JP2005132972A - Resin modifier and polyolefine resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin modifier which has an excellent dispersibility in a polyolefin resin and an adhesiveness with the resin matrix and improves impact resistance, dye-affinity and paintability of the resin while keeping moldability, good appearance and mechanical characteristic of the resin, and to provide a polyolefin resin composition compounded with the modifier. <P>SOLUTION: The resin modifier comprises a graft copolymer made by graft polymerization of a polymer (A) by a monomer (B) which contains at least a (meth)acrylate monomer (a) whose secondary or tertiary carbon atom is bonded with an acryloyloxy or methacryloyloxy group, and the polyolefin resin composition contains the resin modifier and the polyolefin resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention mainly relates to a resin modifier having good dispersibility in a polyolefin resin, and a polyolefin resin composition obtained by adding this resin modifier to a polyolefin resin.

  Polyolefin resins are widely used in various applications such as automobile bumpers and console panels because they are low-cost and easy to mold. In recent years, materials that can be recycled are regarded as important from the viewpoint of environmental problems, and the demand for polyolefin resins that are thermoplastic and highly recyclable is increasing.

  However, since the polyolefin resin has low polarity, it has low paintability, printability, color developability during coloring, and the like. As a result, there is a problem that the range of selection of colors and patterns applied at the time of molding or post-processing after processing is narrow and cannot be freely selected. In addition, the polyolefin resin has flexibility, but has a problem of low scratch resistance and rigidity.

  Therefore, as a method for improving the above-described drawbacks, a vinyl resin having a polarity such as a styrene resin or an acrylic resin, or a rubber having a low Tg (glass transition point) such as a butadiene rubber or a silicone rubber is used as a polyolefin resin. It is possible to blend. However, even if these are simply blended, the compatibility between the polyolefin resin and the vinyl resin or low Tg rubber is not sufficient, so the molded product molded from the blend resin has a poor appearance and causes delamination. As a result, there is a problem that the mechanical properties are greatly deteriorated.

  Further, a method of blending an acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as maleic anhydride into a polyolefin resin is conceivable. However, this blend resin has a problem that the dyeability, paintability, and the like deteriorate due to water absorption depending on the use environment.

  A method for modifying a polyolefin resin by graft polymerization of a (meth) acrylate monomer to the polyolefin resin has been proposed. For example, a modified polyolefin resin obtained by modifying a polyolefin resin with ethyl acrylate or methyl methacrylate is disclosed (for example, see Patent Document 1).

  However, although this modified polyolefin resin is not easily affected by the use environment such as water absorption, the compatibility and dispersibility of the (meth) acrylate homopolymer, which is a by-product, in the polyolefin resin is insufficient, and layer peeling becomes difficult. Accompanying this, the appearance of the molded product deteriorated, and its mechanical properties sometimes deteriorated.

  Further, a resin composition in which polypropylene and (meth) acrylic resin are blended using an olefin / acrylic block polymer synthesized using an organometallic catalyst as a compatibilizing agent has been proposed. As a specific example of such a resin composition, a blend of a propylene / methyl methacrylate block polymer synthesized with a vanadium catalyst as a compatibilizing agent for polypropylene and polymethyl methacrylate (for example, Non-Patent Document 1). reference).

When an olefin / acrylic block polymer is used as a compatibilizing agent, a molded product having no delamination can be obtained. However, in the process of producing an olefin / acrylic block polymer, there are problems such as that a low temperature of about -60 ° C. is required and that the living property is greatly reduced due to mixing of water and oxygen. Industrial production of the polymer has been difficult.
JP-A-2-22316 Polymer Journal, Vol. 23, 1991, pp. 277-284

  The present invention has been made in view of the above circumstances, and the object of the present invention is good dispersibility in polyolefin resin, good adhesion with polyolefin resin matrix, moldability of polyolefin resin, good appearance, Resin modifier that improves the impact resistance, dyeability, paintability, etc. of polyolefin resin while maintaining mechanical properties, and impact resistance while maintaining moldability, good appearance and mechanical properties of polyolefin resin Another object of the present invention is to provide a polyolefin resin composition having excellent dyeability and paintability.

