Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment

Definitions

• the present invention relates to a resin modifier.
• Thermoplastic resins for example, polyolefin resins
• polyolefin resins have excellent moldability, rigidity, heat resistance, chemical resistance, light weight, electrical insulation, etc., and are widely used as molded products of various shapes such as films, fibers, hollow fiber membranes, etc.
• polyolefin resins have problems such as adhesiveness and paintability, and for example, they have poor adhesion to paints, printing inks, adhesives, etc., and cannot be applied without post-treatment surface treatment. It was.
• a method for improving adhesion a method of applying corona treatment or plasma treatment to the surface of a thermoplastic resin, for example, a polyolefin resin molded product (see, for example, Patent Document 1) has been proposed.
• An object of the present invention is to provide a resin modifier that gives a thermoplastic resin excellent adhesion to paints, printing inks, adhesives, and the like.
• the present invention comprises an acid-modified polyolefin (X) containing a polyolefin (A) and an unsaturated carboxylic acid (B) as constituent units, and the ethylene which is a constituent monomer of the polyolefin (A).
• the weight ratio [ethylene / ⁇ -olefin having 3 to 8 carbon atoms] to the ⁇ -olefin having 3 to 8 carbon atoms is 2/98 to 50/50, and the unsaturated carboxylic acid (B) is unsaturated.
• a resin modifier (K) which is a monocarboxylic acid, an unsaturated polycarboxylic acid, and / or an unsaturated polycarboxylic acid anhydride, wherein the acid-modified polyolefin (X) satisfies all of the following requirements (1) to (3). ); Primer for plastic molded products containing the resin modifier (K); Thermoplastic resin composition (Y) containing the resin modifier (K) and the polyolefin resin (D). A molded product obtained by molding the thermoplastic resin composition (Y); and a molded product obtained by painting and / or printing the molded product.
• Acid value is 1 to 100 mgKOH / g; (2) The number average molecular weight (Mn) is 1,000 to 60,000; (3) The isotacticity of the ⁇ -olefin moiety is 1 to 50%.
• the resin modifier (K) of the present invention has the following effects. (1) Excellent substrate adhesion. (2) Excellent solvent solubility. (3) An excellent mechanical strength (impact resistance, bending elasticity, etc.) is imparted to a molded product of a resin composition containing a resin modifier (K). (4) A modifying effect (wetting property and its durability) is given to a molded product of a resin composition containing a resin modifier (K).
• the polyolefin (A) in the resin modifier (K) of the present invention contains ethylene and an ⁇ -olefin having 3 to 8 carbon atoms as a constituent monomer.
• ⁇ -olefin having 3 to 8 carbon atoms will be referred to as " ⁇ -olefin”.
• Examples of the ⁇ -olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.
• the ⁇ -olefin may be used in combination of 1 type, 2 types or more, but 1 type is preferable. Of the above ⁇ -olefins, propylene is preferable from the viewpoint of mechanical strength and industrial aspects of the molded product.
• the weight ratio [ethylene / ⁇ -olefin] of ethylene, which is a constituent monomer of polyolefin (A), to ⁇ -olefin is 2/98 to 50/50, preferably 5/95 to 40/60. , More preferably 10/90 to 30/70.
• the weight ratio [ethylene / ⁇ -olefin] is less than 2/98, the resin modifier (K) is inferior in substrate adhesion, and when it exceeds 50/50, the mechanical strength of the molded product is inferior.
• the weight ratio [ethylene / ⁇ -olefin] can be calculated by, for example, 1 H-MNR (nuclear magnetic resonance spectroscopy).
• the polyolefin (A) may be composed of other monomers in addition to ethylene and ⁇ -olefin.
• the weight of the other monomers is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 1% by weight.
• the other monomer include 2-butene, isobutene, ⁇ -olefin having 9 to 30 carbon atoms (sometimes abbreviated as C) (1-decene, 1-dodecene, etc.), and ⁇ -olefin.
• C4 to 30 unsaturated monomers for example, vinyl acetate.
• the number average molecular weight (Mn) of the polyolefin (A) is preferably 800 to 50,000 from the viewpoint of the mechanical strength of the molded product, the adhesion of the resin modifier (K) to the substrate, and the solvent solubility. It is more preferably 1,500 to 40,000, still more preferably 2,000 to 30,000.
