spectrum of (A) ¹ H-NMR (nuclear magnetic resonance) spectroscopy.
That is, the peak in the spectrum is assigned, and from the integrated value derived from the double bond and the integrated value derived from (A) at 4.5 to 6 ppm of (A), the number of double bonds of (A) and (A) The relative value of the number of carbons is obtained, and the number of double bonds per 1,000 carbons in (A) is calculated.

  Mn of (A) is 1,200 to 200,000, preferably 4,000 to 20,000. When the Mn is less than 1,200, the molded product of the polyolefin resin composition (Y) described later is inferior in mechanical strength, and when the Mn exceeds 200,000, the modified polyolefin (X) modification efficiency described later is inferior.

[Monomer component (B)]
The monomer component (B) in the present invention contains an epoxy group-containing vinyl monomer (b1) as an essential component. In order to increase the grafting efficiency of the epoxy group-containing vinyl monomer, the following vinyl monomers (b2) to (b5) that do not contain an epoxy group may be further contained as optional components.

The epoxy group-containing vinyl monomer (b1) in the present invention is a C3-30 epoxide having one or more polymerizable unsaturated groups. (B1) includes glycidyl group-containing (meth) acrylates having 6 to 20 carbon atoms such as glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate; 4-vinyl-1,2-epoxycyclohexane and 5-vinyl- C6-C20 alicyclic epoxy group-containing vinyl monomer such as 2,3-epoxynorbornane, carbon such as N- (4- (2,3-epoxypropoxy) -3,5-dimethylphenylmethyl) acrylamide Examples include glycidyl group-containing acrylamide of several 6 to 20.
Among these, glycidyl (meth) acrylate is preferable from the viewpoint of the polymerizability with the polyolefin (A) and the modification effect of the modified polyolefin (X) described later.
(B1) may be used alone or in combination of two or more.

  Examples of the vinyl monomer not containing an epoxy group in the present invention include a carboxylic acid (anhydride) group-containing vinyl monomer (b2), a sulfo group-containing vinyl monomer (b3), and an ester having no acid group and acid anhydride group. Examples thereof include a group-containing vinyl monomer (b4) and a vinyl hydrocarbon (b5), and these may be used alone or in combination of two or more.

  As the carboxylic acid (anhydride) group-containing vinyl monomer (b2), an unsaturated monocarboxylic acid having 3 to 30 carbon atoms, an unsaturated dicarboxylic acid and its anhydride and its monoalkyl (1 to 24 carbon atoms) ester, For example, (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoester, citraconic acid, citracone Examples include acid monoalkyl esters and cinnamic acid.

  Examples of the sulfo group-containing vinyl monomer (b3) include alkene sulfonic acids having 2 to 14 carbon atoms, such as vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid; styrene sulfonic acid and its C 1 to 24 carbon atoms. Alkyl-substituted products such as α-methylstyrene sulfonic acid, etc .; sulfo (hydroxy) alkyl (C 1-8)-(meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2- (meth) Acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid; alkyl (C3-C18) (meth) ant Sulfosuccinates; and the like.

As the ester group-containing vinyl monomer (b4) having no acid group and acid anhydride group,
Esters of unsaturated alcohols or hydroxystyrenes with mono- or polycarboxylic acids having 1 to 12 carbon atoms such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, methyl-4 -Vinyl benzoate, vinyl methoxyacetate, vinyl benzoate and acetoxystyrene; unsaturated carboxylic alcohol (1-30 carbon atoms) ester such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth ) Acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrelane , Cyclohexyl (meth) acrylate, methylnorbornene (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, ethyl-α-ethoxy (meth) acrylate, di (cyclo) alkyl fumarate (two alkyl groups are , A linear or branched group having 2 to 8 carbon atoms) and di (cyclo) alkyl maleate (two alkyl groups are a linear or branched group having 2 to 8 carbon atoms); Polyvalent (2-3) alcohol unsaturated carboxylic acid ester, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate and polyethylene Glycol di (meth) acrylate; polyoxyalkylene (2 to 4 carbon) mono- or poly (2-3) ol unsaturated carboxylic acid ester having a degree of polymerization of 5 to 50, such as poly (oxyalkylene) glycol chain (of alkelene) Vinyl monomers having 2 to 4 carbon atoms [poly (oxyethylene) glycol (degree of polymerization 7) mono (meth) acrylate, poly (oxypropylene) glycol (degree of polymerization 9) mono (meth) acrylate, methyl alcohol ethylene oxide 10 Mole adduct (meth) acrylate and lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate;