That is, the resin modifier of the present invention is a (meth) acrylic acid ester monomer (a) in which an acryloyloxy group or a methacryloyloxy group is bonded to a secondary carbon atom or a tertiary carbon atom in the polymer (A). A graft copolymer obtained by graft polymerization of a monomer (B) containing at least
Here, the (meth) acrylic acid ester monomer (a) is preferably a monomer having an alicyclic hydrocarbon group.
Further, the (meth) acrylic acid ester monomer (a) was selected from a cyclohexyl group, 4-t-butylcyclohexyl group, isobornyl group, tricyclodecanyl group, and 3,3,5-trimethylcyclohexyl group. A monomer having at least one kind is desirable.
In the monomer (B) (100% by mass), the ratio of the (meth) acrylic acid ester monomer (a) is preferably 50% by mass or more.
The graft copolymer is preferably a core-shell structure polymer.
The polyolefin resin composition of the present invention is characterized by containing the resin modifier of the present invention and a polyolefin resin.

The resin modifier of the present invention comprises at least a (meth) acrylic acid ester monomer (a) having an acryloyloxy group or a methacryloyloxy group bonded to a secondary carbon atom or a tertiary carbon atom to the polymer (A). Since it comprises a graft copolymer obtained by graft polymerization of the monomer (B) to be contained, the dispersibility in the polyolefin resin and the adhesion to the polyolefin resin matrix are good. Such a resin modifier can improve the impact resistance, dyeability, paintability, etc. of the polyolefin resin while maintaining the moldability, good appearance and mechanical properties of the polyolefin resin.
Further, since the polyolefin resin composition of the present invention contains the resin modifier of the present invention and a polyolefin resin, while maintaining the moldability, good appearance and mechanical properties of the polyolefin resin, Excellent impact, dyeability and paintability.

Hereinafter, the present invention will be described in detail.
<Polymer (A)>
As the polymer (A) in the present invention, various polymers can be selected depending on the purpose of modifying the polyolefin resin.
For example, when the purpose is to modify low temperature impact resistance and softness, the polymer (A) is preferably a polymer having a glass transition temperature of 0 ° C. or lower. Examples of such polymers include polybutadiene, polyisoprene, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, and ethylene-propylene-5-ethylidene-2-norbornene copolymer. Diene copolymers such as acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, styrene-butadiene copolymer; copolymerization with n-butyl acrylate and acrylate monomer copolymerizable therewith Examples thereof include an acrylate rubber that is a coalescence; a silicone rubber having a dimethylsiloxane unit as a main component; and a silicone / acrylic composite rubber of silicone and acrylate.
Among these, a diene copolymer, an acrylate rubber, and a silicone / acrylic composite rubber are preferably used as the polymer (A).

  When the purpose is to improve dyeability and adhesion, the polymer (A) preferably contains oxygen, nitrogen, phosphorus and sulfur atoms in the polymer. Examples of such a polymer include those containing units composed of the following monomers. Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecyl (meth) acrylate, (Meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; maleimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide and Nt-butylmaleimide Hydroxy group-containing simple substances such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Examples thereof include nitrogen-containing substances such as (meth) acrylamide, (meth) acrylonitrile, diacetone acrylamide and dimethylaminoethyl methacrylate; and epoxy group-containing monomers such as allyl glycidyl ether and glycidyl (meth) acrylate. These may be used alone or in combination of two or more.

Among these, (meth) acrylates such as methyl (meth) acrylate and n-butyl (meth) acrylate; hydroxy group-containing monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate Is preferably used as the polymer (A).
Here, (meth) acrylate means acrylate or methacrylate, (meth) acrylamide means acrylamide or methacrylamide, and (meth) acrylonitrile means acrylonitrile or methacrylonitrile.

<Monomer (B)>
The monomer (B) contains at least the (meth) acrylic acid ester monomer (a) in which an acryloyloxy group or a methacryloyloxy group is bonded to a secondary carbon atom or a tertiary carbon atom.
Examples of the (meth) acrylic acid ester monomer (a) in which an acryloyloxy group or a methacryloyloxy group is bonded to a secondary carbon atom include, for example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and cycloheptyl (meth) acrylate. , Cyclooctyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, tricyclodecanyl (meth) acrylate, cyclopentadienyl (meth) acrylate, Examples thereof include a ring structure such as isobornyl (meth) acrylate and adamantyl (meth) acrylate, and a (meth) acrylic acid ester monomer having a polycyclic alicyclic hydrocarbon group. These can be used alone or in combination of two or more.
Among these, cyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, isobornyl from the viewpoint of easy availability and adhesion to polyolefin substrates. (Meth) acrylate, tricyclodecanyl (meth) acrylate and the like are preferable.