• Mn of polyolefin (A) can be measured by GPC (gel permeation chromatography).
• GPC gel permeation chromatography
• the conditions for measuring Mn by GPC in the present invention are as follows. Equipment: High-temperature gel permeation chromatograph ["Alliance GPC V2000", manufactured by Waters Corp.] Detector: Refractive index detector Solvent: Ortodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml Column stationary phase: PLgel 10 ⁇ m, MIXED-B 2 in series [Polymer Laboratories Co., Ltd.] Column temperature: 135 ° C
• the number of double bonds per 1,000 carbon atoms of the polyolefin (A) [the number of carbon-carbon double bonds in the molecular terminal and / or the molecular chain of the polyolefin (A)] is an unsaturated carboxylic acid (described later). From the viewpoint of reactivity with B) and productivity, the number is preferably 0.5 to 20, more preferably 1.0 to 18, and even more preferably 1.5 to 15. Here, the number of double bonds can be determined from the 1 H-NMR spectrum of polyolefin (A).
• the peak in the spectrum is assigned, and the number of double bonds of the polyolefin (A) is determined from the integrated value derived from the double bond and the integrated value derived from the polyolefin (A) at 4.5 to 6 ppm of the polyolefin (A).
• the relative value of the carbon number of the polyolefin (A) is obtained, and the number of double bonds in the molecular end and / or the molecular chain per 1,000 carbons of the polyolefin (A) is calculated.
• the isotacticity of the ⁇ -olefin portion of the polyolefin (A) is preferably 1 to 50%, more preferably 5 to 45, from the viewpoint of substrate adhesion and solvent solubility of the resin modifier (K). %, More preferably 10-40%.
• the isotacticity of the ⁇ -olefin moiety of the polyolefin (A) tends to be directly reflected in the isotacticity of the ⁇ -olefin moiety of the acid-modified polyolefin (X) described later.
• the isotacticity can be calculated using, for example, 13 C-NMR (nuclear magnetic resonance spectroscopy).
• side chain methyl groups are on both sides (triplet, triad), on both sides of the triplet (quintuplet, pentad), and on both sides of the quintuplet (seven-strand, heptad). It is known that peaks are observed at different chemical shifts under the influence of the configuration (meso or racemo) with the methyl group. Therefore, the evaluation of stereoregularity is generally performed on the pentad, and the isotacticity in the present invention is also calculated based on the evaluation of the pentad.
• the carbon peaks derived from the side chain methyl group in the propylene obtained by 13 C-NMR are the pentad peaks (H) of the ⁇ -olefin portion of the polyolefin (A), and the pentad is meso.
• the isotacticity is calculated by the following formula when the peak (Ha) derived from the methyl group in the propylene of the isotactic formed only by the structure is used.
• Isotacticity (%) [(Ha) / ⁇ (H)] x 100 (1)
• Ha is the peak height of the isotactic (pentad is formed only by the meso structure) signal
• H is the peak height of the pentad.
• the isotacticity of the ⁇ -olefin portion of the acid-modified polyolefin (X) described later can also be measured in the same manner as described above.
• polyolefin (A) in the present invention for example, a high molecular weight (preferably Mn of 60,000 to 400,000, more preferably Mn of 80,000 to 250,000) polyolefin (A0) is thermally reduced. There is a way to do it.
• a high molecular weight (preferably Mn of 60,000 to 400,000, more preferably Mn of 80,000 to 250,000) polyolefin (A0) is thermally reduced. There is a way to do it.
• the heat-reducing method includes (1) heating the high-molecular-weight polyolefin (A0) in the absence of an organic peroxide at 300 to 450 ° C. for 0.5 to 10 hours, and (2) organic peroxide.
• a method of heating at 180 to 300 ° C. for 0.5 to 10 hours in the presence of a substance [for example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane] is included.
• the method (1) is preferable because it is easy to obtain one having a larger number of double bonds at the molecular terminal and / or the molecular chain. ..