As vinyl hydrocarbon (b5),
(5-1) Aliphatic vinyl hydrocarbons: alkenes having 2 to 20 carbon atoms such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, and other α-olefins An alkadiene having 4 to 20 carbon atoms, such as butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene and 1,7-octadiene;
(5-2) Alicyclic vinyl hydrocarbons: mono- or dicycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and vinylnorbornene; terpenes such as pinene and limonene;
(5-3) Aromatic vinyl hydrocarbons (8 to 20 carbon atoms): Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products such as α-methylstyrene, vinyltoluene, 2 , 4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene and trivinylbenzene; vinylnaphthalene; and the like.

[Modified polyolefin (X)]
A structure in which polyolefin (A) and monomer component (B) are reacted in the presence of a radical initiator (C) and (A) and (B) are copolymerized and / or (B) is grafted onto (A). A modified polyolefin (X) having the above structure is obtained.

  Examples of the radical initiator (C) include azo compounds [azobisisobutyronitrile, azobisisovaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile)], 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-butylperoxycyclohexyl) propane, di-t-butylperoxyhexahydroterephthalate, diallylperoxydicarbonate and α, α'-bis (t-butylper Oxide-m-isopropyl) benzene and the like]] and the like.

  Among these, from the viewpoint of the reactivity of (A) and (B), preferred are peroxides, and more preferred are di-t-butyl peroxide, lauroyl peroxide, dicumyl peroxide and α, α ′. -Bis (t-butyl peroxide-m-isopropyl) benzene.

  The amount of (C) used is preferably 0.05 to 10%, more preferably 0.2 to 5% based on the total weight of (A) and (B) from the viewpoint of reactivity and side reaction suppression. Especially preferably, it is 0.3 to 3%.

Specific methods for producing the acid-modified polyophine (X) of the present invention include the following methods [1] and [2].
[1] (A) and (B) are mixed with a suitable organic solvent [C3-18, such as hydrocarbon (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbon (di-, tri- Or 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.)]. Turbid or dissolved, and (C) [or (C) dissolved in a suitable organic solvent (the same as above)] and, if necessary, a chain transfer agent (t) and a polymerization inhibitor (f) described later. In addition, heating and stirring (solution method);
[2] A method (melting method) in which (A), (B), (C) and, if necessary, (t) and (f) are mixed in advance and melt-kneaded using an extruder, a Banbury mixer, a kneader or the like.

  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 ° C, more preferably 110 to 210 ° C from the viewpoint of the reactivity of (A) and (B). Especially preferably, it is 120-180 degreeC.

  The reaction temperature in the melting method may be a temperature at which (A) melts, and is preferably 120 to 260 ° C. from the viewpoint of the reactivity of (A) and (B) and the decomposition temperature of the reaction product. Preferably it is 130-240 degreeC.

  Examples of the chain transfer agent (t) include alcohols (C1-24, such as methanol, ethanol, 1-propanol, 2-butanol and allyl alcohol); thiols (C1-24, such as ethylthiol, propiothiol, 1- And 2-butylthiol and 1-octylthiol); aldehydes (C2-18, such as 2-methyl-2-propylaldehyde, 1- and 2-butyraldehyde and 1-pentylaldehyde); phenols (C6-36, such as phenol) And o-, m- or p-cresol); amines (C3-24, such as diethylmethylamine, triethylamine and diphenylamine); disulfides (C2-24, such as diethyldisulfide and di-1-propyldisulfide). The amount of (t) used is preferably 30% or less based on the total weight of (A) and (B), and more preferably 0.1 to 20% from the viewpoint of the reactivity of (A) and (B). is there.

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) and stabilizing radicals [C5-36, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH) and 2,2,6,6 -Tetramethyl-1-piperidinyl oxide (TEMPO)].
The amount of (f) used is preferably 5% or less based on the total weight of (A) and (B), and more preferably 0.01 to from the viewpoints of stability and polymerizability of (A) and (B). 0.5%.