The (meth) acrylic acid ester monomer (a) in which an acryloyloxy group or a methacryloyloxy group is bonded to a tertiary carbon atom includes t-butyl (meth) acrylate, t-amyl (meth) acrylate, dipropyl Methyl (meth) acrylate, tripropylmethyl (meth) acrylate, diisopropylmethyl (meth) acrylate, triisopropylmethyl (meth) acrylate, dibutylmethyl (meth) acrylate, tributylmethyl (meth) acrylate, diisobutylmethyl (meth) acrylate, Examples thereof include (meth) acrylic acid ester monomers having a branched hydrocarbon group such as triisobutylmethyl (meth) acrylate, di-t-butylmethyl (meth) acrylate, and tri-t-butylmethyl (meth) acrylate. These can be used alone or in combination of two or more.
Among these, t-butyl (meth) acrylate and t-amyl (meth) acrylate are preferably used, and t-butyl (meth) acrylate is particularly preferable from the viewpoints of availability and coating properties.

  The monomer (B) includes a (meth) acrylic acid ester monomer (a1) in which an acryloyloxy group or methacryloyloxy group is bonded to a secondary carbon atom, and an acryloyloxy group or methacryloyloxy group is a tertiary carbon. A monomer containing a (meth) acrylic acid ester monomer (a2) bonded to an atom may be used. In that case, these composition ratios may be arbitrarily selected depending on the required performance, but from the viewpoint of adhesion, the acryloyloxy group in the (meth) acrylate monomer (a) (100% by mass). Or it is preferable that the (meth) acrylic acid ester monomer (a1) which the methacryloyloxy group couple | bonded with the secondary carbon atom is 50 mass% or more.

Further, the monomer (B) is a single monomer having, in addition to the (meth) acrylic acid ester monomer (a), another monomer (b) different from the monomer (a). It may be a body mixture.
In this case, the graft copolymer can be obtained by graft copolymerizing the monomer (a) with the other monomer (b) copolymerizable with the polymer (A). it can.

  The monomer (b) is not particularly limited as long as it is a monomer different from the monomer (a) and can be copolymerized with the monomer (a). ) Acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (Meth) acrylates such as (meth) acrylate, stearyl (meth) acrylate and benzyl (meth) acrylate; maleimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide and Nt-butylmaleimide; 2-hydroxyethyl ( (Meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, hydroxy group-containing monomers such as 4-hydroxybutyl (meth) acrylate; (meth) acrylamide, (meth) acrylonitrile, diacetone Nitrogen-containing substances such as acrylamide and dimethylaminoethyl methacrylate; epoxy group-containing monomers such as allyl glycidyl ether and glycidyl (meth) acrylate; diene monomers such as butadiene, isoprene and chloroprene; styrene, α-methylstyrene, etc. And styrene-based monomers. These may be used alone or in combination of two or more.

In the monomer (B) (100% by mass), the proportion of the (meth) acrylic acid ester monomer (a) in which the acryloyloxy group or methacryloyloxy group is bonded to the secondary carbon atom or tertiary carbon atom is From the viewpoint of dispersibility in the resin and interfacial adhesion strength with the polyolefin resin matrix, the content is preferably 50% by mass or more, and more preferably 70% by mass or more.
Acrylic resins usually have poor dispersibility in polyolefin resins, but the monomer (B) has an acryloyloxy group or a methacryloyloxy group bonded to a secondary carbon atom or a tertiary carbon atom (meth). By including at least the acrylate monomer (a), the dispersibility of the resin modifier in the polyolefin resin and the interfacial adhesion strength between the acrylic modifier and the olefin matrix can be improved.

<Resin modifier>
The resin modifier in the present invention comprises at least a (meth) acrylic acid ester monomer (a) in which an acryloyloxy group or a methacryloyloxy group is bonded to a secondary carbon atom or a tertiary carbon atom to the polymer (A). It is the graft copolymer which graft-polymerized the monomer (B) containing. The graft copolymer has a (meth) acrylic acid ester monomer (a) in which an acryloyloxy group or a methacryloyloxy group is bonded to a secondary carbon atom or a tertiary carbon atom, thereby dispersibility in a polyolefin resin. Can be improved.
Here, “graft polymerization” refers to radical polymerization of the monomer (B) in the presence of the polymer (A) to form a graft copolymer. The graft copolymer obtained by graft polymerization of the polymer (A) with the monomer (B) usually includes an unmodified polymer (A) and the monomer (B) together with the graft copolymer. In the present invention, these are referred to as a graft copolymer unless they impair the spirit of the invention.

  The ratio of the polymer (A) and the monomer (B) in the resin modifier is not particularly limited, but the polymer (A) is 5 to 95 mass% in the resin modifier (100 mass%). The monomer (B) is preferably 5 to 95% by mass. If the proportion of the monomer (B) is too small, the dispersibility and adhesion to the polyolefin resin may decrease, and if it is too large, the modification effect may not be obtained.