• the weight ratio [ethylene / ⁇ -olefin] of ethylene and ⁇ -olefin, which are the monomers constituting the polyolefin (A), is the weight ratio [ethylene / ⁇ -olefin] of these monomers in the high molecular weight polyolefin (A0).
• ⁇ -olefin] tends to be maintained as it is. Further, the higher the heat decomposing temperature or the longer the heat decomposing time, the larger the number of double bonds per 1,000 carbon atoms tends to be. Further, the larger the Mn of the high molecular weight polyolefin (A0), the higher the heat decomposing temperature, or the longer the heat decomposing time, the smaller the Mn of the polyolefin (A) tends to be.
• the polyolefin (A) may be used alone or in combination of two or more.
• the unsaturated carboxylic acid (B) in the resin modifier (K) of the present invention means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic acid anhydride.
• the unsaturated carboxylic acid (B) is a monocarboxylic acid of C3 to 24 having one polymerizable unsaturated group, a polycarboxylic acid of C4 to 24 having one polymerizable unsaturated group, and / or a polymerizable unsaturated group. It is preferably a C4 to 24 polycarboxylic acid anhydride having one group.
• the unsaturated monocarboxylic acids include aliphatic monocarboxylic acids (C3 to 24, for example, acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, crotonic acid, isocrotonic acid) and fats.
• Ring-containing monocarboxylic acid C6 to 24, for example, cyclohexenecarboxylic acid
• unsaturated poly (2 to 3 or more) carboxylic acid or acid anhydride thereof includes unsaturated dicarboxylic acid or acid anhydride thereof [aliphatic dicarboxylic acid].
• Acids or their acid anhydrides (C4-24, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and their acid anhydrides), alicyclic-containing dicarboxylic acids or their acid anhydrides (C8-24, For example, cyclohexendicarboxylic acid, cycloheptenedicarboxylic acid, bicycloheptenedicarboxylic acid, methyltetrahydrophthalic acid, and acid anhydrides thereof)] and the like can be mentioned.
• the unsaturated carboxylic acid (B) may be used alone or in combination of two or more.
• unsaturated carboxylic acids (B) unsaturated dicarboxylic acid anhydrides are more preferable from the viewpoint of reactivity with polyolefin (A) and modification characteristics of the resin modifier (K) described later.
• the acid-modified polyolefin (X) in the present invention contains the above-mentioned polyolefin (A) and unsaturated carboxylic acid (B) as constituent units.
• the weight ratio [polyolefin (A) / unsaturated carboxylic acid (B)] of the polyolefin (A) to the unsaturated carboxylic acid (B) in the acid-modified polyolefin (X) is determined by the mechanical strength of the molded product and the resin modification described later. From the viewpoint of the balance between the modifying effect of the quality agent (K) and the adhesion to the substrate, it is preferably 80/20 to 99.5 / 0.5, and more preferably 90/10 to 99/1.
• the acid-modified polyolefin (X) is formed by reacting the polyolefin (A) with the unsaturated carboxylic acid (B) in the absence or presence of the radical initiator (C).
• the acid-modified polyolefin (X) is more preferably an organic solvent suitable for the polyolefin (A) and the unsaturated carboxylic acid (B) in the presence of the radical initiator (C) [for example, C3-18.
• Hydrocarbons hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.
• C3-18 halogenated hydrocarbons di-, tri-, or tetrachloroethane, dichlorobutane, etc.
• C3-18 ketones acetone
• Methyl ethyl ketone di-t-butyl ketone, etc.
• C3-18 ether ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.
• the radical initiator (C) is known, for example, an azo initiator (azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), etc.), a peroxide initiator. (Dicumyl peroxide, etc.) can be mentioned. Of the radical initiators (C), peroxide initiators are preferred.
• the reaction temperature is preferably 100 to 270 ° C., more preferably 120 to 250 ° C., and even more preferably 130 to 240 ° C. from the viewpoint of reactivity and productivity of the polyolefin (A) and the unsaturated carboxylic acid (B).
• the acid-modified polyolefin (X) satisfies all of the following requirements (1) to (3).
• Acid value is 1 to 100 mgKOH / g
• the number average molecular weight (Mn) is 1,000 to 60,000.