  The weight ratio [(A) :( B)] of (A) and (B) in (X) is preferably 80 from the viewpoint of the mechanical strength of the molded article and the modified properties of the modified polyolefin (X) described later. : 20 to 99.5: 0.5, more preferably 85:15 to 99: 1.

  The Mn of the modified polyolefin (X) is preferably from 3,000 to 120,000, more preferably from 4,000 to 110,000, particularly preferably from the viewpoint of the mechanical strength of the molded article and the modified properties of (X). Is 5,000 to 100,000.

[Polyolefin resin composition (Y)]
The polyolefin resin composition (Y) of the present invention comprises a modified polyolefin (X), a polyolefin resin (D), and a fibrous substance (E).

  As polyolefin resin (D) in this invention, the thing similar to the said polyolefin (A0) is mentioned.

  Examples of the fibrous substance (E) in the present invention include carbon fiber, glass fiber, alumina fiber, ceramic fiber, rock fiber, slug fiber, and aramid fiber. From the viewpoint of the mechanical strength of the molded product, it is preferable. Carbon fiber and glass fiber. These fibers may be used alone or in combination of two or more.

Examples of the carbon fiber include various carbon fibers such as carbon fiber made of polyacrylonitrile, rayon, pitch, hydrocarbon gas, graphite fiber, and metal-coated carbon fiber coated with a metal such as nickel, aluminum and copper. Can be mentioned.
Among these, from the viewpoint of mechanical strength, polyacrylonitrile-based carbon fibers and metal-coated carbon fibers obtained by coating them with metal are preferable.

  Specific examples of the glass fiber include glass roving, glass chopped strand, glass milled fiber, glass staple, and glass cloth.

  The shape of (E) is not particularly limited, but the fiber diameter of (E) is preferably 1 to 1,000 μm, more preferably 3 to 500 μm, from the viewpoint of mechanical strength and moldability of the molded product. In addition, the fiber length of (E) is preferably 1 to 100 mm, more preferably 2 to 50 mm, from the viewpoint of mechanical strength and moldability of the molded product.

  The weight ratio of (X) to (E) in (Y) is preferably 0.1 to 40% by weight, more preferably 0 from the viewpoints of the adhesiveness of (E) and (X) and the mechanical strength of the molded product. .3 to 30% by weight, particularly preferably 0.5 to 20% by weight.

The polyolefin resin composition (Y) of the present invention can further contain various additives (F) as necessary within the range not impairing the effects of the present invention.
(F) includes colorant (F1), flame retardant (F2), filler (F3), lubricant (F4), antistatic agent (F5), dispersant (F6) other than (X), antioxidant (F7), an ultraviolet absorber (F8), etc. are mentioned.

Examples of the colorant (F1) include pigments and dyes.
Examples of the pigment include inorganic pigments (such as alumina white and graphite); organic pigments (such as azo lakes).
Examples of the dye include azo dyes and anthraquinone dyes.

  Examples of the flame retardant (F2) 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 [Polyorganosiloxane and the like] and phosphorus-containing [phosphate ester and the like]]; inorganic flame retardants [antimony trioxide, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, etc.] and the like.

  Fillers (F3) 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, quartzite powder, talc, silica, zeolite, woody materials (wood powder, etc.) and mixtures thereof.

  Examples of the lubricant (F4) 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).