  The structure of the resin modifier (graft copolymer) is not particularly limited as long as the monomer (B) is graft-polymerized with the polymer (A), but from the viewpoint of dispersibility and adhesion to a polyolefin resin. Therefore, a core-shell structure in which the polymer (A) is a core layer and the polymer (B) is a shell layer is preferable.

  The method for producing the graft copolymer is not particularly limited, but as a usual method, first, a polymer (A) latex is obtained by emulsion polymerization, and then the monomer (B) is added thereto, thereby radical graft copolymerization technology. The method of radically polymerizing the monomer (B) in one step or in multiple steps may be mentioned. For the resin modifier, this graft copolymer latex is poured into hot water in which an acid such as sulfuric acid or hydrochloric acid or a metal salt such as calcium chloride, calcium acetate or magnesium sulfate is dissolved, and salted out and coagulated. It is obtained by separating and recovering the solidified product. It can also be obtained by a direct drying method such as a spray drying method.

<Polyolefin resin composition>
The resin modifier of the present invention can be used as a modifier for polyolefin resins.
Specific examples of the polyolefin resin include low density polyethylene, ultra low density polyethylene, ultra low density polyethylene, linear low density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene, Propylene-1-butene random copolymer, propylene-ethylene-1-butene random copolymer, copolymer composed of propylene and α-olefin having 5 to 12 carbon atoms, ethylene-nonconjugated diene copolymer, propylene -Non-conjugated diene copolymer, ethylene-propylene-non-conjugated diene copolymer, polybutene, ethylene-vinyl acetate copolymer, ethylene-vinyltrimethoxysilane copolymer, ethylene-methyl acrylate copolymer, ethylene- Ethyl acrylate copolymer, ethylene And the like methacrylic acid methyl copolymer. These may be used alone or in combination of two or more.

  The blending amount of the resin modifier is preferably in the range of 0.1 to 50 parts by mass, more preferably in the range of 1 to 40 parts by mass with respect to 100 parts by mass of the polyolefin resin. If the blending amount of the resin modifier is less than 0.1 parts by mass with respect to 100 parts by mass of the polyolefin resin, the modification effect may be insufficient. On the other hand, when the compounding amount of the resin modifier exceeds 50 parts by mass with respect to 100 parts by mass of the polyolefin resin, moldability, appearance, and mechanical properties may be deteriorated.

  As long as the physical properties are not impaired, conventional stabilizers, fillers and the like can be added to the polyolefin resin composition of the present invention at the time of resin compounding, kneading and molding depending on the purpose.

Examples of the stabilizer include metal stabilizers and other stabilizers.
Examples of metal stabilizers include lead stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, and lead silicate; potassium, magnesium, barium, zinc, cadmium, lead, etc. Of metal soaps derived from 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, and behenic acid Agents: organotin stabilizers derived from alkyl groups, ester groups, fatty acid salts, maleates and sulfides; Ba-Zn, Ca-Zn, Ba-Ca-Sn, Ca-Mg -Sn-based, Ca-Zn-Sn-based, Pb-Sn-based, Pb-Ba-Ca-based complex metal soap-based stabilizers; metal groups such as barium and zinc; and 2-ethylhexa Fragrances such as branched fatty acids such as acids, isodecanoic acid and trialkylacetic acids, unsaturated fatty acids such as oleic acid, ricinoleic acid and linoleic acid, alicyclic acids such as naphthenic acid, coalic acid, benzoic acid, salicylic acid and substituted derivatives thereof Metal salt stabilizers derived from two or more organic acids such as aliphatic acids; these stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols and glycerin derivatives, and are further added to phosphites and epoxy compounds , Color stabilizers, transparency improvers, light stabilizers, antioxidants, plate-out inhibitors, metal salt liquid stabilizers and the like which are blended with stabilizing aids such as lubricants.

Other stabilizers include epoxy resins, epoxidized soybean oil, epoxidized vegetable oil, epoxidized fatty acid alkyl esters, and the like; phosphorus is substituted with an alkyl group, aryl group, cycloalkyl group, alkoxyl group, etc., and propylene Organic phosphites having aromatic compounds such as dihydric alcohols such as glycol, hydroquinone and bisphenol A; hindered phenols such as bisphenol dimerized with BHT, sulfur and methylene groups, etc .; salicylic acid esters, benzophenones, benzoates UV absorbers such as triazole; light stabilizers of hindered amines or nickel complex salts; UV screening agents such as carbon black and rutile type titanium oxide; and many such as trimerolpropane, pentaerythritol, sorbitol, and mannitol Alcohols, β-aminocrotonic acid esters, 2-phenylindoles, diphenylthioureas, dicyandiamides and other nitrogen-containing compounds, dialkylthiodipropionic acid esters and other sulfur-containing compounds, acetoacetic acid esters, dehydroacetic acid, β-diketones, etc. Nonmetallic stabilizers such as compounds, organosilicon compounds, borate esters and the like can be mentioned.
These stabilizers can be used alone or in combination of two or more.