• Isotacticity of ⁇ -olefin moiety is 1 to 50%
• the acid value of the acid-modified polyolefin (X) is 1 to 100 mgKOH / g (hereinafter, only numerical values are shown), preferably 3 to 75, and more preferably 5 to 50.
• the acid value here is a value measured according to JIS K0070. If the acid value is less than 1, the modifying property of the resin modifier (K) is inferior, and if it exceeds 100, the productivity of the acid-modified polyolefin (X) is inferior. Further, the acid value can be appropriately adjusted by the number of double bonds of the polyolefin (A), the weight of the polyolefin (A), the type and weight of the unsaturated carboxylic acid (B).
• the Mn of the acid-modified polyolefin (X) is 1,000 to 60,000, preferably 2,000 to 50,000, and more preferably 3,000 to 40,000. If Mn is less than 1,000, the mechanical strength of the molded product is inferior, and if it exceeds 60,000, the modification characteristics of the resin modifier (K) are inferior.
• the Mn of the acid-modified polyolefin (X) can be measured by GPC in the same manner as the Mn of the polyolefin (A) described above.
• the Mn of the acid-modified polyolefin (X) is controlled by controlling the Mn of the polyolefin (A), the type and amount of the unsaturated carboxylic acid (B), and the reaction between the polyolefin (A) and the unsaturated carboxylic acid (B). , Can be adjusted as appropriate.
• the isotacticity of the ⁇ -olefin moiety of the acid-modified polyolefin (X) is 1 to 50%, preferably 5 to 45%, and more preferably 10 to 40%. If the isotacticity is less than 1%, the substrate adhesion is poor, and if it exceeds 50%, the solvent solubility is poor. Further, the isotacticity of the ⁇ -olefin portion of the acid-modified polyolefin (X) can be appropriately adjusted by the isotacticity of the polyolefin (A) and the high molecular weight polyolefin (A0) as described above.
• the resin modifier (K) of the present invention contains the acid-modified polyolefin (X).
• the resin modifier (K) is preferably used as a modifier for various thermoplastic resins, particularly the polyolefin resin (D) described later. Since the resin modifier (K) is excellent in substrate adhesion and solvent solubility, it can be used for various purposes, such as a primer for a plastic molded product, a molded product of the thermoplastic resin composition (Y) described later, and the like. Gives excellent mechanical strength, modification effect, etc.
• the resin modifier (K) may be used alone or in combination of two or more.
• the content of the acid-modified polyolefin (X) in the resin modifier (K) is preferably 50 to 100% by weight, more preferably 90 to 100% by weight.
• the primer for a plastic molded product of the present invention contains the above resin modifier (K).
• the primer for a plastic molded product preferably contains the above resin modifier (K) and a solvent (S).
• the solvent (S) include known solvents, but aromatic hydrocarbons (toluene, xylene, etc.) are preferable.
• the weight ratio of the resin modifier (K) to the solvent (S) [resin modifier (K) / solvent (S)] is preferably 10/90 to 50. / 50, more preferably 20/80 to 40/60.
• the content of the resin modifier (K) in the primer for plastic molded products is preferably 10 to 50% by weight. Further, if necessary, a resin other than the polyolefin resin (D) and the polyolefin resin (D) may be added to the primer.
• the thermoplastic resin composition (Y) of the present invention contains the above resin modifier (K) and a polyolefin resin (D).
• the polyolefin resin (D) includes, 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 C4 or more. Includes (co) polymers of olefins and the like.
• the constituent unit of the polyolefin resin (D) and the constituent unit of the polyolefin (A) constituting the resin modifier (K) are the same or similar. It is preferable from the viewpoint of compatibility between the polyolefin resin (D) and the resin modifier (K). Therefore, as the polyolefin resin (D), a propylene unit-containing (co) polymer is preferable, and an ethylene / propylene copolymer is particularly preferable.
• the Mn of the polyolefin resin (D) is preferably 10,000 to 500,000, more preferably 20 from the viewpoint of the mechanical strength of the molded product of the present invention described later and the compatibility with the resin modifier (K). It is 000 to 400,000, more preferably 80,000 to 300,000.
• the thermoplastic resin composition (Y) of the present invention may further contain various additives (F), if necessary, as long as the effects of the present invention are not impaired.