Examples of the antistatic agent (F5) include nonionic, cationic, anionic or 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 higher) [saturated and unsaturated, higher Alcohol (C8-18), higher aliphatic amine (C8-24) and higher fatty acid (C8-24) etc.]] (poly) oxyalkylene derivative (AO adduct and polyalkylene glycol higher fatty acid mono- or di-ester) ); (Poly) oxyalkylene derivatives of higher fatty acid (C8-24) ester of polyhydric alcohol (C3-60) (Tween type nonionics, etc.); (poly) oxyalkylene of (alkanol) amide of higher fatty acid (above) Derivatives; (poly) oxyalkylene derivatives of polyhydric alcohols (above) alkyl (C3-60) ethers; And polyoxypropylene polyol [polyoxypropylene derivatives of polyhydric alcohol and polyamine (C2-10) (pluronic type and tetronic nonionics)]; polyhydric alcohol (above) type nonionics (for example, fatty acid ester of polyhydric alcohol) , Polyhydric alcohol alkyl (C3-60) ether and fatty acid alkanolamide); 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 ] Ammonium Salts (sapamine type quaternary ammonium salts) [these salts include, for example, salts of halides (chloride, bromide, etc.), alkyl sulfates (methosulphate, etc.) and organic acids (below); Onyx: primary to tertiary amines [for example, higher aliphatic amines (C12-60), polyoxyalkylene derivatives of aliphatic amines (such as methylamine and diethylamine) [ethylene oxide (hereinafter abbreviated as EO) adducts, etc.] and acylaminoalkyls Or an acyloxyalkyl (above) di (hydroxy) alkyl (above) amine (stearoyloxyethyldihydroxyethylamine, stearamideethyldiethylamine, etc.)] salt of inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc.) and organic acid ( C2-22) salt.

(3) Anionic surfactants Higher fatty acid (above) salts (sodium laurate, etc.), ether carboxylic acids [carboxymethylated products of EO (1-10 mol) adducts, etc.] and their salts; sulfate salts (alkyls) And alkyl ether sulfates, etc.), sulfated oils, sulfated fatty acid esters and sulfated olefins; sulfonates [alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl ester sulfosuccinates, α-olefin (C12-18) sulfones Acid salt, N-acyl-N-methyltaurine (Igepon T type, etc.), etc.], and phosphate ester salts (alkyl, alkyl ether, alkylphenyl ether phosphate, 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)]; sulfate (Salt) type amphoterics [sulfuric ester (salt) of laurylamine, hydroxyethyl imidazoline sulfate (salt), etc.]; sulfonic acid (salt) type amphoterics [pentadecyl sulfotaurine and imidazoline sulfonic acid (salt) ) Etc.]; and phosphate ester (salt) type amphoterics etc. [phosphate ester (salt) etc. of glycerol lauryl ester].

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

  Examples of the dispersant (F6) 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, Etc.) and vinyl resins other than the above polyolefins [polyvinyl halide [polyvinyl chloride, polyvinyl bromide, etc.], polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly (meth) Acrylic acid, poly (meth) acrylic acid ester [poly (meth) methyl acrylate etc.] and styrene resin [polystyrene, acrylonitrile / styrene (AS) resin etc.]; polyester resin [polyethylene terephthalate etc.], polyamide resin 6,6 nylon and 12-nylon or the like], polyether resin [a polyether sulfone, etc.], polycarbonate resin [polycondensate of bisphenol A and phosgene, etc.] and the block copolymer thereof.

  Antioxidants (F7) include hindered phenol compounds [pt-amylphenol-formaldehyde resin, nordihydroguaiaretic acid (NDGA), 2,6-di-tert-butyl-4-methylphenol (BHT). ), 2-t-butyl-4-methoxyphenol (BHA), 6-t-butyl-2,4, -dimethylphenol (24M6B) and 2,6-di-t-butylphenol (26B)]; Compound [N, N′-diphenylthiourea, dimyristylthiodipropionate, etc.]; Phosphorus compound [2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p- Nonylphenyl) phosphite and dioctadecyl-4-hydroxy-3,5-di-t-butylbenzylphosphonate, etc.] It is.

  Examples of the ultraviolet absorber (F8) include salicylate compounds [phenyl salicylate and the like]; benzophenone compounds [2,4-dihydroxybenzophenone and the like]; benzotriazole compounds [2- (2′-hydroxy-5′-methylphenyl)- Benzotriazole, etc.].

The total content of (F) in the polyolefin resin composition (Y) is preferably 20% or less based on the total weight of (Y), and more preferably 0.05 from the viewpoint of the functional expression of each (F). -10%, particularly preferably 0.1-5%.
(F1) is preferably 5% or less, more preferably 0.1 to 3%; (F2) is preferably 8% or less, and more preferably 1 based on the total weight of (Y). (F3) is preferably 5% or less, more preferably 0.1 to 1%; (F4) is preferably 8% or less, more preferably 1 to 5%; (F5) is preferably 8%. Or less, more preferably 1 to 3%; (F6) is preferably 1% or less, more preferably 0.1 to 0.5%; (F7) is preferably 2% or less, more preferably 0.05 to 0. 0.5%; (F8) is preferably 2% or less, more preferably 0.05 to 0.5%.