  Examples of the filler include carbonates such as heavy calcium carbonate, precipitated calcium carbonate, and colloidal calcium carbonate, titanium oxide, clay, talc, mica, silica, carbon black, graphite, glass beads, glass fibers, carbon fibers, Inorganic materials such as metal fibers; organic fibers such as polyamide; organic materials such as silicone; natural organic materials such as wood flour.

  The polyolefin resin composition of the present invention includes other impact strength modifiers, processing aids, plasticizers, lubricants, flame retardants, heat improvers, mold release agents, crystal nucleating agents, fluidity improvers, colorants, An antistatic agent, a conductivity imparting agent, a surfactant, an antifogging agent, a foaming agent, an antibacterial agent, and the like can be added.

Examples of the impact strength modifier include MBS (methyl methacrylate-butadiene-styrene resin), ABS (acrylonitrile-butadiene-styrene resin), AES (acrylonitrile-ethylenepropylene rubber-styrene resin), NBR (acrylonitrile-butadiene rubber). , EVA (ethylene-vinyl acetate copolymer), chlorinated polyethylene, acrylic rubber, polyalkyl (meth) acrylate rubber-based graft copolymer, thermoplastic elastomer, and the like.
Examples of processing aids include (meth) acrylic acid ester copolymers.

  Examples of the plasticizer include alkyl esters of aromatic polybasic acids such as dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, diundecyl phthalate, trioctyl trimellitate, triisooctyl trimellitate, and pyromet; dibutyl adipate Alkyl esters of fatty acid polybasic acids such as dioctyl adipate, dithiononyl adipate, dibutyl azelate, dioctyl azelate, diisononyl azelate; phosphate esters such as tricresyl phosphate; adipic acid, azelaic acid, sebacic acid, phthalate Polycarboxylic acid such as acid and ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol Polyester plasticizers such as polyhydric alcohols with a polycondensate having a molecular weight of about 600 to 8,000 sealed with monohydric alcohol or monocarboxylic acid; epoxidized soybean oil, epoxidized linseed oil And epoxy plasticizers such as epoxidized tall oil fatty acid-2-ethylhexyl; chlorinated paraffin and the like.

  Examples of the lubricant include liquid hydrocarbons such as liquid paraffin and low molecular weight polyethylene, halogenated hydrocarbons, higher fatty acids, fatty acids such as oxyfatty acids, fatty acid amides such as fatty acid amides, polyhydric alcohol esters of fatty acids such as glycerides, fatty acids Esters such as fatty alcohol esters (ester waxes), metal soaps, fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols, fatty acid and polyhydric alcohol partial esters, fatty acids and polyglycols, polyglycerol partial esters, (meta ) Acrylic acid ester-based copolymer.

Examples of the flame retardant include chlorinated paraffin, aluminum hydroxide, antimony trioxide, and halogen compounds.
Examples of the heat resistance improver include (meth) acrylic acid ester copolymers, imide copolymers, styrene / acrylonitrile copolymers, and the like.

The resin modifier of the present invention is not limited to polyolefin resin and can be used for modifying other resins.
Other resins include, for example, hard, semi-rigid, soft vinyl chloride resin (PVC resin); polystyrene (PS), high impact polystyrene (HIPS), (meth) acrylic acid ester / styrene copolymer (MS). Styrene resin (St resin) such as styrene / acrylonitrile copolymer (SAN), styrene / maleic anhydride copolymer (SMA), ABS, ASA (acrylate-styrene-acrylonitrile resin), AES; Acrylic resins such as methyl acid (PMMA) (Ac resins); Polycarbonate resins (PC resins); Polyamide resins (PA resins); Polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) Resin (PEs resin); (Modified) Polypheny Ether resin (PPE resin), polyoxymethylene resin (POM resin), polysulfone resin (PSO resin), polyarylate resin (PAr resin), polyphenylene resin (PPS resin), heat Engineering plastics such as plastic polyurethane resin (PU resin); styrene elastomer, olefin elastomer, vinyl chloride elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, fluorine elastomer, 1,2-polybutadiene, Thermoplastic elastomer (TPE) such as trans 1,4-polyisoprene; PC resin such as PC / ABS / St resin resin alloy, PVC resin such as PVC / ABS / St resin alloy, PA such as PA / ABS Resin Styl resin alloy, PA resin / TPE alloy, PA resin such as PA / PP / Polyolefin resin alloy, PBT resin / TPE, PC resin such as PC / PBT / PEs resin alloy, Polyolefin resin / Alloys of olefin resins such as TPE, PP (polypropylene) / PE (polyethylene), PPE resin alloys such as PPE / HIPS, PPE / PBT, PPE / PA, PVC resins such as PVC / PMMA / Ac resins It can be used for polymer alloys such as alloys.
In the resin composition obtained by adding the resin modifier of the present invention to these resins, a stabilizer, a filler and the like are added at the time of compounding, kneading and molding of the resin depending on the purpose, as long as the physical properties are not impaired. Can be added.