• the additive (F) include a colorant (F1), a flame retardant (F2), a filler (F3), a lubricant (F4), an antistatic agent (F5), a dispersant (F6), and an antioxidant (F7).
• Coloring agents (F1) include inorganic pigments [white pigments, cobalt compounds, iron compounds, sulfides, etc.], organic pigments [azo pigments, polycyclic pigments, etc.], dyes [azo-based, indigoid-based, sulfide-based, alizarin. System, aclysine system, thiazole system, nitro system, aniline system, etc.] and the like.
• Examples of the flame retardant (F2) include halogen-containing flame retardants, nitrogen-containing flame retardants, sulfur-containing flame retardants, silicon-containing flame retardants, and phosphorus-containing flame retardants.
• Examples of the filler (F3) include inorganic fillers (calcium carbonate, talc, clay, etc.) and organic fillers (urea, calcium stearate, etc.).
• lubricant (F4) examples include calcium stearate, butyl stearate, oleic acid amide, polyolefin wax, paraffin wax and the like.
• Nonionic surfactant alkylene oxide (AO) -added nonionics for example, active hydrogen atom-containing compounds having a hydrophobic group (C8 to 24 or more) [saturated and unsaturated, higher alcohols (C8 to more) 18), higher aliphatic amines (C8-24), higher fatty acids (C8-24), etc.]
• AO alkylene oxide
• polyoxyalkylene derivatives AO adducts and higher fatty acid mono- or diesters of polyalkylene glycols
• Anionic surfactant Higher fatty acid (above) salt sodium laurate, etc.
• ethercarboxylic acid [carboxymethylated product of EO (1-10 mol) adduct, etc.] and salts thereof
• sulfate ester salt alkyl
• sulfated oils sulfated fatty acid esters and sulfated olefins
• sulfonates [alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfosuccinic acid dialkyl ester types, ⁇ -olefin (C12-18) sulfates Acid salts, N-acyl-N-methyltaurine (Igepon T type, etc.), etc.]
• phosphate ester salts, etc. alkyl, alkyl ether, alkylphenyl ether phosphate, etc.
• Amphoteric surfactant Carboxylic acid (salt) type amphoterix [Amino acid type amphoterix (laurylaminopropionic acid (salt) etc.) and betaine type amphoterix (alkyldimethylbetaine and alkyldihydroxyethylbetaine etc.)]; Sulfate ester (Salt) type amphoterics [laurylamine sulfate (salt), hydroxyethyl imidazoline sulfate (salt), etc.]; Sulfonic acid (salt) type amphoterix [pentadecylsulfotaurine and imidazoline sulfonic acid (salt) ) Etc.]; and phosphoric acid ester (salt) type amphoterix and the like [phosphate ester (salt) of glycerin lauryl acid ester, etc.].
• the salts in the above anionic and amphoteric surfactants include metal salts such as alkali metals (lithium, sodium and potassium, etc.), alkaline earth metals (calcium and magnesium, etc.) and Group IIB metals (zinc, etc.); Ammonium salts; as well as amine salts and quaternary ammonium salts.
• the dispersant (F6) is a polymer of Mn 1,000 to 20,000, for example, a vinyl resin, and a vinyl resin other than the above-mentioned polyolefin (A) [vinyl 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.] Etc.]; Polyester resin [polyethylene terephthalate, etc.], polyamide resin [6,6-nylon and 12-nylon, etc.], polyether resin [polyether sulfone, etc.], polycarbonate resin [polycondensate of bisphenol A and phosgen, etc.] And their block copolymers and the
• antioxidant (F7) examples include phenol compounds [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.)) and bisphenol [2,2'-methylenebis (4-methyl-6-t-butylphenol). ) Etc.], Polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc.], etc.], Sulfur compound (dilauryl 3) , 3'-thiodipropionate, etc.), phosphorus compounds (triphenylphosphite, etc.), amine compounds (octylated diphenylamine, etc.) and the like.
• lower (C1-4) alcohol esters of fatty acids C8-24) (butyl stearate, etc.) and polyvalent (divalent to tetravalent or higher) fatty acids (C2-24).