  When the additives are the same and overlap between (F1) to (F8) above, the amounts of the respective additives exhibiting the corresponding additive effects are not used as they are, but the effects as other additives are simultaneously achieved. Considering what is obtained, the amount used is adjusted according to the purpose of use.

  As a manufacturing method of the polyolefin resin composition (Y) of the present invention, (1) the (X), (D), (E) and, if necessary, (F) are mixed together to obtain the polyolefin resin composition (Y) (2) Master batch polyolefin resin containing a high concentration of (X) by mixing part of (D), the total amount of (X) and, if necessary, part or all of (F) There is a method (masterbatch method) in which a composition is once prepared, and then the remaining (D), (E) and, if necessary, the remaining (F) are added and mixed to obtain a polyolefin resin composition (Y). The method (2) is preferred from the viewpoint of the mixing efficiency of (X).

As a specific mixing method in the method for producing the polyolefin resin composition (Y),
(I) For each component to be mixed, for example, a powder mixer [“Henschel Mixer” [trade name “Henschel Mixer FM150L / B”, Mitsui Mining Co., Ltd., after changing the company name, manufactured by Nippon Coke Industries, Ltd.], “ After mixing with “Nauter Mixer” [trade name “Nauter Mixer DBX3000RX”, manufactured by Hosokawa Micron Co., Ltd.] and “Banbury Mixer” [trade name “MIXTRON BB-16MIXER”, manufactured by Kobe Steel, Ltd.], etc.] A method of kneading preferably at 120 to 220 ° C. for 2 to 30 minutes using a melt kneader [batch kneader and continuous kneader (single screw kneader, twin screw kneader, etc.)];
(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.

  The polyolefin resin composition (Y) of the present invention is excellent in the dispersibility of the fibrous substance (E), and the molded product using (Y) is excellent in mechanical strength and thermal characteristics. The mechanical strength of the molded product can be evaluated by the tensile strength, bending strength, bending elastic modulus and the like described later.

[Molded articles and molded articles]
The molded article of the present invention is formed by molding the polyolefin resin composition (Y).
Examples of the molding method include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.) and the like. Molding, multilayer molding, foam molding and the like can be performed by any method that incorporates means. Examples of the shape of the molded product include a plate shape, a sheet shape, a film, a woven fabric, 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 a 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 commonly used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint, and these so-called relatively high-polarity paints can also be used. Further, paints with low polarity (such as olefins) can also be used.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is preferably 10 to 50 μm.

In addition, 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 , Screen printing, pad printing, dry offset printing, offset printing, and the like.
As the printing ink, those 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”.

[Polyolefin (A)]
Production Example 1
In a reaction vessel, 100 parts of polyolefin (A0-1) [trade name “Sun Allomer PZA20A”, manufactured by Sun Allomer Co., Ltd., Mn 100,000] having 98 mol% propylene and 2 mol% ethylene as structural units are charged in a nitrogen atmosphere. The melt was heated and melted with a mantle heater while aeration of nitrogen in the gas phase portion, and thermal degradation was performed at 360 ° C. for 40 minutes with stirring to obtain polyolefin (A-1). The number of double bonds in the molecular end and / or polymer chain per 1,000 carbon atoms of (A-1) was 1.2, and Mn was 15,000.

Production Example 2
Except having changed the heat degradation time from 40 minutes to 100 minutes, it carried out like manufacture example 1 and obtained polyolefin (A-2). The number of double bonds in the molecular terminal and / or polymer chain per 1,000 carbon atoms of (A-2) was 12, and Mn was 1,500.

Production Example 3
Except having changed the heat degradation time from 40 minutes to 10 minutes, it carried out similarly to manufacture example 1 and obtained polyolefin (A-3). The number of double bonds in the molecular terminal and / or polymer chain per 1,000 carbon atoms of (A-3) was 0.2, and Mn was 80,000.