There is no restriction | limiting in particular in the preparation method of the polyolefin resin composition of this invention, A normal method can be used satisfactorily. Among these, the melt mixing method is desirable. A small amount of solvent can also be used.
Examples of the apparatus used for preparing the resin composition include an extruder, a Banbury mixer, a roller, a kneader, and the like. The resin composition can be prepared by operating these apparatuses batchwise or continuously. The mixing order of each component at the time of preparation is not specifically limited.

  In the resin modifier of the present invention described above, an acryloyloxy group or a methacryloyloxy group is bonded to a secondary carbon atom or a tertiary carbon atom in the branch portion of the graft copolymer that is the resin modifier. Because it contains the (meth) acrylic acid ester monomer (a) unit, the polyolefin resin has impact resistance, dyeability, paintability, etc. while maintaining the moldability, good appearance, and mechanical properties of the polyolefin resin. At the same time, it is possible to achieve both the effects that were difficult to achieve in the past, such as good dispersibility in polyolefin resin and good adhesion to polyolefin resin matrix.

  In the polyolefin resin composition of the present invention, since the resin modifier of the present invention is added to the polyolefin resin, the moldability, good appearance, and mechanical properties of the polyolefin resin are improved. While maintaining it, it excels in impact resistance, dyeability, paintability, etc.

  Hereinafter, although a reference example, an example, and a comparative example explain the present invention still in detail, the present invention is not restricted by these examples. In the following description, “part by mass” is abbreviated as “part”, and “mass%” is abbreviated as “%”.

In Examples and Comparative Examples, various evaluations were performed by the following methods (1) to (5).
(1) Appearance:
A sheet-like test piece (130 mm × 13 mm × thickness 3 mm) obtained by molding the obtained resin composition was bent by 20 ° by hand, and it was judged by visually observing whether the test piece was whitened. did. In the evaluation, a case where no whitening was observed was indicated by ◯, and a case where whitening was observed was indicated by ×.
(2) Layer peeling:
Whether or not the sheet-shaped test piece (130 mm × 13 mm × thickness 3 mm) obtained by molding the obtained resin composition was bent by hand, and the skin (skin layer) of the test piece was peeled in layers Was determined by visual observation. In the evaluation, the case where it did not peel into layers was indicated as ◯, and the case where it was peeled into layers was indicated as ×.

(3) Tensile test:
This was performed according to ASTM D638.
(4) Izod impact test:
This was performed according to JIS K-7110.
(5) Dyeability:
A sheet-like test piece (130 mm × 13 mm × thickness 3 mm) molded from the obtained thermoplastic resin composition was kept in a 0.1% aqueous solution of Emulgen 909 at 80 ° C. for 1 hour to clean the surface. Then, it dye | stained in the autoclave at 100 degreeC for 4 hours with the terracy blue (1% with respect to a sample) aqueous solution. Thereafter, it was washed with water, and the color change was visually observed and evaluated. In the evaluation, the case where it was colored blue was marked with ◯, and the case where it did not change was marked with ×.