• examples thereof include alcohol esters (hardened castor oil and the like), glycol (C2 to 8) esters of fatty acids (C2 to 24) (ethylene glycol monostearate and the like), liquid paraffins and the like.
• Antibacterial agents include benzoic acid, sorbic acid, phenol halides, organic iodine, nitriles (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylenebisthianocyanate), N-halo.
• Examples thereof include alkylthioimides, copper agents (8-oxyquinoline copper, etc.), benzimidazoles, benzothiazoles, trihaloallyl, triazoles, organic nitrogen sulfur compounds (suraoff 39, etc.), quaternary ammonium compounds, pyridine compounds and the like.
• the compatibilizer (F10) includes a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group: for example.
• polar group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group: for example.
• ultraviolet absorber (F11) examples include benzotriazole [2- (2'-hydroxy-5'-methylphenyl) benzotriazole, etc.], benzophenone [2-hydroxy-4-methoxybenzophenone, etc.], salicylate [phenylsalicylate, etc.] Etc.], acrylate [2-ethylhexyl-2-cyano-3,3-diphenylacrylate, etc.] and the like.
• the total content of the additive (F) in the thermoplastic resin composition (Y) is preferably, for example, 20% by weight or less based on the total weight of the thermoplastic resin composition (Y), and each additive (F). ) Is more preferably 0.05 to 10% by weight, still more preferably 0.1 to 5% by weight from the viewpoint of functional expression and industry.
• the amount of each additive used based on the total weight of the thermoplastic resin composition (Y) is, for example, 5% by weight or less, preferably 0.1 to 3% by weight of (F1); (F2) is, for example, 8.
• % Weight or less preferably 1 to 3% by weight;
• (F3) is, for example, 5% by weight or less, preferably 0.1 to 1% by weight;
• (F4) is, for example, 8% by weight or less, preferably 1 to 5% by weight.
• (F5) is, for example, 8% by weight or less, preferably 1 to 3% by weight;
• (F6) is, for example, 1% by weight or less, preferably 0.1 to 0.5% by weight;
• F7 is, for example. 2% by weight or less, preferably 0.05 to 0.5% by weight;
• (F8) is, for example, 5% by weight or less, preferably 0.01 to 3% by weight;
• (F9) is, for example, 25% by weight or less, preferably.
• (F10) is, for example, 15% by weight or less, preferably 0.5 to 10% by weight;
• (F11) is, for example, 2% by weight or less, preferably 0.05 to 0.5% by weight
• the amount of each compound exerting the corresponding additive effect is not used as it is, but the effect as another additive can be obtained at the same time. In consideration of this, the amount used shall be adjusted according to the purpose of use.
• thermoplastic resin composition (Y) of the present invention As a method for producing the thermoplastic resin composition (Y) of the present invention, (1) A method of collectively mixing the total amount of the polyolefin resin (D) and the resin modifier (K) and, if necessary, (F) to obtain a resin composition (collective method); (2) A part of the polyolefin resin (D), the whole amount of the resin modifier (K), and if necessary, a part or the whole amount of the additive (F) are mixed to obtain a high-concentration resin modifier (K). Examples thereof include a method (masterbatch method) in which a masterbatch resin composition to be contained is once prepared, and then the remaining polyolefin resin (D) and, if necessary, the rest of the additive (F) are added and mixed to obtain a resin composition. .. From the viewpoint of the mixing efficiency of the resin modifier (K), the method (2) is preferable.
• the weight ratio [resin modifier (K) / polyolefin resin (D)] of the resin modifier (K) to the polyolefin resin (D) in the thermoplastic resin composition (Y) of the present invention is resin modification. From the viewpoint of the modifying characteristics of the agent (K) and the mechanical strength of the molded product described later, it is preferably 0.1 / 99.9 to 50/50, more preferably 1/99 to 40/60.
• thermoplastic resin composition (Y), (I) For example, a powder mixer ["Henshell Mixer” [trade name “Henshell Mixer FM150L / B", Mitsui Mine Co., Ltd., after the company name change, manufactured by Nippon Coke Industries Co., Ltd.], " After mixing with "Nautamixa” [trade name “Nautamixa DBX3000RX”, manufactured by Hosokawa Micron Co., Ltd.], “Banbury Mixer” [trade name "MIXTRON BB-16MIXER”, manufactured by Kobe Steel Co., Ltd.], etc. A method of kneading at 120 to 220 ° C.