Production Example 4
Polyolefin (A0-2) containing 80 mol% of propylene and 20 mol% of 1-butene as a structural unit (trade name “Tafmer XM-5080”, manufactured by Mitsui Chemicals, Inc., Mn90,000, same as below. ] Was performed in the same manner as in Production Example 1, except that the polyolefin (A-4) was obtained. The number of double bonds in the molecular terminal and / or polymer chain per 1,000 carbon atoms of (A-4) was 1.2, and Mn was 15,000.

  Table 1 summarizes the types of polyolefin (A0) used in Production Examples 1 to 4, the thermal degradation conditions, and the properties of polyolefin (A).

[Modified polyolefin (X)]
Example 1
In a reaction vessel, 100 parts of (A-1) was charged, and after substitution with nitrogen, the mixture was heated to 180 ° C. and dissolved under nitrogen flow. After 10 parts of glycidyl methacrylate (B-1) was added and mixed uniformly, α, α′-bis (t-butylperoxide-m-isopropyl) benzene [trade name “Perbutyl P”, NOF Corporation [Production] A solution prepared by dissolving 1 part of (C-1) in 5 parts of xylene was added dropwise over 10 minutes, and stirring was continued at 180 ° C for 3 hours. Thereafter, xylene and unreacted glycidyl methacrylate were distilled off under reduced pressure (1.5 kPa, the same shall apply hereinafter), and then taken out from the reaction vessel.
After the obtained resin was dissolved in xylene heated to 120 ° C., the xylene solution was dropped into acetone and reprecipitated to remove the glycidyl methacrylate homopolymer to obtain a modified polyolefin (X-1). . The Mn of (X-1) was 18,000.

Example 2
A modified polyolefin (X-2) was obtained in the same manner as in Example 1 except that (A-1) was replaced with (A-2). Mn of (X-2) was 3,500.

Example 3
A modified polyolefin (X-3) was obtained in the same manner as in Example 1 except that (A-1) was replaced with (A-3). The Mn of (X-3) was 90,000.

Example 4
A modified polyolefin (X-4) was obtained in the same manner as in Example 1 except that (A-1) was replaced with (A-4). Mn of (X-4) was 18,000.

Example 5
A modified polyolefin (X-5) was obtained in the same manner as in Example 1 except that (B-1) was replaced with glycidyl acrylate (B-2). The Mn of (X-5) was 17,000.

Example 6
A modified polyolefin (X-6) was obtained in the same manner as in Example 1 except that (B-1) was replaced with 4-vinyl-1,2-epoxycyclohexane (B-3). The Mn of (X-6) was 18,000.

Example 7
The modified polyolefin was obtained in the same manner as in Example 1 except that (B-1) was replaced with N- (4- (2,3-epoxypropoxy) -3,5-dimethylphenylmethyl) acrylamide (B-4). (X-7) was obtained. The Mn of (X-7) was 18,000.

Example 8
In addition to 100 parts of (A-1), 10 parts of (B-1) and 1 part of (C-1), the same procedure as in Example 1 was carried out except that 10 parts of methacrylic acid (B-5) was used. Modified polyolefin (X-8) was obtained. The Mn of (X-8) was 20,000.

Example 9
In addition to 100 parts of (A-1), 10 parts of (B-1) and 1 part of (C-1), the same procedure as in Example 1 was carried out except that 10 parts of vinyl acetate (B-6) was used. Modified polyolefin (X-9) was obtained. The Mn of (X-9) was 21,000.

Example 10
(A-1) In the same manner as in Example 1 except that 10 parts of 1-decene (B-7) was used in addition to 100 parts of (B-1) and 1 part of (C-1). The modified polyolefin (X-10) was obtained. The Mn of (X-10) was 19,000.

Example 11
In addition to 100 parts of (A-1), 10 parts of (B-1) and 1 part of (C-1), this was carried out in the same manner as in Example 1 except that 10 parts of styrene (B-8) was used. Polyolefin (X-11) was obtained. The Mn of (X-11) was 19,000.

Example 12
The modified polyolefin (X-12) was prepared in the same manner as in Example 1 except that (C-1) was replaced with dicumyl peroxide [trade name “Park Mill D”, manufactured by NOF Corporation] (C-2). ) The Mn of (X-12) was 16,000.