(Reference Example 1)
(1) Synthesis of polymer (A-1) latex:
780 parts of deionized water was added to a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, and dripping device, the inside of the reaction vessel was purged with nitrogen, the temperature was raised to 75 ° C., and sulfuric acid was added to the reaction vessel. A reducing agent aqueous solution consisting of 0.0004 parts of ferrous iron, 0.0012 parts of ethylenediaminetetraacetic acid disodium salt, 0.8 parts of Rongalite and 20 parts of deionized water was added. While maintaining the temperature in the reaction vessel at 75 ° C., 1.2 parts of methyl methacrylate (MMA), 1.8 parts of butyl acrylate, 0.8 part of 1,3-butanediol dimethacrylate, A mixture of 2 parts, 0.1 part cumene hydroperoxide, and 6 parts emulsifier LO-529 (manufactured by Toho Chemical Co., Ltd.) was added dropwise over 8 minutes and held at 75 ° C for 15 minutes. Then, a mixture of MMA 10.8 parts, butyl acrylate 162 parts, 1,3-butanediol dimethacrylate 7.2 parts, allyl methacrylate 1.8 parts, cumene hydroperoxide 0.116 parts was dropped over 120 minutes, Thereafter, the inside of the reaction vessel was kept at 75 ° C. for 60 minutes. Further, a mixture of 28 parts of MMA, 12 parts of butyl acrylate, 0.3 part of allyl methacrylate and 0.05 part of cumene hydroperoxide was added dropwise to the reaction vessel over 45 minutes. The polymer (A-1) latex was obtained by holding for 5 minutes.

(2) Synthesis of resin modifier (C-1):
Next, a monomer comprising 144 parts of 4-t-butylcyclohexyl acrylate and 1.6 parts of butyl acrylate, 0.24 parts of cumene hydroperoxide, n- A mixture of 0.5 part of octyl mercaptan was added dropwise over 90 minutes, and then the inside of the reaction vessel was kept at 75 ° C. for 60 minutes. The inside of the reaction vessel is cooled to 40 ° C., the product is filtered through a 300 mesh nylon cloth, the average particle size is 140 nm, and the ratio of the polymer is based on the total mass (total of 100 mass% of the polymer and water). As a result, 33% by mass of latex was obtained.
This latex was added to a calcium acetate aqueous solution at a concentration of 3% at 80 ° C. so that the mass ratio of the latex to the aqueous solution was 1: 3, then the temperature was raised to 90 ° C. to coagulate, and washing was repeated with water. After that, the solid content was separated and dried at 65 ° C. for 24 hours to obtain a resin modifier (C-1).
Table 1 shows the composition ratio of the resin modifier (C-1).

(Reference Example 2)
(1) Synthesis of polymer (A-2) latex:
In a pressure-resistant sealed reaction vessel, 4500 parts of ion-exchanged water, 1350 parts of 1,3-butadiene, 1650 parts of butyl acrylate, 4 parts of isopropylbenzene hydroperoxide as a polymerization initiator, 28 parts of potassium oleate as an emulsifier, and N -A mixture of 12 parts lauroyl sarcosinate was charged and the apparatus was sealed. The temperature was raised in a water bath, and when the internal temperature reached 43 ° C., 0.072 parts of ferrous sulfate, 7.2 parts of sodium pyrophosphate, and 2Na: ethylenediaminetetraacetic acid disodium dihydrate 0071 parts of the mixture and 1.2 parts of Rongalite and 4.8 parts of dextrose were added. Next, the temperature was raised and the polymerization was held at an internal temperature of 55 ° C. for 2 hours, and then the temperature was raised and the polymerization was held at an internal temperature of 60 ° C. for 6 hours to co-polymerize 1,3-butadiene and butyl acrylate. Combined latex (A-2) was obtained. The polymer conversion was measured and found to be 99%.

(2) Synthesis of resin modifier (C-2):
After 3500 parts of the polymer (A-2) latex (1400 parts as a solid content), 360 parts of water, and 3.5 parts of N-lauroyl sarcosinate were charged into the reactor, and the inside of the reaction vessel was purged with nitrogen, The temperature was raised to 70 ° C. Next, a mixture of 0.003 part of ferrous sulfate, 0.009 part of 2Na: ethylenediaminetetraacetic acid disodium salt dihydrate, 2.1 part of Rongalite, and 50 parts of water was added to the reaction vessel. Thereafter, a mixture of 280 parts of 4-t-butylcyclohexyl acrylate and 2.8 parts of cumene hydroperoxide was continuously added over 90 minutes, and then the inside of the reaction vessel was kept at 70 ° C. for 100 minutes to complete the polymerization. The inside of the reaction vessel is cooled to 40 ° C., the product is filtered through a 300 mesh nylon cloth, the average particle size is 140 nm, and the ratio of the polymer is based on the total mass (total of 100 mass% of the polymer and water). A latex of 40% by mass was obtained.
This latex was added to a calcium acetate aqueous solution at a concentration of 3% at 80 ° C. so that the mass ratio of the latex to the aqueous solution was 1: 3, then the temperature was raised to 90 ° C. to coagulate, and washing was repeated with water. After that, the solid content was separated and dried at 65 ° C. for 24 hours to obtain a resin modifier (C-2).
Table 1 shows the composition ratio of the resin modifier (C-2).