• the molded product of the present invention is a molded product of the above-mentioned thermoplastic resin composition (Y). That is, the molded product of the present invention is a molded product of the above-mentioned thermoplastic resin composition (Y).
• the molding method include injection molding, compression molding, calender molding, slush molding, rotary molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), and a single layer depending on the purpose. It can be molded by any method incorporating means such as molding, multi-layer molding or foam molding. Examples of the form of the molded product include plate-shaped, sheet-shaped, film, fiber (including non-woven fabric and the like) and the like. Since the molded product of the present invention contains the resin modifier (K) having the above-mentioned carboxyl group and the like, it has an excellent affinity with paints, inks and the like having relatively high polarity due to the modifying effect.
• the molded product of the present invention has excellent mechanical strength, good paintability and printability, and a molded product can be obtained by painting and / or printing the molded product.
• 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.
• the paint include paints generally used for painting plastics such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint, and even these so-called paints with relatively high polarity can be used. It can also be used with low-polarity paints (olefins, etc.).
• the coating film thickness dry film thickness
• any printing method generally used for printing plastics can be used, for example, gravure printing and flexo printing. Examples include printing, screen printing, pad printing, dry offset printing and offset printing.
• 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.
• the part in the embodiment represents a weight part.
• Mn number average molecular weight
• the number of double bonds of polyolefin the isotacticity
• the acid value were measured by the above method.
• Example 1 100 parts of polyolefin (A-1) and 2 parts of maleic anhydride (B-1) were charged in a reaction vessel, and after nitrogen substitution, the temperature was raised to 180 ° C. under nitrogen aeration to uniformly dissolve the mixture.
• a radical initiator [Dicmil peroxide, trade name "Parkmill D", manufactured by Nichiyu Co., Ltd.]
• the acid-modified polyolefin (X-1) had an acid value of 11, Mn of 7,000, and an isotacticity of 16%.
• Example 2 100 parts of polyolefin (A-1) and 3 parts of maleic anhydride (B-1) were charged in a reaction vessel, heated to 200 ° C. under nitrogen aeration, and stirred for 10 hours. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa, the same applies hereinafter) to obtain a resin modifier (K-2) containing an acid-modified polyolefin (X-2). It was.
• the acid-modified polyolefin (X-2) had an acid value of 16, Mn of 6,000, and an isotacticity of 18%.
• Examples 3 to 13 Comparative Examples 1 to 2> According to Table 2, the reactions were carried out in the same manner as in Example 1 except that the raw materials used were used, and the resin modifiers (K-3) to (K-13) containing each acid-modified polyolefin (X) were contained. ), (Ratio K-1) to (Ratio K-2) were obtained. Each of the obtained resin modifiers was evaluated by the following method. The results are shown in Table 2.
• ⁇ Evaluation method> ⁇ 1> Solvent solubility 30 g of each resin modifier obtained in Examples 1 to 13 and Comparative Examples 1 and 2 and 70 g of xylene are placed in a container, stirred at 40 ° C. for 3 hours, and then at room temperature (1). It was allowed to stand at 25 ° C. for 3 hours. Further, the properties of the contents of the container aged at 25 ° C. for 1 day were observed, and the solvent solubility was evaluated according to the following ⁇ evaluation criteria>.
• ⁇ Evaluation criteria> ⁇ : The solution is transparent and has fluidity. ⁇ : The solution is slightly hazy and fluid. ⁇ : The solution is hazy and has no fluidity. X: Almost insoluble.
• a polyurethane paint [trade name "U-coat UX-150” manufactured by Sanyo Chemical Industries, Ltd.] was spray-applied using a similar sprayer, dried at 80 ° C. for 10 minutes (urethane paint film thickness after drying).
• An adhesion test (a grid test) was performed on a painted surface of 100 ⁇ m) by a grid tape method based on JIS K5400, and the adhesion was evaluated according to the following evaluation criteria.