Example 13
(C-1) The modified polyolefin was carried out in the same manner as in Example 1 except that 1 part was replaced with di-t-butyl peroxide [trade name “Perbutyl D”, manufactured by NOF Corporation] (C-3). (X-13) was obtained. The Mn of (X-13) was 15,000.

  Table 2 summarizes the types and amounts used of the raw materials used in Examples 1 to 13 and the Mn of the resulting modified polyolefin.

[Polyolefin resin composition and molded product]
Examples 14 to 29 and Comparative Example 1
Using the modified polyolefins obtained in Examples 1 to 13 and the following raw materials [polyolefin resin (D) and fibrous substance (E)], the side feeder was used in accordance with the composition shown in Table 2 (units of numerical values are parts). A polyolefin resin composition was obtained by melt kneading in a twin screw extruder under the conditions of 220 ° C., 100 rpm, and a residence time of 5 minutes. Each polyolefin resin composition was molded at a cylinder temperature of 220 ° C. and a mold temperature of 50 ° C. using an injection molding machine [trade name “PS40E5ASE”, Nissei Plastic Industry Co., Ltd.]. Tensile strength, flexural modulus and flexural strength were measured by the test method. The results are shown in Table 3.

<Raw materials>
[Polyolefin resin (D)]
(D-1): Commercially available polypropylene [trade name “Sun Aroma VMD81M”,
Sun Allomer Co., Ltd., Mn 300,000]
(D-2): commercially available polyethylene [trade name “NOVATEC HJ490”,
Nippon Polyethylene Co., Ltd., Mn 300,000]
(D-3): Commercially available ethylene / propylene copolymer [trade name “Sun Allomer PB222A
”, Manufactured by Sun Allomer Co., Ltd., Mn 350,000]
[Fibrous material (E)]
(E-1): Carbon fiber [trade name “Pyrofil TRW40 50LAJA”, Mitsubishi Chemi
Cull Co., Ltd., fiber diameter 7 μm] cut to 5 mm fiber length (E-2): Glass fiber [trade name “230QR-483AS”, Nittobo Co., Ltd.,
Fiber diameter 13 μm] cut to 5 mm fiber length.

<Test method>
(1) Tensile strength (unit: MPa)
Measured according to ASTM D638.
(2) Flexural modulus (unit: GPa)
Measured according to ASTM D790.
(3) Bending strength (unit: MPa)
Measured according to ASTM D790.

  The modified polyolefin (X) of the present invention imparts excellent adhesion to the fibrous material (E) to the polyolefin resin (D), and the modified polyolefin (X), polyolefin resin (D) and fibrous material (E). The molded product formed by molding a polyolefin resin composition containing the resin has excellent mechanical strength, so it is widely used for electrical and electronic equipment, transportation materials, household materials, automotive parts and building materials. Since it can be suitably applied to the field, it is extremely useful.

Claims (7)

  A radical reaction product of a polyolefin component (A) having 1 to 20 double bonds per 1,000 carbon atoms and a monomer component (B) containing an epoxy group-containing vinyl monomer (b1), (A) And (B) a modified polyolefin (X) having a structure in which (B) is copolymerized and / or a structure in which (B) is grafted to (A).   The modified polyolefin according to claim 1, wherein the polyolefin (A) has a number average molecular weight of 1,200 to 200,000.   The monomer component (B) further includes a carboxylic acid (anhydride) group-containing vinyl monomer (b2), a sulfo group-containing vinyl monomer (b3), and an ester group-containing vinyl monomer having no acid group and acid anhydride group. The modified polyolefin according to claim 1 or 2, comprising at least one vinyl monomer selected from the group consisting of (b4) and a vinyl hydrocarbon (b5).   A polyolefin resin composition (Y) comprising the modified polyolefin (X) according to any one of claims 1 to 3, a polyolefin resin (D), and a fibrous substance (E).   The polyolefin resin composition according to claim 4, wherein a weight ratio of the modified polyolefin (X) to the fibrous substance (E) is 0.1 to 40% by weight.   A molded product formed by molding the polyolefin resin composition (Y) according to claim 4 or 5.   A molded article obtained by coating and / or printing the molded article according to claim 6.