(Reference Example 3)
Synthesis of resin modifier (C-3):
The same procedure as in Reference Example 2 was conducted except that 4-t-butylcyclohexyl acrylate was changed to cyclohexyl acrylate, the average particle diameter was 150 nm, and the ratio of the polymer was based on the total mass (100% by mass in total of the polymer and water). A latex of 40% by mass was obtained. Thereafter, the solid content was separated and dried in the same manner as in Reference Example 2 to obtain a resin modifier (C-3).
Table 1 shows the composition ratio of the resin modifier (C-3).

(Reference Example 4)
A graft copolymer (D-1) different from that of the resin modifier of the present invention was obtained in the same manner as in Reference Example 1 except that 4-t-butylcyclohexyl acrylate was changed to MMA.
Table 1 shows the composition ratio of the graft copolymer (D-1).

  In the table, MMA is methyl methacrylate, BA is butyl acrylate, 1,3-BD is 1,3-butanediol dimethacrylate, AMA is allyl methacrylate, BD is 1,3-butadiene, tBCHA is 4-t-butylcyclohexyl acrylate , CHA represents cyclohexyl acrylate.

(Example 1)
10 parts of the resin modifier (C-1) synthesized in Reference Example 1 was blended with 90 parts of polypropylene (PP; MA-03 manufactured by Nippon Polychem Co., Ltd.) and supplied to a twin screw extruder set at 220 ° C. Then, after melt-kneading to form pellets, an evaluation test piece was obtained by injection molding. Table 2 shows the physical property evaluation results of the obtained evaluation test pieces.
(Example 2)
An evaluation test piece was obtained in the same manner as in Example 1 except that the resin modifier (C-1) was changed to the resin modifier (C-2). It shows in Table 2 about the physical-property evaluation result of the obtained evaluation test piece.

(Example 3)
20 parts of a resin modifier (C-2) is blended with 80 parts of polypropylene (PP; MA-03 manufactured by Nippon Polychem Co., Ltd.), supplied to a twin screw extruder set at 220 ° C., melt-kneaded, and pellets Then, injection molding was performed to obtain an evaluation test piece. Table 2 shows the physical property evaluation results of the obtained evaluation test pieces.
Example 4
An evaluation test piece was obtained in the same manner as in Example 3 except that the resin modifier (C-2) was changed to the resin modifier (C-3). It shows in Table 2 about the physical-property evaluation result of the obtained evaluation test piece.

(Comparative Example 1)
An evaluation test piece was obtained in the same manner as in Example 1 except that the resin modifier (C-1) was changed to the graft copolymer (D-1). It shows in Table 2 about the physical-property evaluation result of the obtained evaluation test piece.
(Comparative Example 2)
Evaluation test pieces were obtained in the same manner as in Example 1 except that the resin modifier and the graft copolymer were not blended with PP. It shows in Table 2 about the physical-property evaluation result of the obtained evaluation test piece.

The resin modifier of the present invention has good dispersibility in a polyolefin resin and good adhesion to a polyolefin resin matrix, while maintaining the moldability, good appearance and mechanical properties of the polyolefin resin. Since impact properties, dyeability, paintability, etc. can be improved, it is very useful as a modifier for polyolefin resins.

Claims (6)

  The polymer (A) is grafted with a monomer (B) containing at least a (meth) acrylic acid ester monomer (a) in which an acryloyloxy group or a methacryloyloxy group is bonded to a secondary carbon atom or a tertiary carbon atom. A resin modifier comprising a polymerized graft copolymer.   The resin modifier according to claim 1, wherein the (meth) acrylic acid ester monomer (a) is a monomer having an alicyclic hydrocarbon group.   The (meth) acrylic acid ester monomer (a) is at least one selected from a cyclohexyl group, 4-t-butylcyclohexyl group, isobornyl group, tricyclodecanyl group, and 3,3,5-trimethylcyclohexyl group. The resin modifier according to claim 1, which is a monomer having a seed.   The resin modification according to any one of claims 1 to 3, wherein a proportion of the (meth) acrylic acid ester monomer (a) is 50% by mass or more in the monomer (B) (100% by mass). Agent.   The resin modifier according to any one of claims 1 to 4, wherein the graft copolymer is a polymer having a core-shell structure. A polyolefin resin composition comprising the resin modifier according to any one of claims 1 to 5 and a polyolefin resin.