• the number of portions of the grid 100 where the coating film has not peeled off is represented by 0 to 100, and the larger the value, the better the adhesion between the base material and the coating film. In the above ⁇ 1>, those having an evaluation of ⁇ or ⁇ could not be sprayed, so the substrate adhesion was not evaluated.
• A0-1 Polyolefin containing 85% propylene and 15% ethylene as constituent units, trade name "Vistamaxx6202", manufactured by ExxonMobil, Mn76,000, isotacticity 20%
• A0-2 Polyolefin containing 91% propylene and 9% ethylene as constituent units, trade name "Vistamaxx3980", manufactured by ExxonMobil, Mn113,000, isotacticity 50%
• A0-3 Polyolefin containing 84% propylene and 16% ethylene as constituent units, trade name "Vistamaxx6102", manufactured by ExxonMobil, Mn 70,000, isotacticity 29%
• Ratio A0-1 Polyolefin containing 98% propylene and 2% ethylene as constituent units, trade name "SunAllomer PZA20A”, manufactured by SunAllomer Ltd., Mn100,000, isotacticity 90% Ratio A0
• thermoplastic resin composition is blended for 3 minutes with a Henshell mixer according to the compounding composition (part) of 3 and then melt-kneaded with a twin-screw extruder with a vent at 180 ° C., 100 rpm, and a residence time of 5 minutes.
• Each thermoplastic resin composition is molded at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. using an injection molding machine [trade name “PS40E5ASE”, Nissei Resin Industry Co., Ltd.] to prepare a predetermined test piece, which will be described later. It was evaluated according to the evaluation method of. The results are shown in Table 3.
• Impact resistance (unit: kJ / m 2 ) The Izod impact value was measured according to JIS K7110.
• Flexural modulus (unit: MPa) The bending elasticity was evaluated by measuring according to JIS K7171.
• Wetness (Unit: °) The wettability was evaluated by measuring the water contact angle in accordance with JIS R2357. The smaller the water contact angle, the better the wettability. 4.
• Persistence of wettability (unit: °) The film was immersed in water, the surface was washed with a cotton cloth, and then dried under reduced pressure (1 kPa, 80 ° C., 1 hour). The temperature of this test piece was adjusted (23 ° C., 50 RH%, 24 hours), and the above 3. The water contact angle was measured in the same manner as in.
• the resin modifier (K) of the present invention was superior in substrate adhesion and solvent solubility as compared with those of Comparative Examples. Further, it was found that the molded product of the thermoplastic resin composition was given excellent mechanical strength (impact resistance, bending elasticity, etc.) and a modifying effect (wetting property, its durability).
• the resin modifier (K) of the present invention has various uses, preferably a resin modifier, a chlorinated polypropylene raw material, a polyurethane raw material, a cured resin raw material, an adhesive raw material, a pressure-sensitive adhesive raw material, an emulsion raw material, and an adhesive. It can be suitably used for chemical applications, and has excellent wettability (particularly persistent wettability), adhesiveness, and adhesion (painting) to the molded product without impairing the mechanical strength and good appearance of the molded product of the thermoplastic resin. Gender) and their persistence can be imparted. It is particularly useful as a primer for plastic molded products, a wettability modifier, and a coatability improver.
• the wettability is improved, the wettability of PP for the battery separator is improved, the wettability of PE and PVDF of the water treatment film is improved, the wettability of the short fiber polyolefin for fiber reinforcement is improved, and the vinyl house (plastic). It is also suitable for improving the wettability of house) and the wettability of food packaging films.
• thermoplastic resin composition (Y) of the present invention has good coatability and printability, various molding methods [injection molding, compression molding, calender molding, slush molding, rotary molding, extrusion molding, blow molding, foaming] Housing products (for home appliances / OA equipment, game equipment, office equipment, etc.) molded by molding and film molding (cast method, tenter method, inflation method, etc.), plastic container materials [Trays used in clean rooms (IC trays) Etc.) and other containers, etc.], various cushioning materials, covering materials (packaging materials, protective films, etc.), flooring sheets, artificial turf, mats, tape base materials (for semiconductor manufacturing processes, etc.) and various molded products (for semiconductor manufacturing processes, etc.) It can be widely used as a material for automobile parts, etc.) and is extremely useful.

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• 2020
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